WP 2A Pyrolysis Biorefinery - Pyne Biorefinery... · Percent Feedstock Utilized ... eugenol (propenylguaiacol) ... Pyrolysis demonstration will lead to biorefinery Product separation

PyNe -- Innsbruck PyNePyNe ---- Innsbruck Innsbruck

WP 2A Pyrolysis Biorefinery

Doug ElliottSeptember 28, 2005

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Presentation OrganizationPresentation OrganizationPresentation Organization

Biorefinery basics

U.S. Department of Energy program

Earlier PyNe efforts

Other Biorefinery concepts

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Important to Note:Important to Note:Important to Note:

In both PRESENT and FUTURE biorefineries:

Fuels production provides for large economies of scale

Bio-based products, while smaller in volume, provide greater rates of return and drive profit

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The Potential Role of PyrolysisThe Potential Role of PyrolysisThe Potential Role of Pyrolysis

Part of a sugars-based biorefinery

Part of a Petroleum Refinery

Stand-alone facilities

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An Example of a Current BiorefineryAn Example of a Current BiorefineryAn Example of a Current Biorefinery

Corn Wet Mill

starch corn oilcorn glutenmeal

corn gluten feed

food & industrial starches

hydrolysis

glucose

fuelethanol

High fructosecorn syrup

sorbitol

• foodstuffs• pharma.

polyols isosorbide

hydrogenation

Othersweeteners

citric acid lysine

xanthan gumsitaconic acid

& other fermentation

products

industrial oils

lactic acid

PLApolymers

•resins & plasticsapplications

•polyesters•surfactants•pharmaceuticals

deicerssolventscoatings

glycerolfood oilsfeed oils

Corn Wet Mill

starch corn oilcorn glutenmeal

corn gluten feed

food & industrial starches

hydrolysis

glucose

fuelethanol

fermentation

sorbitol

• foodstuffs• pharma.

polyols isosorbide

hydrogenation

citric acid lysine

xanthan gumsitaconic acid

& other fermentation

products

industrial oils

lactic acid

PLApolymers

•resins & plasticsapplications

•polyesters•surfactants•pharmaceuticals

deicerssolventscoatings

glycerolfood oilsfeed oils

T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005

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Current Ethanol ProcessCurrent Ethanol ProcessCurrent Ethanol Process

Corn Dry Grind Liquefaction Scarification

Fermentation PrimaryDistillation

DistillationRectifier

MolecularSieves

Centrifuge

Triple EffectEvaporator

DDGDryer

DDGAnimal Feed Ethanol

Solids

50%EtOH

95%EtOH

100%EtOH

Liquids

Water Recycle

Solids


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Current Status of Ethanol Dry MillsCurrent Status of Ethanol Dry MillsCurrent Status of Ethanol Dry Mills

Economics are difficult� Current ethanol facilities are limited to only two products,

ethanol and DDG� Economics are highly dependent of value of the co-

product DDG� Significant energy costs are associated with the drying of

DDG� Markets for DDG are not always favorable and will

deteriorate as additional ethanol facilities come on line


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Strategies for Creating Additional ValueStrategies for Creating Additional ValueStrategies for Creating Additional Value

Modify dry mills to include a quick steeping process that allows germ recoveryAdd an intermediate filtration process to recovery non-starch derived sugars (hemicellulose)Develop new fermentations for utilization of five carbon sugars (itaconic acid, succinic acid, etc)Develop new chemistry to produce value added products from hemi-cellulose (sugar alcohols, polyols)Include an energy component-pyrolyze “DDG or modified DDG” to produce bio-oil


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The Holistic Ethanol FacilityThe Holistic Ethanol FacilityThe Holistic Ethanol Facility

Corn Quick Steep Scarification

Filtration Fermentation EthanolRecovery

MolecularSieves

“Fiber” Hydrolysis New DDGAnimal Feed

Ethanol

StarchEtOH 95%

EtOH100%EtOH

GermSeparation

Fermentation

CatalyticConversions

Pyrolysis

Fuel/PowerEG, PG

Glycerol, Etc

ItaconicSuccinic, Etc

Oil


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% Lignin

% Oil

% Sugars

05

101520253035404550

Ove

rall

Pla

nt R

OI

0

7 3

6

11 3

9

15 3

10

22 3

11

29 3

12

37 3

13

44 3

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Percent Feedstock Utilized

EtOH BDO Oil Lignin

Integrated Biorefinery“Back of the Envelope Economics”

EtOH, BDO, Oil, Lignin

Integrated BiorefineryIntegrated Biorefinery“Back of the Envelope Economics”“Back of the Envelope Economics”

EtOHEtOH, BDO, Oil, Lignin, BDO, Oil, Lignin

2122 Tons/Day2122 Tons/Day$30/Dry Ton$30/Dry TonBDO @ $0.60/lbBDO @ $0.60/lb


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The Present View of the BiorefineryThe Present View of the BiorefineryThe Present View of the Biorefinery

LignocellulosicBiomass

Hydrolysis Fermentation

Ethanol Fuel

Distillation

Products

lignin

sugars

?

