Holtzapple 3Mar2011 AIChE 136pp

Richard SmalleyRichard Smalley

1943 to 2005Nobel Prize in Chemistry in 1996

Buckeyballs

Smalleys Top Ten Human ProblemsSmalleys Top Ten Human Problems

1.1. EnergyEnergy2.2. WaterWater3.3. FoodFood4.4. EnvironmentEnvironment5.5. PovertyPoverty

6.6. Terrorism/WarTerrorism/War7.7. DiseaseDisease8.8. EducationEducation9.9. DemocracyDemocracy10.10.PopulationPopulation

http://cohesion.rice.edu/NaturalSciences/Smalley/emplibrary/120204%20MRS%20Boston.pdf

Smalleys Bold ClaimSmalleys Bold Claim

All of these problems can be All of these problems can be addressed with energy that isaddressed with energy that is

Clean Clean AffordableAffordable AbundantAbundant


1.1. EnergyEnergy2.2. WaterWater3.3. FoodFood4.4. EnvironmentEnvironment5.5. PovertyPoverty

6.6. Terrorism/WarTerrorism/War7.7. DiseaseDisease8.8. EducationEducation9.9. DemocracyDemocracy10.10.PopulationPopulation



1.1. EnergyEnergy2.2. EnergyEnergy3.3. EnergyEnergy4.4. EnergyEnergy5.5. EnergyEnergy

6.6. EnergyEnergy7.7. EnergyEnergy8.8. EnergyEnergy9.9. EnergyEnergy10.10.EnergyEnergy


EnergyEnergy

Mark HoltzappleDepartment of Chemical Engineering

Texas A&MCollege Station, TX

OutlineOutline

BackgroundBackgroundBiofuelsBiofuelsAdvanced EnginesAdvanced Engines

Driving ForcesDriving Forces

Growing populationGrowing population Rising standard of livingRising standard of living Oil importsOil imports Peak oilPeak oil Global warmingGlobal warming

Global PopulationGlobal Population

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4 million

6.90 billion

http://en.wikipedia.org/wiki/World_population

Global Population MilestonesGlobal Population Milestones

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1.0 billion1815

Global Population MilestonesGlobal Population Milestones

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6.90 billion


2.8 billion

1956

Big PictureBig Picture

Energy and WealthEnergy and Wealth

Energy Flow in the United States(2009)

http://www.eia.doe.gov/emeu/aer/pdf/pages/sec1_3.pdf

Energy Flow in the United States(2009)

Net Imports = (25.16 4.21)/35.27 = 59.4%

Historical Oil PriceHistorical Oil Price

http://en.wikipedia.org/wiki/Oil_price_increases_of_2004-2006

July 2008~$147/bbl

Jan 2009~$45/bbl

Jan 2011~$90/bbl

U.S. Oil Trade Deficit (2009)U.S. Oil Trade Deficit (2009)

ybillion/da 1.1$bbl90$

nconsumptio bblimport bbl 59.0

daynconsumptio bbl mill 6.20





$400 billion/yr Oil imports





$400 billion/yr Oil imports

$379 billion/yr Total importshttp://www.americaneconomicalert.org/ticker_home.asp

American geophysicist

Shell Oil research laboratory

Houston, TX

M. King Hubbert (1903-89)M. King Hubbert (1903-89)

US Oil Production Data through 1956 US Oil Production Data through 1956

1870 90 1910 30 50 70 90 2010 30 50Year

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Actual

Source: Deffeyes, Hubberts Peak (2001)

US Oil Production Hubberts Prediction (1956) US Oil Production Hubberts Prediction (1956)

1870 90 1910 30 50 70 90 2010 30 50Year

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US Oil Production How well did he do? US Oil Production How well did he do?

