Challenge 2: Fargione et al; Land Use Change Penalty. CO 2 debt is created when land is cleared

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2 Green Gasoline at NSF ACS Green Chemistry and Engineering Conference University Park, MD John R. Regalbuto Catalysis and Biocatalysis Program Directorate for Engineering National Science Foundation June 25 th, 2009

3 Current Situation in Biofuels U.S. oil consumption = 7 billion barrels of oil a year DOE Billion Ton Study 1.3 billion tons of biomass sustainably available Forest waste Agricultural residue Energy crops (switch grass, short rotation poplar trees) Energy equivalent = 4 billion barrels of oil Converted at 50% efficiency: 2 billion barrels = about half of imported oil Even when light-duty vehicles go electric or plug-in hybrid, need diesel and jet fuel for planes, trains, trucks, boats

4 Current Situation in Biofuels Energy Independence and Security Act of billion gallons of renewable fuel by billion cap on corn ethanol Increase average gas mileage from 25 to 35 MPG Flex fuel: 25 MPG 18 MPG Renewable fuels must be exempted from CAFE increase Challenge 1: How to produce a renewable biofuel without incurring a loss in gas mileage.

5 Challenge 2: Fargione et al; Land Use Change Penalty CO 2 debt is created when land is cleared This CO 2 debt can be considerable: rainforest woods or thick grassland Will take a long time to repay if: land is heavily wooded payback is slow (soy based diesel, corn ethanol)

6 Avoidance of Land Use Change Penalty Use fallow/abandoned farmland and marginal land with high debtpaying energy crops: Lignocellulose: Switchgrass Sorghum Avoid land use change altogether: Forest waste Agricultural residue time banked" energy crops on marginal land (?) (?) forest waste and ag residue Optimal regime of operation Fargione et al: biofuels made from waste biomass or grown on abandoned lands planted with perennials incur little or no carbon debt

7 Challenge for Biofuels: Mass produce a renewable biofuel which incurs penalties in neither gas mileage or lifecycle greenhouse gas emissions. Utilization of existing fuel infrastructure (pipelines, refineries, engines) would be advantageous The Solution: Produce hydrocarbons from lignocellulose grown with minimal land use change

8 Roadmap for Hydrocarbon Production 2007 NSF/ENG and DOE/EERE Cosponsored Workshop in June, 2007 Workshop participants: 71 invited participants 27 academics from 24 universities 19 companies, small and large 13 representatives from 5 national labs 10 program managers (NSF, DOE, USDA) Workshops Goals: Articulate the role of chemistry and catalysis in the mass production of green gasoline, diesel and jet fuel from lignocellulose. Understand the key chemical and engineering challenges. Develop a roadmap for the mass production of next generation hydrocarbon biofuels. Final Report Released April 1, Input for Interagency Working Group on Biomass Conversion

9 The Catalyst: Heart of a Catalytic Converter NO + CO N 2 + CO 2 N N O Rh O C Pt Pt/Rh/Al 2 O 3 catalyst washcoat

10 Catalysts: Heart of Petroleum Refineries Fuels, Chemicals, Materials (Textiles)

11 forest waste switch- grass corn stover lignocellulose dissolution Biofuel Production Alternatives gasification to syngas (CO + H 2 ) pyrolysis, fast or slow gases bio-oil Fisher-Tropsch methanol Jet Fuel Diesel alga Sugar/Starch corn grain starch Lipids sugarcane soy beans saccharification liquid phase processing sugar hydrotreating transesterfication lignin fermentation Biodiesel Heat/Power Gasoline Ethanol butanol thermal routes catalytic routes biological routes synthetic biology

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13 DOE/SC/BES Funding Catalytic Partial Oxidation of Biomass to Synthesis Gas Joshua L. Colby, Paul J. Dauenhauer, Lanny D. Schmidt University of Minnesota Department of Chemical Engineering and Materials Science November,