D.J. Stevens, PyNe, 2005

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The Present View of the BiorefineryThe Present View of the BiorefineryThe Present View of the Biorefinery



Mixed Alcohol Synthesis

Gasification

Ethanol Fuel

Distillation

Products

Products(higher alcohols)

lignin

sugars

syngasAdditionalBiomass

Heat, electricity


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Possible Future BiorefineryPossible Future BiorefineryPossible Future Biorefinery



UpgradingPyrolysis

Ethanol FuelDistillation

Products

Products

lignin

sugars

bio-oilAdditionalBiomass

Motor Fuel

Heat, electricity


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Hydrogenation Pathways with Ruthenium Catalyst

Hydrogenation Pathways with Hydrogenation Pathways with Ruthenium CatalystRuthenium Catalyst

OH

OCH3

CH2

OH

propyl guaiacol

propylmethoxycyclohexanoleugenol (propenylguaiacol)

methoxycyclohexanol

cyclohexanol

guaiacol

methyl-guaiacol

methylmethoxycyclohexanolmethylcyclohexanol

cyclohexanediol

methylcyclohexanediol

propylcyclohexanol

propylcyclohexanediol

D.C. Elliott, STCBC, September 2004

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Cyclohexanol MarketCyclohexanol MarketCyclohexanol Market

price $0.81-0.83/lb from benzenecost ~$0.35/lb w/25% ROIvolume 852 million lb (1972 est. U.S.)

6,400 million lb world (incl cyclohexanone)1992sales 20 million lb (incl cyclohexanone)1992

(most is used internally for adipic acid)uses adipic acid for nylon, esters for

plasticizers, cyclohexanone for caprolactam, cyclohexylamine for emulsion stabilizer

D.C. Elliott, STCBC, September 2004

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Part of a Petroleum Refinery� Biomass first would be converted to bio-oil, possibly at

distributed locations at small scale� Bio-oil can be partially upgraded by catalytic

hydrotreatment at larger scale in proximity of a petroleum refinery

� Upgraded bio-oil then would be co-fed with petroleum feedstocks through a catalytic process to produce conventional refinery product slate

� The global petroleum industry is showing more interest� From the Department of Energy perspective, this is a

medium-term approach

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Pyrolysis/Petroleum BiorefineryPyrolysis/Petroleum BiorefineryPyrolysis/Petroleum Biorefinery


Upgrading and Refining with Petroleum

Fast Pyrolysis Products

bio-oil

Motor Fuel

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Stand-alone facilities� Small size makes economics of fuel production difficult� May be more appropriate for heat and power

applications� High-value specialty chemicals may provide the

economic driver� Unlikely to gain strong support from DOE in the U.S.

because of current focus on petroleum displacement

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Concept of a BiorefineryConcept of a BiorefineryConcept of a Biorefinery

D. Radlein, Fast Pyrolysis Handbook, 1999

Pyrolyzer

Fuel Gas

Char Converter

Bio-oil

Ash Activatedcarbon

Biomass AnhydrosugarsHydrolysis & Fermentation

Reaction

Reaction

Reaction

Separation

Separation

Catalytic Reforming

NH3

lime

alcohol

water

Ethanol

Slow Release Fertilizers(N, Ca, Zn, Fe ...)

Noxolene™(NOx reduction)

BioLime™(NOx/SOx reduction)

Fuel EnhancersFlavor ChemicalsChemicalsFlavors

Adhesives

Diesel/boiler FuelSpecialty

Synthesis GasHydrogen

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Other Chemicals Produced from Bio-oilOther Chemicals Produced from BioOther Chemicals Produced from Bio --oiloil

Wood Preservative (Ensyn patent)Road deicers (Waterloo patent)Resin formulations (many patents)Levoglucosan and Levoglucosenone

Czernik & Bridgwater, Fast Pyrolysis Handbook 3, 2005

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Integrated Pyrolysis Combined CycleIntegrated Pyrolysis Combined CycleIntegrated Pyrolysis Combined Cycle

Biomass

char

chemicals

Bio-oil

gasrecycle

gas and steam turbines

electricityR.C. Brown et al. Iowa State UniversityInternational Journal of Power & Energy Systems24 (3) 2004

Forschungszentrum Karlsruhein der Helmholtz-Gemeinschaft

ITC-CPV HEFW

FW

fast pyrolysis

biomass preparation

liquid fuel synthesissingle pass operation

rail transport from many pyrolysis plants

to large, central plant for syngas generation and us e

entrained flow gasification~ 1200 °C, ≥ ≥ ≥ ≥ 60 bar, ττττ 2 - 3 s

gas cleaningwith heat recovery

electricity generationCC turbine, engine, FC

BACKBONE OF A BIOMASS REFINERYDifferent biomass and carbon feedstock

bio-oil/char -slurry

lignocellulosic biomass:wood, straw, hay ....

fossilfuel:

other biomass:coal ... starch, oil ...

pulverised coalcoal/water slurry

organic waste:paper, plastics, dung ...

co-generation of a marketable product mix

synthesis products:synfuel, chemicals, H 2

electricitylow Theat

O2

CO2

specialchemicals

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The University of GeorgiaBiorefinery/Carbon Cycling Program

The University of GeorgiaThe University of GeorgiaBiorefinery/Carbon Cycling ProgramBiorefinery/Carbon Cycling Program

Biorefinery

Biomass

Bio-Oil

Industrial emitter of greenhouse gases

Stack emissions are convertedto carbon based fertilizer

carbon fertilizer back into fields

NH3 and CO2scrubbing media

vanillic acidacetic acidguaiacolphenol ...

Hydrogen and Fischer-Tropsch Diesel

E.D. Threadgill / P. Harrell, U. Georgia website

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SummarySummarySummary

Numerous opportunities involving:� incorporation into sugar biorefinery� incorporation into a petroleum refinery� stand-alone with chemical, fuel, and power production� incorporation into a gasification and synthesis plant

Pyrolysis demonstration will lead to biorefineryProduct separation and recovery is a major hurdleFinding the right niche is key

Documents

WP 2A Pyrolysis Biorefinery - Pyne Biorefinery... · Percent Feedstock Utilized ... eugenol (propenylguaiacol) ... Pyrolysis demonstration will lead to biorefinery Product separation