Biomass Conversion Opportunities & Options

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Biomass Conversion Opportunities & Options Hawaii HCEI/DBEDT Biomass/ Biofuels Training Program John Ashworth and Scott Turn April 10, 2012 NREL is a national laboratory of the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy operated by the Alliance for Sustainable Energy, LLC

National Renewable Energy Laboratory Transportation Fuels

National Renewable Energy Laboratory Ethanol is the Most Mature Biofuel Technology

U.S. Biomass Resource Assessment Baseline Case Over 1 billion tons of biomass could be available annually in the future at $60/dry ton or less High Yield Case

Significance of the Billion Ton Scenario National Renewable Energy Laboratory Billion Barrel of Oil Equivalents

National Renewable Energy Laboratory Primary Biomass Conversion Routes to Liquid Fuels Transformation through Intermediates (sugars) Biochemical conversion Gasification (reduction to CO, H 2 ) and Pyrolysis Thermochemical conversion

Biofuels Transportation Options Biomass Feedstocks Lignocellulosic Biomass (wood, agri, waste, grasses, etc.) Ag residues, (stover, bagasse) Gasification Pyrolysis & Liquefaction Intermediates Syn Gas Bio-Oils Lignin Fermentation Catalytic synthesis FT synthesis MeOH synthesis HydroCracking/Treating Catalytic upgrading Transportation Fuels Ethanol & Mixed Alcohols Diesel* Methanol MTG Gasoline* Diesel* Gasoline* & Diesel* Sugar/Starch Crops (corn, sugar cane, etc.) Hydrolysis Sugars APP Catalytic pyrolysis APR Diesel* Gasoline* Hydrogen Fermentation Ethanol, Butanol, Hydrocarbons Natural Oils (plants, algae) Transesterification Hydrodeoxygenation Biodiesel Green diesel * Blending Products 7

National Renewable Energy Laboratory Transportation Fuels Biochemical Routes

Biofuels Transportation Options Biomass Feedstocks Lignocellulosic Biomass (wood, agri, waste, grasses, etc.) Ag residues, (stover, bagasse) Gasification Pyrolysis & Liquefaction Intermediates Syn Gas Bio-Oils Lignin Fermentation Catalytic synthesis FT synthesis MeOH synthesis HydroCracking/Treating Catalytic upgrading Transportation Fuels Ethanol & Mixed Alcohols Diesel* Methanol MTG Gasoline* Diesel* Gasoline* & Diesel* Sugar/Starch Crops (corn, sugar cane, etc.) Hydrolysis Sugars APP Catalytic pyrolysis APR Diesel* Gasoline* Hydrogen Fermentation Ethanol, Butanol, Hydrocarbons Natural Oils (plants, algae) Transesterification Hydrodeoxygenation Biodiesel Green diesel * Blending Products 9

National Renewable Energy Laboratory Near-Term Focus on Ethanol Near Term Long Term Ethanol as a blending agent from either grain or cellulosic material from Agriculture and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making low-sulfur diesel/gasoline in petroleum refinery Pyrolysis Liquids as a boiler fuel or an alternative feedstock to petroleum refinery or gasification facility; also a future source of aromatics and/or phenols Synthesis Gas for conversion to Fischer Tropsch liquids, MeOH/DME, or mixed alcohols Algae as alternative source of triglycerides for biodiesel or green diesel Hydrocarbons from hydrogenation of carbohydrates or lignin

Current Biofuels Status Biodiesel 173 Companies; 1.1 billion gallons of production (2011), 2.69 billion gallons/yr capacity Corn ethanol2 209 commercial plants operating 13.9 billion gal/yr. production (2011) Additional 1-2 billion gal/yr shut-in, planned or under construction Cellulosic ethanol (current technology) Projected commercial cost ~$2.50 /gallon Key DOE Goals 2012 goal: cellulosic ethanol $2.15/ETOH gallon 2022 goal: 36B gal Renewable Fuel; 21B gal Advanced Renewable Fuel 2007 Energy Independence and Security Act 2030 goal: 60 billion gal ethanol (30% of 2004 gasoline) NREL Research Thrusts The biorefinery and cellulosic ethanol Solutions to under-utilized waste residues Energy crops Updated January 2012 Sources: 1- National Biodiesel Board, 2 - Renewable Fuels Association, all other information based on DOE and USDA sources NATIONAL RENEWABLE ENERGY LABORATORY 11 Innovation for Our