1870 90 1910 30 50 70 90 2010 30 50Year

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World Oil Production Deffeyes Prediction (2001) World Oil Production Deffeyes Prediction (2001)

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1860 80 1900 20 40 60 80 2000 20 40 60YearSource: Deffeyes, Hubberts Peak (2001)

November 24, 2005

How good was his prediction?How good was his prediction?

http://www.hubbertpeak.com/

(May)


Growing populationGrowing population Rising standard of livingRising standard of living Oil importsOil imports Peak oilPeak oil Global warming Global warming

Recent CO2 ConcentrationRecent CO2 Concentration380

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Mauna Loa Observatory

Recent CorrelationRecent Correlation

1860 80 1900 20 40 60 80 2000 Year

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Global Warming ProjectionsGlobal Warming Projections

Intergovernmental Panel on Climate ChangeBusiness-as-usual scenario

How much Energy does an Average American Consume?


Primary Energy = 11.2 kW heatPrimary Energy = 11.2 kW heat



Work = 2.24 kWWork = 2.24 kW

OutlineOutline


Oil RefineryOil Refinery

Crude Oil Fuels

Chemicals

Polymers

Oil Refinery$635/tonne

$90/bbl$2.14/gal

$665/tonne$101/bbl$2.42/gal

Oil RefineryOil Refinery

Crude Oil Fuels

Chemicals

Polymers

Oil Refinery

Crack Spread = 11/bbl

$635/tonne$90/bbl

$2.14/gal


Biomass RefineryBiomass Refinery

Biomass Fuels

Chemicals

Polymers

Biomass Refinery$60/tonne

$20/bbl*$0.49/gal*

* Equivalent energy basisFiber

Feed

Pharmaceuticals

Food



Biomass Fuels

Chemicals

Polymers

Biomass Refinery$60/tonne

$20/bbl*$0.49/gal*


Feed

Pharmaceuticals

Food

Crack Spread = $81/bbl



Biomass Fuels

Chemicals

Polymers

$60/tonne$20/bbl*

$0.49/gal*


Feed

Pharmaceuticals

Food

Crack Spread = $81/bbl


MixAlco ProcessMixAlco Process

HydrogenHydrogenBiomassBiomass

HydrocarbonHydrocarbonFuelsFuels

Thermal Thermal ConversionConversionDewaterDewater

FermentFermentPretreatPretreat

LimeLime

CarboxylateCarboxylateSaltsSalts

HydrogenateHydrogenate OligomerizeOligomerize

KetonesKetones AlcoholsAlcohols





FermentFermentPretreat

LimeLime




Advanced Lime Treatment Advanced Lime Treatment

Biomass + Lime

Gravel

Air

Building the PileBuilding the Pile

~100 ft

Building the PileBuilding the Pile

Lignin RemovalLignin Removal

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25oC

50oC57oC 25oC

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No Air Air





FermentPretreatPretreat

LimeLime







Thermal ConversionDewaterDewater


LimeLime

CarboxylateSalts

Hydrogenate Oligomerize

Ketones Alcohols

Environments where organic acids naturally form Environments where organic acids naturally form

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

anaerobic sewage digestorsanaerobic sewage digestors swampsswamps termite gutstermite guts

Why are organic acids favored?Why are organic acids favored?

The actual stoichiometry is more complexThe actual stoichiometry is more complex

CC66 HH1212 OO66

2 C2 C22 HH55 OH + 2 COOH + 2 CO22 G = G = --48.56 kcal/mol48.56 kcal/mol

CC66 HH1212 OO66 3 C3 C22 HH33 OOH OOH G = G = --61.8 kcal/mol61.8 kcal/mol

CC66 HH1212 OO66

acetate + propionate + butyrate + COacetate + propionate + butyrate + CO22 + CH+ CH 4 4 + H+ H22 O + HO + H22

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Why are organic acids favored?Why are organic acids favored?

