MixAlco Process Waste Biomass to Fuels and ChemicalsMixAlco Process Waste Biomass to Fuels and Chemicals

Technology DevelopmentMark Holtzapple and Richard DavisonDepartment of Chemical EngineeringTexas AampM University

LicenseeDavid Carrabba PresidentTerrabon LLC

MarketingWilliam Settles Jim GloverStandard-Gen Inc Harvest Chemicals Ltd

Looking for treasures in the TRASH

Waste Generation

integral part of a developed society

Municipal Solid Waste Generation in the US

0

40

80

120

160

200

240

1960 1970 1980 1990 1995 1997 1998 2000 2005

Milli

on T

ons

year

Total generation

Net genetration (afterrecycling)

2395

1628

MSW Management in the US

5050Land DisposalLand Disposal3030RecoveryRecovery

1616CombustionCombustion

Total Generation 217 million tons EPA

Municipal Solid Waste

Disposal costs

$10-$110wet ton

gt 45 lb MSW(personbullday)

OtherOtherGlassGlass

Food WasteFood WasteWoodWood

MetalsMetalsPlasticsPlastics

Yard WastesYard WastesPaper wastesPaper wastes

Paper Wastes

Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper

gt 100 millions tonsyear

30 MSW

50 recovery in the year 2000

Sewage Sludge

69 million dry tons generated in 1998

Municipal wastewater treatment

Disposal costs $80-$440dry ton

Combine Wastes

Carbohydrate Rich

MSW

(40ndash80)

Nutrient Rich

Sewage Sludge

(20ndash60)

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Looking for treasures in the TRASH

Waste Generation

integral part of a developed society

Municipal Solid Waste Generation in the US

0

40

80

120

160

200

240

1960 1970 1980 1990 1995 1997 1998 2000 2005

Milli

on T

ons

year

Total generation

Net genetration (afterrecycling)

2395

1628

MSW Management in the US

5050Land DisposalLand Disposal3030RecoveryRecovery

1616CombustionCombustion

Total Generation 217 million tons EPA

Municipal Solid Waste

Disposal costs

$10-$110wet ton

gt 45 lb MSW(personbullday)

OtherOtherGlassGlass

Food WasteFood WasteWoodWood

MetalsMetalsPlasticsPlastics

Yard WastesYard WastesPaper wastesPaper wastes

Paper Wastes

Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper

gt 100 millions tonsyear

30 MSW

50 recovery in the year 2000

Sewage Sludge

69 million dry tons generated in 1998

Municipal wastewater treatment

Disposal costs $80-$440dry ton

Combine Wastes

Carbohydrate Rich

MSW

(40ndash80)

Nutrient Rich

Sewage Sludge

(20ndash60)

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Waste Generation

integral part of a developed society

Municipal Solid Waste Generation in the US

0

40

80

120

160

200

240

1960 1970 1980 1990 1995 1997 1998 2000 2005

Milli

on T

ons

year

Total generation

Net genetration (afterrecycling)

2395

1628

MSW Management in the US

5050Land DisposalLand Disposal3030RecoveryRecovery

1616CombustionCombustion

Total Generation 217 million tons EPA

Municipal Solid Waste

Disposal costs

$10-$110wet ton

gt 45 lb MSW(personbullday)

OtherOtherGlassGlass

Food WasteFood WasteWoodWood

MetalsMetalsPlasticsPlastics

Yard WastesYard WastesPaper wastesPaper wastes

Paper Wastes

Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper

gt 100 millions tonsyear

30 MSW

50 recovery in the year 2000

Sewage Sludge

69 million dry tons generated in 1998

Municipal wastewater treatment

Disposal costs $80-$440dry ton

Combine Wastes

Carbohydrate Rich

MSW

(40ndash80)

Nutrient Rich

Sewage Sludge

(20ndash60)

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Municipal Solid Waste Generation in the US