The Problem National Renewable Energy Laboratory Corn Prices and Ethanol Prices are Decoupled the Example of 2006 Corn Prices Ethanol Production Cost (Nat Gas $4) Ethanol Production Cost (Nat Gas $7) Gasoline Rack Price Ethanol Contract Prices $4.00 $3.50 ($/gallon or $/bushel) $3.00 $2.50 $2.00 $1.50 $1.00 $0.50 $0.00 Jan Feb March April May June July Aug Sept Oct Nov Dec

National Renewable Energy Laboratory We Must Transition to Cellulosic Biomass Today & Near Term Corn Ethanol Biochemical Conversion Existing Distribution Infrastructure 2012 and Beyond Cellulosic Ethanol Agricultural residues, energy crops, natural oils, wood/forestry resources Advanced Biochemical Conversion and Thermochemical Conversion Expanded, Advanced Distribution Infrastructure Cellulosic ethanol will help meet future biofuels demand

Biomass Fractionation in Pretreatment National Renewable Energy Laboratory

Pretreatment Converts hemicellulose to fermentable sugars Makes cellulose susceptible to enzymatic hydrolysis National Renewable Energy Laboratory

Conversion of Biomass National Renewable Energy Laboratory 100 g raw solids (dry) feedstock 60 g pretreated solids (dry) cellulose + lignin 27 g residue solids (dry) lignin co-product

Enzymatic Hydrolysis Research NREL worked with Genencor and Novozymes for 4 years Focusing on enzyme biochemistry, cost, and specific activity Investigating the interaction of biomass pretreatment and enzymatic hydrolysis Result 20-fold reduction in cost contributions of enzymes ($/gal ethanol) E1 from A. cellulotiticus CBH1 from T. reesei $40 million R&D effort cost-shared by the Office of the Biomass Program and the enzyme manufacturers National Renewable Energy Laboratory

Fermentation National Renewable Energy Laboratory Introduced xylose utilization - 1994 Introduced arabinose utilization - 1995 Combined pentose utilization - 1997 Stabilization by integration - 1999 Development of Zymomonas Further Development in CRADA with DuPont 2002-2007

Significant Cost Reduction of Cellulosic Ethanol Resulting from R&D BC Conversion to Cellulosic Ethanol Historic State of Technology $10.00 $9.16 Conversion Feedstock $9.00 Bench Scale - Enzymes Minimum Ethanol Selling Price (2007$ per gallon) $8.00 $7.00 $6.00 $5.00 $4.00 $3.00 $2.00 $6.90 $5.33 $4.27 $3.85 Scale Up Pretreatment $3.64 $3.57 Scale Up Saccharification $3.18 $2.77 $2.56 $2.15 $1.00 $0.00 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Butanol (n, iso) Industrial Participants: Butamax (DuPont, BP), Tetravitae (now Eastman), Gevo, Cobalt, Butylfuel Green Biologics, etc Advantages (compared to ethanol): Higher energy content, More compatible with existing infrastructure Multiple higher-value markets, valuable platform intermediate for fuels (gasoline, jet) and commodity chemicals Disadvantages / Technical Challenges (in comparison to ethanol): Toxicity Yield Demonstrated largely on conventional feedstocks (corn starch, sugar) and less on biomass-derived sugars

Advanced biofuels from sugar Starch Sugarcane Sugar Fermentation Ethanol Cellulosics Aqueous-Phase Reforming Fermentation with engineered microbes Dark Algae Oil Gasoline Gasoline Diesel Diesel Biodiesel Jet Jet Diesel Virent Benefits Infrastructure-compatible Highly controlled fuel properties LS9, Amyris Solazyme Challenges Feedstock availability Compatibility with cellulosic sugar Lower yields (compared to ethanol), higher costs