The actual stoichiometry is more complexThe actual stoichiometry is more complex

CC66 HH1212 OO66

2 C2 C22 HH55 OH + 2 COOH + 2 CO22 G = G = --48.56 kcal/mol48.56 kcal/mol

CC66 HH1212 OO66 3 C3 C22 HH33 OOH OOH G = G = --61.8 kcal/mol61.8 kcal/mol

CC66 HH1212 OO66

acetate + propionate + butyrate + COacetate + propionate + butyrate + CO22 + CH+ CH 4 4 + H+ H22 O + HO + H22

glucose ethanolglucose ethanol

glucose acetic acidglucose acetic acid

Methanogen inhibitor

Typical Product Spectrum at Different Culture Temperatures Typical Product Spectrum at Different Culture Temperatures

40oC 55oC C2 Acetic 41 wt % 80 wt %C3 Propionic 15 wt % 4 wt %C4 Butyric 21 wt % 15 wt %C5 Valeric 8 wt %




Thermal Thermal ConversionConversionDewater


LimeLime




VaporVapor--Compression DesalinationCompression Desalination

Salt water

Distilled waterBrine

High pressureLow pressure

Heat

T = 100oCP = 1.00 atm

T = 101oCP = 1.04 atm

Dropwise Dropwise CondensationCondensation

Filmwise Filmwise CondensationCondensation

~2,000 Btu/(hft2oF) ~42,000 Btu/(hft2oF)

Laredo Desalination ProjectLaredo Desalination Project




Thermal ConversionDewaterDewaterFerment


LimeLime




Thermal Conversion Stoichiometry Thermal Conversion Stoichiometry

HH33 CCOCaOCCHCCOCaOCCH33

CCCHCCCH33 + CaCO+ CaCO33

OO

Calcium Acetate AcetoneCalcium Acetate Acetone

OO OO

HH33 CCHCCH22 COCaOCCHCOCaOCCH22 CHCH33

CCHCCH22 CCHCCH22 CHCH33 + CaCO+ CaCO33Calcium Propionate Diethyl KetoneCalcium Propionate Diethyl Ketone

OO OO OO

HH33 CCHCCH22 CHCH22 COCaOCCHCOCaOCCH22 CHCH22 CHCH33

CCHCCH22 CHCH22 CCHCCH22 CHCH22 CHCH33 + CaCO+ CaCO33Calcium Butyrate DipropCalcium Butyrate Dipropyl Ketoneyl Ketone

OO OO OO

Thermal Conversion KineticsThermal Conversion Kinetics

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LimeLime


Hydrogenate OligomerizeOligomerize


Ketone Hydrogenation Stoichiometry Ketone Hydrogenation Stoichiometry

O OHH3 CCCH3 + H2 H3 CCCH3

HAcetone Isopropanol

H3 CCCH2 CH3 + H2 H3 CCCH2 CH3H

O OH

Methyl Ethyl Ketone 2-Butanol

H3 CCH2 CCH2 CH3 + H2 H3 CCH2 CCH2 CH3O

H

OH

Diethyl Ketone 3-Pentanol

Ketone HydrogenationKetone Hydrogenation

HH22

Liquid KetonesLiquid Ketones

Catalyst = 200 g/L Raney nickelCatalyst = 200 g/L Raney nickelTemperature = 130Temperature = 130ooCCTime = 35 min (@ P = 15 atm) Time = 35 min (@ P = 15 atm)






LimeLime


HydrogenateHydrogenate Oligomerize


Oligomerizaton ChemistryOligomerizaton Chemistry

OHH3 CCCH3 H3 CHC=CH2 + H2 O

H

Isopropanol Propylene

H3 CHC=CH2 + H3 CHC=CH2 H3 CCH2 CH2 HC=CHCH3Propylene Propylene Hexene

H3 CCH2 CH2 HC=CHCH3 + H2 H3 CCH2 CH2 CH2 CH2 CH3Hexene Hexane

Dehydrate

Dimerize

Saturate

Mixed Alcohols to HydrocarbonsMixed Alcohols to Hydrocarbons

Mixed alcoholsfrom MixAlco process Hydrocarbon


Unreacted alcohol

Paraffins

Total

Aromatics


Components of jet fuel


Components of gasoline

MixAlco AdvantagesMixAlco Advantages

Can use wet feedstocksCan use wet feedstocks Wide range of feedstocksWide range of feedstocks Energy efficientEnergy efficient No genetically modified organismsNo genetically modified organisms Many productsMany products Distributed processingDistributed processing

treestrees grassgrass agricultural residuesagricultural residues energy cropsenergy crops

animal manureanimal manure sewage sludgesewage sludge municipal solid wastemunicipal solid waste algae algae bodiesbodies