0

40

80

120

160

200

240

1960 1970 1980 1990 1995 1997 1998 2000 2005

Milli

on T

ons

year

Total generation

Net genetration (afterrecycling)

2395

1628

MSW Management in the US

5050Land DisposalLand Disposal3030RecoveryRecovery

1616CombustionCombustion

Total Generation 217 million tons EPA

Municipal Solid Waste

Disposal costs

$10-$110wet ton

gt 45 lb MSW(personbullday)

OtherOtherGlassGlass

Food WasteFood WasteWoodWood

MetalsMetalsPlasticsPlastics

Yard WastesYard WastesPaper wastesPaper wastes

Paper Wastes

Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper

gt 100 millions tonsyear

30 MSW

50 recovery in the year 2000

Sewage Sludge

69 million dry tons generated in 1998

Municipal wastewater treatment

Disposal costs $80-$440dry ton

Combine Wastes

Carbohydrate Rich

MSW

(40ndash80)

Nutrient Rich

Sewage Sludge

(20ndash60)

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

MSW Management in the US

5050Land DisposalLand Disposal3030RecoveryRecovery

1616CombustionCombustion

Total Generation 217 million tons EPA

Municipal Solid Waste

Disposal costs

$10-$110wet ton

gt 45 lb MSW(personbullday)

OtherOtherGlassGlass

Food WasteFood WasteWoodWood

MetalsMetalsPlasticsPlastics

Yard WastesYard WastesPaper wastesPaper wastes

Paper Wastes

Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper

gt 100 millions tonsyear

30 MSW

50 recovery in the year 2000

Sewage Sludge

69 million dry tons generated in 1998

Municipal wastewater treatment

Disposal costs $80-$440dry ton

Combine Wastes

Carbohydrate Rich

MSW

(40ndash80)

Nutrient Rich

Sewage Sludge

(20ndash60)

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Municipal Solid Waste

Disposal costs

$10-$110wet ton

gt 45 lb MSW(personbullday)

OtherOtherGlassGlass

Food WasteFood WasteWoodWood

MetalsMetalsPlasticsPlastics

Yard WastesYard WastesPaper wastesPaper wastes

Paper Wastes

Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper

gt 100 millions tonsyear

30 MSW

50 recovery in the year 2000

Sewage Sludge

69 million dry tons generated in 1998

Municipal wastewater treatment

Disposal costs $80-$440dry ton

Combine Wastes

Carbohydrate Rich

MSW

(40ndash80)

Nutrient Rich

Sewage Sludge

(20ndash60)

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Paper Wastes

Office paperNewspapers MagazinesBooksBoxesCardboardPackaging Paper

gt 100 millions tonsyear

30 MSW

50 recovery in the year 2000

Sewage Sludge

69 million dry tons generated in 1998

Municipal wastewater treatment

Disposal costs $80-$440dry ton

Combine Wastes

Carbohydrate Rich

MSW

(40ndash80)

Nutrient Rich

Sewage Sludge

(20ndash60)

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Sewage Sludge

69 million dry tons generated in 1998

Municipal wastewater treatment

Disposal costs $80-$440dry ton

Combine Wastes

Carbohydrate Rich

MSW

(40ndash80)

Nutrient Rich

Sewage Sludge

(20ndash60)

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Combine Wastes

Carbohydrate Rich

MSW

(40ndash80)

Nutrient Rich

Sewage Sludge

(20ndash60)

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

MixAlco ProcessMixAlco Process

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversion

CarboxylicCarboxylicAcid Acid SaltsSalts

DewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

PatentsPatents

598613359691896262313

59623075874263

58658985693296

60433926395926

HydrogenHydrogen

BiomassBiomass

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

HydrogenateHydrogenate

MixedMixedKetonesKetonesThermalThermal

ConversionConversionDewaterDewaterFermentFermentPretreatPretreat

Calcium CarbonateCalcium CarbonateLimeLime

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

PretreatmentPretreatment

FermentFerment DewaterDewaterPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Lime TreatmentLime Treatment