14 Process Overview Chemistry Reactor Transport Heat Volatilization: (C 6 H 10 O 5 ) n Gases + VOC + Char Volatilization: (C 6 H 10 O 5 ) n Gases + VOC + Char Char O 2 Gases Char + O 2 Gases Fuel + O2 + Co-feed (C 6 H 10 O 5 ) n + O 2 + H 2 O Generation Conduction Convection Endothermic Oxidation: VOC + O 2 Gases Oxidation: VOC + O 2 Gases Reforming: VOC + H 2 O Gases Reforming: VOC + H 2 O Gases CO + H 2 O CO 2 + H 2 CO + H 2 O CO 2 + H 2 Global Chemistry: (C 6 H 10 O 5 ) n + O 2 + H 2 O CO + CO 2 + H 2 + H 2 O Catalyst Synthesis Gas Exothermic Endothermic 14

15 CPOx of Cellulose w/ Steam Biomass Drying/Grinding/Pretreatment Gasification One-Step Tars Catalytic Cleanup Gasification Water-Gas-Shift Synthesis CO + H 2 O CO 2 + H 2 Power Fuel Separation

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17 forest waste switch- grass corn stover lignocellulose dissolution Biofuel Production Alternatives gasification to syngas (CO + H 2 ) pyrolysis, fast or slow gases bio-oil Fisher-Tropsch methanol Jet Fuel Diesel alga Sugar/Starch corn grain starch Lipids sugarcane soy beans saccharification liquid phase processing sugar hydrotreating transesterfication lignin fermentation Biodiesel Heat/Power Gasoline Ethanol butanol thermal routes catalytic routes biological routes synthetic biology

18 Gasoline from Cellulose by Catalytic Fast Pyrolysis in a Single Reactor Cellulose Pyrolysis to Sugars, Adsorption into catalyst Glucose in ZSM-5 Catalytic Conversion Gasoline, CO 2, Water

19 Aromatic Selectivity 50 Selectivity (%) Glucose Cellobiose Cellulose Xylitol Benzene Toluene Xylenes, Ethylbenzene Methyl-ethylbenzene, trimethylbenzene Indanes Napthalenes

20 BCC = Biomass Catalytic Cracking CA-Biomass

21 KiOR connects the Biomass and Oil Industry Crude oil Bio Crude Bio-Crude compatible with refining streams (but no Sulfur, metals etc) Technology based on existing refining technology Compatibility with existing infra-structure lower entry barrier fast Time-To-Market! KiOR creates feedstock diversity for oil refiners!

22 Courtesy of Laurel Harmon, UOP

23 Lignocellulosic Biomass to Fuels Via Pyrolysis Corn Stover P P P Refinery P Deoxygenate Biomass Pyrolysis Mixed Woods P Stabilization P Biocrude Other Refinery Processes Gasoline Diesel Jet Chemicals Collaboration with DOE, NREL, PNNL JV with Ensyn 23UOP

24 Envergent s Commercialization Plan Biomass Pyrolysis Unit Green Electricity Available Now Corn Stover Fuel Oil Mixed Woods Stage 1 Upgrader Heating Oil Marine Fuels Timeline Stage 2 Upgrader Transport Fuels 2011 Rolling Deployment 24

25 forest waste switch- grass corn stover lignocellulose dissolution Biofuel Production Alternatives gasification to syngas (CO + H 2 ) pyrolysis, fast or slow gases bio-oil Fisher-Tropsch methanol Jet Fuel Diesel alga Sugar/Starch corn grain starch Lipids sugarcane soy beans saccharification liquid phase processing sugar hydrotreating transesterfication lignin fermentation Biodiesel Heat/Power Gasoline Ethanol butanol thermal routes catalytic routes biological routes synthetic biology