MixAlco FeedstocksMixAlco Feedstocks

treestrees grassgrass agricultural residues energy cropsenergy crops



Sugarcane BagasseSugarcane Bagasse

~100 ft

treestrees grassgrass agricultural residuesagricultural residues energy crops



ProductivityProductivity

Corn grain Sorghum Energy cane

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Current-Generation BiofuelsCurrent-Generation Biofuels

http://petroleum.berkeley.edu/papers/patzek/CRPS416-Patzek-Web.pdf

CornfieldCornfield

Bart and Phillip

Corn Land Area Required to Supply 100% of US Gasoline Corn Land Area Required to Supply 100% of US Gasoline

Competition with FoodCompetition with Food



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SorghumSorghum

Source: William Rooney, Soil and Crop Sciences, Texas A&M University

Grows in ~35 US states

Yield = 2025 dry ton/(acreyr)



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Energy Cane

treestrees grassgrass agricultural residuesagricultural residues energy cropsenergy crops

animal manureanimal manure sewage sludgesewage sludge municipal solid waste algae algae bodiesbodies


15.7 MJ heat

1000 kg water

Dewatering EnergeticsDewatering Energetics

Ethanol Distillation (5% to 99.9%)

3 = 8.4 = 28.5% of the combustion heatkg steam

L ethanol

MJ heat

kg ethanol

MixAlco: Carboxylate Salt Vapor-Compression Dewatering (5% to 100%)

Source: B.L. Maiorella, Ethanol, Comprehensive Biotechnology, Vol. 3, Pergamon Press (1985).

95 kg water

5 kg acid=

0.3 MJ

kg acid= 1.7% of the combustion heat

Work = 5.5 kWh/thous gal = 1.45 kWh/m3 Assume heat to work is 33% efficient

ChemistryChemistry

Carboxylate Salt

Carboxylic AcidKetone

AldehydeFormic Acid Formic Acid

Secondary Alcohol

H2

Primary Alcohol

Ester H2

Ether

Olefins

Paraffins Cyclics Aromatics

Hydrocarbons

= Fuel

MixAlco Logistics (Example)MixAlco Logistics (Example)

OilRefinery Carboxylate Salts Pipeline

Ketones, Acids, or Alcohols PipelineExisting Oil Pipeline

MixAlco Plant

Satellite FermentorsBayou

Ocean

Competes with oil at about $70/bbl without subsidies

Brief History of MixAlco ProcessBrief History of MixAlco Process

1991 1991 Laboratory research beganLaboratory research began2000 2000 Pilot plant construction beganPilot plant construction began2008 2008 Demonstration plant construction beginsDemonstration plant construction begins

Brief History of MixAlco ProcessBrief History of MixAlco Process

1991 1991 Laboratory research beganLaboratory research began2000 2000 Pilot plant construction beganPilot plant construction began2008 2008 Demonstration plant construction beganDemonstration plant construction began

Fermentor StructureFermentor Structure

105 ft

50 ft

Construction has begun!!Construction has begun!!

