Ethanol: Fuel or Chemical Intermediate

1. Ethanol Market Opportunities Beyond GasolineGovernors’ Ethanol Coalition MeetingAugust 1, 2003, Sioux Falls, South DakotaPresenter: Ted AulichUniversity of North DakotaEnergy & Environmental Research CenterGrand Forks, North Dakota

2. 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

3. 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

4. Corn Dual Fermentation Biorefinery Saccharification (amylase) Hydrolysate Glucose Ethanol Process Carboxylic Acid Process Bacterial Fermentation Yeast Fermentation Distillation and Evaporation NH4OH Dehydration Ammonium Ethanol Lactate/Succinate Distillation and/or Product Esterification Tower Pervaporation Vapor Excess Ethyl Ethanol Fuel Ethanol Lactate/Succinate Optional Optional Lactic Acid Succinic Acid

5. 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

6. Dual Fermentation Product Options(Partial List) Price, $/pound Fuel ethanol 0.19 Lactic acid 0.79 Succinic acid 2.70 Ethyl lactate 1.00 Ethyl succinate ?? Ethyl butyrate 2.00 Ethyl acetate 0.60 Methyl acrylate 0.85 (from methyl lactate)

7. Guerbet Catalytic Condensation(Ethanol-Based) Catalytic Ethanol Condensation Butanol and Ethanol Distillation and Catalytic Butanol Dehydration Condensation 2-Ethylhexanol

8. Guerbet Catalytic Condensation(Methanol- and Ethanol-Based) Catalytic Ethanol Condensation + Methanol Isobutanol or Propanol and Ethanol + Methanol Distillation and Isobutanol or Propanol Dehydration

9. 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

10. Catalytic Condensation Product Options(Partial List) Price, $/pound Fuel ethanol 0.19 Propanol 0.65 Butanol 0.48 Isobutanol 0.45 2-Ethylhexanol 0.48 Isobutyl acrylate 0.95 (from isobutanol and methyl acrylate)

11. 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

12. 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

13. 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?

14. 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

15. Domestic Renewable Fuels—Changing Perspectives “…..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

16. Contact: Ted Aulich Energy & Environmental Research Center PO Box 9018 Grand Forks, ND 58202-9018 Phone: (701) 777-2982 Fax: (701) 777-5181 E-mail: taulich@undeerc.org EERC Web Site: www.undeerc.org