TT = 100= 100ooCCtt = 1 h= 1 hLime loading = 01 g Ca(OH)Lime loading = 01 g Ca(OH)22g biomassg biomassWater loading = 5 to 15 g HWater loading = 5 to 15 g H22Og biomassOg biomass

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

In situ DigestionIn situ Digestion

bullbull Weigh ~ 2 g of biomassWeigh ~ 2 g of biomassbullbull Place biomass in ldquotea bagrdquoPlace biomass in ldquotea bagrdquobullbull Place ldquotea bagsrdquo in porous sackPlace ldquotea bagsrdquo in porous sackbullbull Place porous sacks in cattle rumenPlace porous sacks in cattle rumenbullbull IncubateIncubatebullbull Remove porous sackRemove porous sackbullbull Wash ldquotea bagsrdquoWash ldquotea bagsrdquobullbull DryDrybullbull Weigh residueWeigh residue

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

In-Situ DigestionIn-Situ Digestion4848

-- h D

iges

tion

h D

iges

tion

(g d

iges

ted

g fe

d)(g

dig

este

dg

fed)

0606040402020000

10100808

UntreatedUntreated

SugarSugar--canecanebagassebagasse

AfricanAfricanmilletmilletstrawstraw

SorghumSorghumstrawstraw

TobaccoTobaccostalksstalks

LimeLime--treatedtreated

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

FermentationFermentation

Ferment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Environments where organic acids naturally formEnvironments where organic acids naturally form

bullbull animal rumenanimal rumen-- cattlecattle-- sheepsheep-- deerdeer-- elephantselephants

bullbull anaerobic sewageanaerobic sewage digestorsdigestorsbullbull swampsswampsbullbull termite gutstermite guts

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Why are organic acids favoredWhy are organic acids favored

The actualThe actual stoichiometrystoichiometry is more complexis more complex

CC66HH1212OO66 rarrrarr 2 C2 C22HH55OH + 2 COOH + 2 CO22 ∆∆G = G = --4856 kcalmol4856 kcalmol

CC66HH1212OO66 rarrrarr 3 C3 C22HH33OOH OOH ∆∆G = G = --618 kcalmol618 kcalmol

5 C5 C66HH1212OO66 rarrrarr 6 acetate + 2 propionate + butyrate + 5 CO6 acetate + 2 propionate + butyrate + 5 CO22 + 3 CH+ 3 CH 4 4 + 6 H+ 6 H22OO(67 mol) (22 mol) (11 mol)(67 mol) (22 mol) (11 mol)

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Typical Product Spectrumat Different Culture TemperaturesTypical Product Spectrumat Different Culture Temperatures

40oC 55oC C2 ndash Acetic 41 wt 80 wt C3 ndash Propionic 15 wt 4 wt C4 ndash Butyric 21 wt 15 wt C5 ndash Valeric 8 wt lt1 wt C6 ndash Caproic 12 wt lt1 wt C7 ndash Heptanoic 3 wt lt1 wt

100 wt 100 wt

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Countercurrent FermentationCountercurrent Fermentation

FreshFreshBiomassBiomass

LiquidLiquidHarvestHarvest

SpentSpentSolidsSolids

Fresh Fresh LiquidLiquid

Product Concentration

Biomass Digestion

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Suppress MethaneSuppress Methane

bullbull Bromoethane sulfonicBromoethane sulfonic acidacidbullbull MonensinMonensinbullbull BromoformBromoformbullbull IodoformIodoform

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Fermentation GoalsFermentation Goals

bullbull High product concentrationHigh product concentrationbullbull High conversionHigh conversionbullbull Suppress methaneSuppress methanebullbull AffordableAffordable fermentorsfermentors

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Affordable FermentorsAffordable Fermentors