26 fermentation Oxygenated Fuels Ethanol/ Butanol Ethers DMF Jim Dumesic: Carbohydrates to Fuels dehydration/ hydrodeoxygenation aqueous phase reforming Alkane Fuels C 1 methane C 2 -C 4 LPG Carbohydrates aqueous phase reforming H 2 :CO 2 (process-h 2 ) gasification dehydration carbonyl formation reforming+ft synthesis Synthesis Gas (H 2 :CO) ketones/ aldehydes furfural compounds Fischer-Tropsch synthesis targeted alkane synthesis 1. C-C coupling 2. hydrogenation 3. dehydration/ hydrogenation C 5 -C 6 5 -C 12 gasoline C 9 -C 16 jet fuel C 10 -C 20 diesel fuel >C 20 wax Oxygenated Intermediates

27 Jim Dumesic: Science October Issue

28 Virent Energy Systems Overview Founded in 2002 by Dr. Randy Cortright and Professor Jim Dumesic from the Department of Chemical Engineering of the University of Wisconsin

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30 Cane Sugar to Green Gasoline

31 Green Gasoline Composition Same Components as Standard Unleaded Gasoline Unleaded Gasoline 115,000 BTUs/Gal Unleaded Gasoline Bioforming Green Gasoline Bioforming Green Gasoline 115,000 BTUs/Gal Ethanol 76,000 BTUs/Gal

32 forest waste switch- grass corn stover lignocellulose dissolution Biofuel Production Alternatives gasification to syngas (CO + H 2 ) pyrolysis, fast or slow gases bio-oil Fisher-Tropsch methanol Jet Fuel Diesel alga Sugar/Starch corn grain starch Lipids sugarcane soy beans saccharification liquid phase processing sugar hydrotreating transesterfication lignin fermentation Biodiesel Heat/Power Gasoline Ethanol butanol thermal routes catalytic routes biological routes synthetic biology

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37 Virent Shell: 100 MM GPY, Envergent (UOP/Ensyn): 100 MM GPY, 2011 for licens (major oils interested) KiOR (Petrobras): 100 MM GPY, 2011 Amyris - Crystalsev:?? MM GPY, 2011 Choren:?? MM GPY (Gasification/FTS) Saphire Oil (Algae): 100 MM GPY, 2016, 1 B GPY, 2022

38 Biofuels Funding Next Generation Hydrocarbon Biofuels have been written into the National Action Plan of the Biomass R&D Board Sec. Chu has testified to the priority of infrastructure-compatible compatible hydrocarbon biofuels NSF/ENG: EFRI Program FY 09 Hydrocarbons from Biomass ($14 - $16 million in 2009) Regular programs: Catalysis and Biocatalysis ($6 million/year) Energy for Sustainability ($10 million/year) Environmental Sustainability ($6 million/year) ERC: Center for BioRenewable Chemicals (CBiRC) ($17 million/ 5 years) DOE/Office of Science: 3-4 $20 million Energy Frontier Research Centers on advanced biofuels DOE/EERE/Office of Biofuels Program: $800 million in Recovery Funding for advanced biofuels

39 Summary Thoughts Green Gasoline vision: Cellulosic Gasoline Utilize existing corn EtOH plants for blending at E10 (15 billion gal/yr) With lignocellulose, make green gasoline, diesel, jet Feedstocks exist, conversion costs coming down Hydrocarbon biofuels from algae also possible Feedstock production costs still too high; conversion is cheap Recent indications: HYDROCARBON BIOFUELS ARE IMMINENT! Long range vision: Light vehicles: electric or plug in hybrid (much less demand for gasoline) Still need diesel and jet fuel for planes, trains, trucks, and boats Use biomass for 100% of liquid transportation fuels

40 Potential advantages of hydrocarbons Self-separation from water - no distillation required. Less energy input: lowers processing cost improves the C balance ~30% higher energy density; won t suffer a commensurate loss of gas mileage Reduction of water use Green gasoline/diesel/jet fuel fit into current infrastructure; no need for engine modifications or new distribution systems

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