National Renewable Energy Laboratory Transportation Fuels Thermochemical Routes

Biofuels Transportation Thermochemical Options Biomass Feedstocks Lignocellulosic Biomass (wood, agri, waste, grasses, etc.) Ag residues, (stover, bagasse) Gasification Pyrolysis & Liquefaction Intermediates Syn Gas Bio-Oils Lignin Fermentation Catalytic synthesis FT synthesis MeOH synthesis HydroCracking/Treating Catalytic upgrading Transportation Fuels Ethanol & Mixed Alcohols Diesel* Methanol MTG Gasoline* Diesel* Gasoline* & Diesel* Sugar/Starch Crops (corn, sugar cane, etc.) Hydrolysis Sugars APP Catalytic pyrolysis APR Diesel* Gasoline* Hydrogen Fermentation Ethanol, Butanol, Hydrocarbons Natural Oils (plants, algae) Transesterification Hydrodeoxygenation Biodiesel Green diesel * Blending Products 23

Other Near-Term Biofuel Technologies Near Term Ethanol as a blending agent from either grain or cellulosic material from Agriculture and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making low-sulfur diesel/gasoline in petroleum refinery Long Term National Renewable Energy Laboratory

Market Status of Biodiesel Roughly 2 billion gallon per year resource Market demand is leading to increased grease collection Potential for new oil-seed crops or increased oil content in conventional crops Corn oil recovery from ethanol production Longer-term, algae may provide a large feedstock resource Renewable Fuel Standard mandates 1 billion gallon market in 2012 More than 1.1 billion gallons produced in U.S. in 2011 Monthly Production, Million Gallons 100 80 60 40 20 0 Record volume in May 2011 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

Performance of Biodiesel Mature ASTM specification eliminates performance problems seen in the past 90+% of production volume meets ASTM requirements 80% of production today is from BQ-9000 companies Ensures B100 meets ASTM quality requirements Modern emission controls largely eliminate fuel effects on emissions No biodiesel effect on NOx, even for B100 in some tests Ongoing research to ensure no effect on catalyst durability B20 had impact on fuel economy for this car 2010 VW Jetta 2.0L TDI, DOC+DPF+LNT, Tier II Bin 5

Oils, Fats & Greases as Bio-Renewable Petroleum Refinery Feedstocks Oils and Greases ISBL Petroleum Refinery Catalytic Cracker Distillate Hydrotreater Green Gasoline & Olefins Green Diesel Co-processing of oils and greases with petroleum fractions Utilize existing process capacity Potential for lower conversion costs (than FAME) Higher quality diesel blending component G/D flexibility Based on Presentations at 1 st International Biorefinery Workshop, Washington DC, July 20-21, 2005 - Future Energy for Mobility, James Simnick, BP - From Bioblending to Biorefining, Veronique Hervouet, Total - Opportunities for Biorenewables in Petroleum Refineries, Jennifer Holmgren, UOP National Renewable Energy Laboratory

Market Status of Renewable Diesel Commercial production in US from poultry fat at one location 70 million gal/year capacity Meets ASTM specification for diesel fuel (D975) Hydrocarbon with very low oxygen, sulfur, and other impurities High cetane number Cloud point can be varied seasonally Pilot scale production from sugar (via biochemical route) Product is a single hydrocarbon compound Excellent diesel fuel properties Very low freezing point, potential use as jet fuel Smaller scale production from sugar (catalytic reforming) and biomass (fast pyrolysis/hydrotreating) We have not yet been able to test these materials 28

Performance of Renewable Diesel High cetane number and low aromatic content cause reduction in formation of NOx and fine particles High purity materials: No impact on catalyst durability Require additives for lubricity, conductivity, and corrosion protection as does conventional diesel Will typically be used as a blend component because of high quality Small reduction in fuel economy in some engines Lower btu/gal than petroleum diesel 29 NO x, Percent Change Relative to ULSD HDDT Cycle 2 0-2 -4-6 -8-10 -12 A RD20 A RD100 B RD20 B RD35 D RD20 D RD100 2008 Pickup Truck Engine, DOC-DPF, HD engine certification

Mid-Term Biofuel Technologies Near Term Ethanol as a blending agent from either grain or cellulosic material from Agriculture and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making lowsulfur diesel/gasoline in petroleum refinery Pyrolysis Liquids as a boiler fuel or an alternative feedstock to petroleum refinery or gasification facility; also a future source of aromatics and/or phenols Long Term National Renewable Energy Laboratory