AboveAbove--ground stainless steelground stainless steel

AboveAbove--ground carbon steelground carbon steel

AboveAbove--ground concreteground concrete

InIn--ground plastic

$380m$380m33

$125m$125m33

$ 69m$ 69m33

$ 12m$ 12m3ground plastic 3

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

CPDM ModelingCPDM ModelingPr

oduc

tPr

oduc

t Con

cC

onc

Initi

al S

ubst

rate

Initi

al S

ubst

rate

Con

cC

onc

rrrr

xPP

TimeTime

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Rate EquationRate Equation

r a xb P

= minus+( )

( )

1

1

6 0

4 38

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

4-Stage Countercurrent Fermentors (MSWSS)4-Stage Countercurrent Fermentors (MSWSS)

0

5

10

15

20

25

30

35

40

025 035 045 055 065 075Digestion (fraction of VS)

LRT (days)

75

1125

15

1875225

34

567375

89

Solids loading rate(g(Lmiddotd))

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

DewateringDewatering

FermentFerment DewaterPretreatPretreat ThermalThermalConversionConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Heat RequirementsHeat Requirements

BtuBtulb water removedlb water removed

SingleSingle--effect evaporator 1000effect evaporator 1000TripleTriple--effect evaporator effect evaporator 333333Amine dewateringAmine dewatering 6060

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Thermal ConversionThermal Conversion

FermentFerment DewaterDewaterPretreatPretreat ThermalConversion HydrogenateHydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Thermal ConversionStoichiometryThermal ConversionStoichiometry

HH33CCOCaOCCHCCOCaOCCH33 rarr Ηrarr Η33CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33CCHCCH22COCaOCCHCOCaOCCH22CHCH33 rarr Ηrarr Η33CCHCCH22CCHCCH22CHCH33 + CaCO+ CaCO33

Calcium Propionate DiethylCalcium Propionate Diethyl KetoneKetone

OO OO OO

HH33CCHCCH22CHCH22COCaOCCHCOCaOCCH22CHCH22CHCH33 rarr Ηrarr Η33CCHCCH22CHCH22CCHCCH22CHCH22CHCH33 + CaCO+ CaCO33

Calcium ButyrateCalcium Butyrate Dipropyl KetoneDipropyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Thermal Conversion KineticsThermal Conversion Kinetics

001001

0101

11

1010

100100

10001000

1000010000

Hal

f Life

(min

)H

alf L

ife (m

in)

AcetateAcetate

PropionatePropionate

ButyrateButyrate

380 400 420 440 380 400 420 440 460460Temperature ( Temperature ( o o C)C)

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

HydrogenationHydrogenation

FermentFerment DewaterDewaterPretreatPretreat ThermalThermalConversionConversion Hydrogenate

Lime KilnLime Kiln

MixedMixedAlcoholAlcoholFuelsFuels

MixedMixedKetonesKetones

CarboxylicCarboxylicAcid Acid SaltsSalts

BiomassBiomass

HydrogenHydrogenCalcium CarbonateCalcium CarbonateLimeLime

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Ketone HydrogenationStoichiometryKetone HydrogenationStoichiometry

OHOH3CCCH3 + H2 rarr H3CCCH3

HAcetone Isopropanol

H3CCCH2CH3 + H2 rarr H3CCCH2CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3CCH2CCH2CH3 + H2 rarr H3CCH2CCH2CH3

O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Ketone HydrogenationKetone Hydrogenation

Liquid Liquid KetonesKetones

Catalyst = 200 gL Raney nickelCatalyst = 200 gL Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min ( P = 15Time = 35 min ( P = 15 atmatm) )

HH22

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Advantages of MixAlcoApproachAdvantages of MixAlcoApproach

bullbull nonsterilenonsterile fermentationfermentationbullbull no spoiled batchesno spoiled batchesbullbull inexpensive tanksinexpensive tanksbullbull robust plant operationrobust plant operationbullbull adaptable microorganismsadaptable microorganismsbullbull stable microorganismsstable microorganismsbullbull microorganisms selfmicroorganisms self--generategeneratebullbull no enzyme additionno enzyme addition