ConstructionConstruction

Fermentor Interior

Fermentor Interior

Completed Fermentor Completed Fermentor

Giant Cattle RumenGiant Cattle Rumen

Dedication (November 2008)Dedication (November 2008)

Governor SpeakingGovernor Speaking

Holtzapple SpeakingHoltzapple Speaking

Naming the Demonstration PlantNaming the Demonstration Plant

Holtzapple Family with GovernorHoltzapple Family with Governor

Holtzapples with GovernorHoltzapples with Governor

OutlineOutline


Sorghum Land AreaSorghum Land Area

30 mpg*

Conventional Car

93 gallons

* at 70 miles per hour

comp = exp = 82%

engine = 57 66%


90 mpg*

StarRotor Engine

31 gallons



12 gallons


235 mpg*

Loremowith

StarRotor Engine


8 gallons


380 mpg*

Apterawith

StarRotor Engine

ApteraAptera

Thank you for yourtime and attention

Richard SmalleySmalleys Top Ten Human ProblemsSmalleys Bold ClaimSmalleys Top Ten Human ProblemsSmalleys Top Ten Human ProblemsEnergy OutlineDriving ForcesGlobal PopulationGlobal Population MilestonesGlobal Population MilestonesDriving ForcesBig PictureEnergy and WealthEnergy and WealthDriving ForcesSlide Number 17Slide Number 18Historical Oil PriceU.S. Oil Trade Deficit (2009)U.S. Oil Trade Deficit (2009)U.S. Oil Trade Deficit (2009)Driving ForcesM. King Hubbert (1903-89)US Oil Production Data through 1956US Oil ProductionHubberts Prediction (1956)US Oil ProductionHow well did he do?World Oil ProductionDeffeyes Prediction (2001)How good was his prediction?Driving ForcesRecent CO2 ConcentrationRecent CorrelationGlobal Warming ProjectionsHow much Energy does an Average American Consume?How much Energy does an Average American Consume?How much Energy does an Average American Consume?How much Energy does an Average American Consume?OutlineOil RefineryOil RefineryBiomass RefineryBiomass RefineryBiomass RefineryMixAlco ProcessMixAlco ProcessMixAlco ProcessAdvanced Lime Treatment Building the PileBuilding the PileLignin RemovalMixAlco ProcessMixAlco ProcessEnvironments where organic acids naturally formWhy are organic acids favored?Why are organic acids favored?Typical Product Spectrumat Different Culture TemperaturesMixAlco ProcessVapor-Compression DesalinationDropwise CondensationLaredo Desalination ProjectLaredo Desalination ProjectMixAlco ProcessThermal Conversion StoichiometryThermal Conversion KineticsSlide Number 65MixAlco ProcessKetone Hydrogenation StoichiometryKetone HydrogenationSlide Number 69MixAlco ProcessOligomerizaton ChemistryMixed Alcohols to HydrocarbonsMixed Alcohols to HydrocarbonsMixed Alcohols to HydrocarbonsMixed Alcohols to HydrocarbonsMixAlco AdvantagesMixAlco AdvantagesMixAlco FeedstocksMixAlco FeedstocksSugarcane BagasseMixAlco FeedstocksProductivityProductivityCurrent-Generation BiofuelsCornfieldCorn Land Area Required to Supply 100% of US GasolineCompetition with FoodProductivitySorghumProductivitySlide Number 91Slide Number 92MixAlco FeedstocksSlide Number 94MixAlco AdvantagesDewatering EnergeticsMixAlco AdvantagesMixAlco AdvantagesChemistryMixAlco AdvantagesSlide Number 101MixAlco AdvantagesMixAlco AdvantagesEconomicsEconomicsBrief History of MixAlco ProcessBrief History of MixAlco ProcessSlide Number 108Brief History of MixAlco ProcessBrief History of MixAlco ProcessFermentor StructureConstruction has begun!!ConstructionConstructionConstructionConstructionConstructionConstructionFermentor InteriorCompleted Fermentor Giant Cattle RumenDedication (November 2008)Governor SpeakingHoltzapple SpeakingNaming the Demonstration PlantHoltzapple Family with GovernorHoltzapples with GovernorOutlineSorghum Land AreaSlide Number 130Sorghum Land AreaSorghum Land AreaSorghum Land AreaApteraApteraSlide Number 136

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Holtzapple 3Mar2011 AIChE 136pp