Fast Pyrolysis and Bio-Oil as Feed to Power Plant or Petroleum Refinery National Renewable Energy Laboratory Bio-oil is comprised of many oxygenated organic chemicals, with water-miscible and oil-miscible fractions Dark brown mobile liquid Based on research at NREL (1990-2006) Combustible Not 100% miscible with hydrocarbons Modest heating value ~ 17 MJ/kg High density ~ 1.2 kg/l Acidic, ph ~ 2.5 Pungent odor Ages viscosity increases with time

National Renewable Energy Laboratory Mid-Term Biofuel Technologies Near Term Long Term Ethanol as a blending agent from either grain or cellulosic material from Agriculture and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making lowsulfur diesel/gasoline in petroleum refinery Pyrolysis Liquids as a boiler fuel or an alternative feedstock to petroleum refinery or gasification facility, also a future source of aromatics and/or phenols Synthesis Gas for conversion to mixed alcohols, Fischer Tropsch liquids, MeOH, or DME

Gasification Offers Many Feed & Product Options National Renewable Energy Laboratory Primary Energy Source Syngas Step Conversion Technology Products Natural Gas Syngas to Liquids (GTL) Process Fischer Tropsch (FT) Upgrading Diesel Naphtha Lubes Coal Syngas to Chemicals Technologies Syngas (CO + H 2 ) Acetic Acid Biomass Methanol Hydrogen Extra Heavy Oil M ixed Alcohols (e.g. ethanol, propanol) Others (e.g. Triptane, DM E, etc) Slide courtesy of BP Corporation

Advanced biofuels from synthesis gas Methanol Dry Organic Material Syngas gasification Mixed Alcohol Synthesis Ethanol Cellulosics Propanol+ Fischer-Tropsch Synthesis Methanol Synthesis Fermentation Gasoline Diesel Methanol-to- Gasoline Ethanol Jet Solena, Choren Gasoline Coskata, INEOS Benefits Product versatility Proven technology Challenges Biomass collection radius dictates smallish plant size Limited economy of scale

National Advanced Biofuels Consortium Project Objective Develop cost-effective technologies that supplement petroleum-derived fuels with advanced drop-in biofuels that are compatible with today s transportation Consortium Leads Pall Corporation infrastructure and are produced in a National Renewable Energy Laboratory Pacific Northwest National Laboratory sustainable manner. Consortium Partners Albemarle Corporation Amyris Biotechnologies Argonne National Laboratory BP Products North America Inc. RTI International Tesoro Companies Inc. University of California, Davis UOP, LLC Virent Energy Systems Washington State University Catchlight Energy, LLC ARRA Colorado School of Mines Funded: - 3 year effort Iowa State University - DOE Funding $35.0M - Cost Share $12.5M Total $47.5M Los Alamos National Laboratory 35 NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

Integration With Existing Fuels Infrastructure National Advanced Biofuels Consortium (NABC), www.nabcprojects.org Biomass Refinery-Ready Intermediates Finished Fuels and Blendstocks Insertion Point #1: Insertion Point #2: Insertion Point #3: Crude Oil Atmospheric and Vacuum Distillation Gas L Naphtha H Naphtha LGO VGO Atm. Res. Vac. Res. Reform FCC Alky/Poly HT/HC Coker Gasoline Jet Fuel Diesel Fuel Existing Refinery Infrastructure 36

Mid-Term Biofuel Technologies National Renewable Energy Laboratory Near Term Long Term Ethanol as a blending agent from either grain or cellulosic material from Agriculture and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making lowsulfur diesel/gasoline in petroleum refinery Pyrolysis Liquids as a boiler fuel or an alternative feedstock to petroleum refinery or gasification facility, also a future source of aromatics and/or phenols Synthesis Gas for conversion to mixed alcohols, Fischer Tropsch liquids, methanol, or dimethyl ether Algae to Fuels either to biodiesel or as a lipid source for green diesel or synthetic gasoline Hydrocarbons from hydrogenation of carbohydrates or lignin

A Novel Approach for Making Jet Fuel from Biomass Combine two technologies: Algae & Green Diesel National Renewable Energy Laboratory Microalgae 60% Triglyceride CO 2 Cultivation Ponds 40% Carbohydrates and Protein Jet Fuel (JP-8) Ethanol Power Food Green Diesel

Thank you for the opportunity. National Renewable Energy Laboratory Are there any questions?