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Potential ProductsPotential Products

bullbull KetonesKetonesalcohol fuelsalcohol fuelsbullbull Organic acidsOrganic acids

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Carboxylic Acid ProductionCarboxylic Acid Production

BiomassBiomass PretreatPretreat FermentFerment DewaterDewater ldquoSpringingrdquoldquoSpringingrdquo

CarboxylateCarboxylateSaltSalt

COCO22

Carboxylic AcidCarboxylic Acid

Lime KilnLime Kiln

CaOCaO

COCO22

CaCOCaCO33

acetic acidacetic acidpropionicpropionic acidacidbutyric acidbutyric acid

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Acid ldquoSpringingrdquoAcid ldquoSpringingrdquo

Ca(Ac)2

CO2 CaCO3

R3N

H2O

R3NHAc

HAc

R3NHAc

R = - CH2CH3

R= - CH2CH2CH2CH2CH2CH2CH2CH3 R3N

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Chemical FlowchartChemical Flowchart

BBIIOOMMAASSSS

CalciumCalciumAcetateAcetate

AceticAceticAcidAcid

EthanolEthanol

EthylEthylAcetateAcetate

CalciumCalciumMagnesiumMagnesiumAcetateAcetate

AcetoneAcetone

HH22

IsopropanolIsopropanol

IsopropylIsopropylTertiaryTertiaryButylButylEtherEther

IsobutyleneIsobutylene

HH22

DiisopropylDiisopropylEtherEther

CalciumCalciumPropionatePropionate

PropionicPropionicAcidAcid

nn--PropanolPropanolPropylPropylPropionatePropionate

DiethylDiethyl KetoneKetone 33--PentanolPentanol

HH22

HH22

CalciumCalciumButyrateButyrate

ButyricButyricAcidAcid

nn--ButanolButanolButylButylButyrateButyrate

DipropylDipropylKetoneKetone

HH2244--HeptanolHeptanol

HH22

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Alcohol Production from Municipal Solid Waste

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Plant CapacityPlant Capacity

((tonnetonneh) (mill galyr) City Populationh) (mill galyr)Plant CapacityPlant Capacity

City Population

2 11 400002 11 400001010 5656 20000020000040 223 80000040 223 800000

160 893 3200000160 893 3200000800 4467 16000000800 4467 16000000

Base Base CaseCase

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Optimization (40 tonneh)Optimization (40 tonneh)

0

5

10

15

20

25

30

10 15 20 25 30 35Product Concentration (gL)

Cos

t ($

tonn

e)

TotalTotal

DewateringDewateringFermentationFermentation

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Capital Cost of Each Section (mill $)(40 tonneh) Capital Cost of Each Section (mill $)(40 tonneh)

Pretreat Pretreat Ferment Dewater Dry Thermal HydrogenFerment Dewater Dry Thermal HydrogenConvConv

147147

23235050

3030 39391010

Total = $30 millTotal = $30 mill

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Cost of Each Section ($tonne feed)(15 ROI 40 tonneh) Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)

12021202

AdminAdmin Pretreat Pretreat Ferment Dewater Ferment Dewater Dry Thermal HydrogenDry Thermal HydrogenConvConv

184184

862862 910910686686 600600 524524

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Effect of Scale on Capital CostEffect of Scale on Capital Cost

1

10

100

1000

1 10 100 1000Plant Capacity (tonneh)

Cap

ital C

ost (

mill

$)

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Effect of Scale on Alcohol Price(15 ROI free biomass)Effect of Scale on Alcohol Price(15 ROI free biomass)

$054L$054L$205gal$205gal

$028L$028L$105gal$105gal $019L$019L

$071gal

2 10 40 160 8002 10 40 160 800Plant Capacity (Plant Capacity (tonnetonneh)h)

