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Ethanol Market Opportunities Beyond Gasoline
Governors’ Ethanol Coalition MeetingAugust 1, 2003, Sioux Falls, South Dakota
Presenter: Ted AulichUniversity of North Dakota
Energy & Environmental Research CenterGrand Forks, North Dakota
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Ethanol: Fuel or Chemical Intermediate
• Fuel markets bigger, chemical values higher
• Less processing for fuel, more for chemicals
• Cost of increased processing versus increase in chemical product value
• Process compatibility with integration into ethanol plant
• Current chemical markets and prices based on petroleum
• New and larger markets with lower prices?
Gretz, Warren
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Ethanol Utilization Options
• Dual fermentation – Split glucose solution into ethanol and carboxylic acid production routes
• Guerbet catalytic condensation – React ethanol or ethanol–methanol mixtures to produce bigger alcohols
• Fuel cells – Where does ethanol fit best?• Hydrogen production – Integrate ethanol production
with refueling station-scale hydrogen production• Diesel fuel – What’s best way to put ethanol in
diesel? • Aviation fuel – Premium (up to $3.50/gallon) market
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Dual Fermentation Biorefinery
Corn
Saccharification(amylase)
Yeast Fermentation
Distillation andDehydration
Ethanol
Bacterial Fermentation
Evaporation
HydrolysateGlucoseEthanol Process Carboxylic Acid Process
NH4OH
Ammonium Lactate/Succinate
Esterification TowerProductVapor
Distillation and/orPervaporation
Fuel Ethanol
Optional
Lactic AcidSuccinic Acid
Optional
Ethanol Ethyl Lactate/Succinate
Excess
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Direct Esterification with Ethanol
• Ethanol needed to pull carboxylic acids out of fermentation broth as esters
• Low-temperature/pressure reaction• Continuous-process reaction in flow-
through column containing bed of solid catalyst
• Use ethanol, methanol, butanol, other alcohols
• Final product: ester or alcohol and acid
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Dual Fermentation Product Options(Partial List)
Price, $/poundFuel ethanol 0.19 Lactic acid 0.79Succinic acid 2.70Ethyl lactate 1.00Ethyl succinate ??Ethyl butyrate 2.00Ethyl acetate 0.60Methyl acrylate 0.85
(from methyl lactate)
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Guerbet Catalytic Condensation(Ethanol-Based)
CatalyticCondensation
Ethanol
Distillation andDehydration
Butanoland
Ethanol
Butanol CatalyticCondensation
2-Ethylhexanol
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Guerbet Catalytic Condensation(Methanol- and Ethanol-Based)
CatalyticCondensation
Ethanol+ Methanol
Distillation andDehydration
Isobutanol or Propanoland Ethanol + Methanol
Isobutanolor Propanol
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Catalytic Condensation with Ethanol and/or Ethanol + Methanol
• Low-temperature/pressure reaction• Continuous-process reaction in flow-
through column containing bed of solid catalyst
• Amoco and Exxon interested in alcohol condensation, as evidenced by recent patents on catalyst systems
• Final product: higher alcohol or ester produced via direct esterification with carboxylic acid
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Catalytic Condensation Product Options
(Partial List) Price, $/pound
Fuel ethanol 0.19 Propanol 0.65Butanol 0.48Isobutanol 0.452-Ethylhexanol 0.48Isobutyl acrylate 0.95
(from isobutanol and methyl acrylate)
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Ethanol and Fuel Cells• What is best fit for ethanol in emerging
fuel cell markets?– Proton exchange or solid oxide fuel
cells– Transportation or auxiliary,
distributed, back-up, or military power• Ethanol as hydrogen carrier versus
gasoline, natural gas, propane, diesel fuel, methanol– Can be reformed (converted to
hydrogen) at lower temperature than most carriers except methanol
– Oxygen in ethanol means less air addition required
– Ethanol water miscibility is advantage— can simplify reformer design
– Sulfur-free if denatured with methanol
Ethanol-Based Hydrogen Station• On-board-stored hydrogen for buses in 3 years, for
cars in 10 years• Natural gas most economical feedstock for near-term
on-site hydrogen production/dispensing?• Integration of ethanol and hydrogen production will
alter economics, especially with natural gas price increases. Use 50/50 water/ethanol mix for hydrogen production– Use heat from rectifier/distillation column– Much lower reforming temperature for
ethanol– No desulfurization step required
with ethanol– Ethanol compatible with high-pressure
hydrogen production process under development at EERC
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Ethanol and Diesel Fuel
• Ethanol-blended diesel—vapor pressure increase, fuel economy reduction, low cetane, overall economics?
• Ethanol-based biodiesel—higher cost and lower esterification efficiency of ethanol versus methanol, but possible economic benefits with integration of ethanol and biodiesel production
• Ethanol-based ethers—use Guerbet catalytic condensation to produce butanol, convert to di-n-butylether: High cetane, lower pour point, reduce particulate emissions, what about NOx?
Aviation-Grade Ethanol (AGE)• AGE (about 87% ethanol, 12% petroleum, 1% biodiesel) is
high-performance alternative to leaded avgas• EPA wants to ban leaded avgas, but no economic alternative
developed in over 25 years of trying• At FAA request and in partnership with FAA, USDA,
ConocoPhillips, Textron Lycoming, and South Dakota Corn Growers, ongoing efforts to 1) evaluate AGE and 2) develop and achieve consensus approval of an American Society of Testing and Materials (ASTM) specification for AGE
• Current general aviation fuel market about 400 million gallons per year
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“…..back in the late 1980s, when I was employed by an oil company, I believed those laws {Clean Air Act and Energy Policy Act} were the stuff of lobbyists, tree huggers, and the granola crowd. Not anymore.”
J. Scott Susich, Advanced Energy Commerce, Inc., in Natural Gas Fuels, May 2003
Domestic Renewable Fuels—Changing Perspectives
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Contact: Ted Aulich
Energy & Environmental Research CenterPO Box 9018
Grand Forks, ND 58202-9018
Phone: (701) 777-2982Fax: (701) 777-5181E-mail: [email protected] Web Site: www.undeerc.org