$071gal $016L$016L$059gal$059gal

$013L$013L$048gal$048gal

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Mixed Alcohol Selling Price(40 tonneh)

Mixed Alcohol Selling Price(40 tonneh)

-02-01

0010203040506

-100 -80 -60 -40 -20 0 20 40

Biomass Cost ($tonne)

Alc

ohol

Sel

ling

Pric

e ($

L) 6060

454530301515

ROI ()ROI ()

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Average MSW Tipping FeesAverage MSW Tipping Fees

State Tipping FeeState Tipping Fee($dry($dry tonnetonne))

New York 12468New York 12468Massachusetts Massachusetts 96299629New Jersey New Jersey 91859185Connecticut 8899Connecticut 8899Minnesota 8135Minnesota 8135Delaware 8044 Delaware 8044 Source Source Solid Waste DigestSolid Waste Digest August 1996 August 1996

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Net Tipping Fee (New York)Net Tipping Fee (New York)

060060

024024

016016Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

NonrecyclableNonrecyclable+ Raw Tipping Fee = $125+ Raw Tipping Fee = $125

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $20$20

$53

RecyclableRecyclable

$53

$53 $53 $ 88 $ 88

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Net Tipping Fee (Average US)Net Tipping Fee (Average US)

Basis = 1 dryBasis = 1 dry tonnetonne raw MSWraw MSW

060060

024024

016016NonrecyclableNonrecyclable+ Raw Tipping Fee = $63+ Raw Tipping Fee = $63

-- Sorting = $52Sorting = $52-- NonrecyclableNonrecyclable Disposal = Disposal = $10$10

$ 1

RecyclableRecyclable

$ 1

$ 1 $ 1 $ 153 $ 153

0606 tonnetonne biodegradablebiodegradable==BiodegradableBiodegradable

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Scenarios(40 tonneh)Scenarios(40 tonneh)

New York New York Average US Average US Bagasse Bagasse

--88 60 004 01688 60 004 016--2 15 018 0692 15 018 069

+26 15 029 109 +26 15 029 109

Net Feed ROI Alcohol Sales PriceNet Feed ROI Alcohol Sales PriceCostCost

($($tonnetonne) () ($L) ($gal)) () ($L) ($gal)

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Energy Content

Energy(MJL) (Btugal)

GasolineGasoline

Mixed AlcoholsMixed Alcohols

Ethanol

349 125000

290 104000

234 84300Ethanol

Energy Content

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Properties of Fuel OxygenatesProperties of Fuel Oxygenates

Blending Blending ReidBlending Blending ReidOctane Vapor PressureOctane Vapor Pressure(R + M)2 ((R + M)2 (psipsi))

EthersEthersMethyl tertiary butyl ether (MTBE)Methyl tertiary butyl ether (MTBE) 110110 88

Isopropyl tertiary butyl ether (IPTBE) 113 Isopropyl tertiary butyl ether (IPTBE) 113 2525AlcoholsAlcohols

MethanolMethanol 108 31108 31++

Ethanol Ethanol 115 17115 17Isopropanol Isopropanol 106106 1414

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Acid Production from Los Angeles Yard Waste

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

FeedstockFeedstock

Yard ClippingsYard Clippings

hdry tonne16

h 8000yr

yrd 280

ton11tonne

wet tondry ton50

dwet ton1000

=timestimestimestimes

Sewage Sludge

hdry tonne8

h 8000yr

yrd 365

ton11tonne

wet tondry ton30

dwet ton650

=timestimestimestimes

htonne 24 Total =

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Estimated Capital CostEstimated Capital Cost

$30 million$20 million for mixed acid production$10 million for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Key AssumptionsKey Assumptions

fedtonnedigestedtonne075 Conversion =

fedtonneacidstonne065 y Selectivit =

fed tonneacidstonne490

digested tonneacidstonne065

fed tonnedigestedtonne075 Yield =times=

Solid residue will be burned for process heat sold as compost or landfilled

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Expected Product Yields (mesophilic 40oC)Expected Product Yields (mesophilic 40oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill85

acid totallbC2lb410

yracid totallb mill207 C2 =times=

yrlbmill3700 (23)

yrlbmill31

acid totallbC3lb150

yracid totallb mill207 C3 =times=

yrlbmill250 (124)

yrlb mill91

acid totallbC4 lb 440

yracid totallb mill207 C4 =times=

++

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Expected Product Yields (thermophilic 55oC)Expected Product Yields (thermophilic 55oC)

yrlbmill 207

tonnelb2200

biomass tonneacidtonne490

yrh8000

hbiomasstonne24 Acid Total =timestimestimes=

US ProductionPlant Production

yrlbmill166

acid totallbC2lb800

yracid totallb mill207 C2 =times=

yrlbmill3700 (45)

yrlbmill38

acid totallbC3lb040

yracid totallb mill207 C3 =times=

yrlbmill250 (33)

yrlb mill33

acid totallbC4 lb 160

yracid totallb mill207 C4 =times=

++

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Tipping Fee IncomeTipping Fee Income

Both sewage sludge and clippings have a tipping fee of $22wet ton

yrmill 15$

dry tonne80$

yrh8000

hsludgesewage dry tonne8 =timestimes

yrmill 16$

dry tonne48$

yrh8000

hclippingsdry tonne16 =timestimes

yrmill$112 Total =

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Income from Acid Sales(mesophilic 40oC)Income from Acid Sales(mesophilic 40oC)

Price Basis

yrmill315$

lb180$

yrlb mill852C =times=

yrmill09$

lb290$

yrlb mill313C =times=

yrmill34$

lb0470$

yrlb mill914C =times=+

yrmill$286 Total =

69 of spot price

69 of spot price

Fuel value $44mill Btu

Chemical Market Reporter

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Income from Acid Sales(thermophilic 55oC)Income from Acid Sales(thermophilic 55oC)

Price Basis

yrmill30$

lb180$

yrlb mill1662C =times= 69 of spot price

yrmill42$

lb290$

yrlb mill383C =times= 69 of spot price

yrmill61$

lb0470$

yrlb mill334C =times=+ Fuel value $44mill Btu

yrmill$34 Total = Chemical Market Reporter

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

ExpensesExpenses

yrmill 219$

biomass tonne100$

yrh8000

hbiomasstonne24 Expense =timestimes=

$70tonne for mixed acid production$30tonne for product purification

Holtzapple et al Applied Biochemistry and Biotechnology vol 77-79 p 609 (1999)

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

ProfitabilityProfitability

Mesophilic Thermophilic($ millyr) ($ millyr)

Tipping Fee Income +112 +112Product Sales + 286 + 340Expenses ndash 192 ndash 192Profit +206 +260

87mill 30$millyr$260 ROI ==69

mill 30$millyr$206 ROI ==

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Recent Improvements

Recent Improvements

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Steam-Sorted Real MSW

0

5

10

15

20

25

30

35

0 02 04 06 08 1

Conversion

LRT(days)

12 8

35

6 5 4 3 10

3025

15

VSLRg VS(Ld)

12 10

46

53

8

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

Steam-Sorted Real MSW

ldquoSynthetic MSWrdquo

Dr Michael EleyUniversity of Alabama Huntsvillesorting cost = ~$20ton

Terrestrial inocula200 g VSL

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Synthetic MSWSynthetic MSW

Cardboard 210 584Newspaper 139 583Packaging 107 577Printed paper 101 389Leaves 78 106Wood 63 806Misc non-packaging 63 360Books Magazines 50 262Grass 44 805Food Waste 40 1028Tissue paper 31 389Brush 27 960Greens 19 117

Component Amount() a

MoistureContent ()

Fats and oils b 27 -

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Marine Inocula

0

10

20

30

40

50

60

70

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L)

456812

1510

2530

35LRT (days)

VSLR g(Lmiddotd) 456812

Marine

Terrestrial

300 g VSL liquid

ldquoSynthetic MSWrdquo

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Advanced Lime Treatment

0

10

20

30

40

50

60

0 02 04 06 08 1

Conversion

Tota

l car

boxy

lic a

cid

conc

entr

atio

n (g

L) 35

128 6 5

3025

15

104 3

LRT (days)

VSLRg(Ld) 12 8 6 5 4 3

Advanced Lime

Conventional Lime

200 g VSLMarine Inocula

ldquoSynthetic MSWrdquo

bull Handles high-lignin biomassbull Less equipment

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Jet Ejector DewateringJet Ejector Dewatering

SaltSolution(FermentorBroth)

Jet Ejector

High-PressureSteam

Distilled Water

Filter

Salt Crystals

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Advantages of Jet EjectorAdvantages of Jet Ejector

bullFew stepsbullLow capitalbullLow energybullRobustbullOther applications

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Advanced BioreactorAdvanced Bioreactor

bullLess solids handlingbullEasier solids handlingbullLower cost

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Next StepsNext Steps

bull Complete pilot plant bull 6 mo $200000

bull Operate pilot plant bull1 yr $100000

bull Preliminary process economics bullNofsinger $30000

bull Market assessment bullChemical Market Resources Inc $20000

Note All costs are estimates

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

ConclusionsConclusionsbull Well-developed technology

bull Pilot plant under constructionbull 12 years of research

bull 13 MS theses completedbull 10 PhD dissertations completedbull ~90 personmiddotyears invested

bull Profitablebull Simple processing stepsbull Intellectual property definedbull Large market for productsbull Improvements will lower costs

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions

Thank you for yourtime and attention

• MixAlco Process Waste Biomass to Fuels and Chemicals
• Potential Products
• MixAlco Process
• Patents
• Lime Treatment
• In situ Digestion
• In-Situ Digestion
• Environments where organic acids naturally form
• Why are organic acids favored
• Typical Product Spectrumat Different Culture Temperatures
• Fermentation Goals
• Countercurrent Fermentation
• Fermentation Goals
• Suppress Methane
• Fermentation Goals
• Affordable Fermentors
• CPDM Modeling
• Rate Equation
• 4-Stage Countercurrent Fermentors (MSWSS)
• Heat Requirements
• Thermal Conversion Stoichiometry
• Thermal Conversion Kinetics
• Ketone Hydrogenation Stoichiometry
• Ketone Hydrogenation
• Advantages of MixAlco Approach
• Potential Products
• Carboxylic Acid Production
• Acid ldquoSpringingrdquo
• Chemical Flowchart
• Economics
• Plant Capacity
• Optimization (40 tonneh)
• Capital Cost of Each Section (mill $)(40 tonneh)
• Cost of Each Section ($tonne feed)(15 ROI 40 tonneh)
• Effect of Scale on Capital Cost
• Effect of Scale on Alcohol Price(15 ROI free biomass)
• Mixed Alcohol Selling Price(40 tonneh)
• Average MSW Tipping Fees
• Net Tipping Fee (New York)
• Scenarios (40 tonneh)
• Energy Content
• Properties of Fuel Oxygenates
• Economics
• Feedstock
• Estimated Capital Cost
• Key Assumptions
• Expected Product Yields (mesophilic 40oC)
• Expected Product Yields (thermophilic 55oC)
• Tipping Fee Income
• Income from Acid Sales(mesophilic 40oC)
• Income from Acid Sales(thermophilic 55oC)
• Expenses
• Profitability
• Recent Improvements
• Synthetic MSW
• Advantages of Jet Ejector
• Advanced Bioreactor
• Next Steps
• Conclusions