Production fuel from cellulosic biomass

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1 Production fuel from cellulosic biomass Rick Gustafson School of Forest Resources 22 ctober 2009

2 Motivation for biofuels Climate Change

3 Biomass is renewable and can be carbon neutral

4 Corn ethanol Cellulosic ethanol Source: National Geographic

5 Motivation for biofuels Economic utilization Economic utilization of waste biomass

6 Motivation for biofuels Energy Independence

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8 Motivation for biofuels Expensive oil? Running out of oil? Peak il Is a Waste of Energy NY Times 24 August 2009 BP Finds Giant il Field Deep in Gulf of Mexico NY Times 2 Sept. 2009

9 Washington State Climate change mitigation Fires 33.5 M mt/2006 Figure Washington historic C2e emissions by sector with fire emissions superimposed (adapted from Waterman-Hoey and Nothstein 2007, Wiedinmyer and Neff 2007).

10 Climate change mitigation: C 2 emission goals relative to current emissions WA GHG Reduction Goals 2020 to to 75% to 50% 1990 Waterman Hoey and Nothstein Washington s Greenhouse Gas Emissions: Sources and Trends WA Dept. of Community, Trade and Economic Development. lympia, WA. 18 pp.

11 Current Market verview Current ethanol capacity = 10.6 billion gal/year Current biodiesel capacity = 700 million gal/year Source: Ethanol futures, $/gal

12 Energy Independence and Security Act 2007 (Now they aretalking about 60 billion gals/year!!!!) 40 Year) EPAct RFS Current Ethanol Production 2007 RFS - Conventional 2007 RFS - Cellulosic Biofuels 2007 RFS - Biomass-based Diesel 2007 RFS - Unaffiliated Renewable Fuel (B Billion Gallons per Estim mated Cellulosic Corn Total US oil consumption = 320 billion gals/year Total US oil imports = 220 billion gals/year

13 U.S. Biomass Resource Assessment Updated d resource assessment - April 2005 Jointly developed by U.S. DE and USDA Referred to as the Billion Ton Study Current biomass production less than 500 million tons/year 13

14 The BillionTon potential represents about1/3 of ourpetroleum use when converted to liquid fuels Billion Barrel of il Equivalents Based on RNL & USDA Resource Assessment Study by Perlach et.al. (April 2005)

15 Washington State situation is different Source: WSU, WA DE.

16 Replace oil with biofuels in Washington State??? 18 million tons of biomass available annually Assume 90 gallons fuel/ton biomass Total biofuel = 1,620,000,000 gallons/year Total WA oil consumption = 6,500,000, gallons/year

17 Range of Biorefinery Concepts Biomass Feedstock Trees Grasses Agricultural Crops Residues Animal Wastes Municipal i Solid Waste Conversion Processes Enzymatic Fermentation Gas/liquid Fermentation Acid Hydrolysis/ Fermentation Gasification Pyrolysis Combustion Co-firing Uses Fuels Ethanol Renewable Diesel Mixed Alcohols l Dimethyl Ether Power Electricity Heat Chemicals Plastics Solvents Chemical Intermediates Phenolics Adhesives Furfural Fatty Acids Acetic Acid Carbon Black Etc. Food and Feed 10/29/

18 Adapted from Holmgren etal (2008); Hydrocarbon Processing, Sep.

19 What is biomass made of? Representation of Cell Wall Components Cellulose Hemicelluloses Lignin

20 Cellulose For Chemists Very long straight chain polymer of glucose: approximately 10,000in a row in wood. Cotton is nearly pure cellulose. Cellulose molecules link up in bundles and bundles of bundles and bundles of bundles of bundles to make fibers Cellulose forms tight bundles which are very resistant to chemical attack Cellobiose Unit H H β CH 2 H H H β CH 2 H β CH 2 H H H β Cellulose CH 2 H 2 H H β

21 Hemicelluloses for Chemists Branched little uncolored sugar polymers (~ 50 to 300 sugar units) Composition varies between wood species 5 carbon sugars: s: xylose, yose,aab arabinose 6 carbon sugars: mannose, galactose, glucose Uronic Acids: galacturonic acid, glucuronic acid Acetyl and methoxyl groups (acetic acid & methanol) H H H H H H H H H 3 C C 2 H HH 2 C H H

22 Lignin for Chemists HC H 3 C H 3 C CH HC HC HH 2 C CH 2 H 4 HCH H 6 H CH HC CH 2 H 5 7 HC H 2 C H CH CH H 3 C CH 2 H 2 1 HCH HCH H 2 C C CH CH 2 H 3 H 3 C H 2 CH CH CH CH 3 CH 16 3 CH H 3 C HC H CH 3 HC HC H 2 C H 3 C H 3 C CH 3 CH 2 CH CH 8 15 H 3 C HC CH CH 2 H H 3 C H 2 CH HC HC 11 H 10 C CH CH 2 Carbohydrate CH 2 H HC 14 CH 13 CH 2 H CH H 3 C CH 9 H H 3 C H H 3 C CH HCH CH 3 CH 2 H 12 H 3 C 19 H 2 CH CH 2 CH 2 H 26 H 3 C H 2 CH HC CH 17 HCH CH 18 H 2 CH H H 2 CH CH CH CH H 2 CH H 2 CH HC HCH 23 HC CH 2 CH HC H 2 CH HCH 20 H HC HC CH 24 CH 3 H 2 CH H C 21 CH 3 H C CH 2 H CH 27 CH CH CH 22 CH 3 CH 3 CH 3

23 Chemical composition Feedstock Glucan (cellulose) (%) Xylan (hemicellulose) (%) Lignin (%) Corn stover Corn fiber Pine wood Poplar Wheat straw Switchgrass Chemical composition of biomass (adapted from Mosier et al., 2005).

24 Approaches to cellulosic biofuels Ethanol J.A. Dumesic / Catalysis Today 111 (2006)

25 Pretreatment Bioconversion of biomass to ethanol (hydrolysis) Liquid phase Sugars Eth l Ethanol Fermentation Biomass Solid phase Lignin Cellulose Recovery Hydrolysis Fermentation Sugars Ethanol

26 Pretreatment Schematic of goals of pretreatment on lignocellulosic material (adapted from Hsu et al., 1980).

27 Various pretreatment methods Increases accessible surface area Decrystalizes cellulose Removes hemicellulose Uncatalyzed steam explosion Liquid hot water ND Removes lignin Alters lignin structure ph controlled hot ND ND water Flow-through liquid ND hot water Dilute acid Flow-through acid AFEX ARP Lime ND Minor effect Major effect Adapted from Mosier et al., 2005

28 Pretreatment Bioconversion of biomass to ethanol (hydrolysis) Liquid phase Sugars Eth l Ethanol Fermentation Biomass Solid phase Lignin Cellulose Recovery Hydrolysis Fermentation Sugars Ethanol

29 Enzyme Function There are a large number of fungal enzymes responsible for the breakdown of each wood component. Each enzyme plays specific roles:» Endo beta 1,4 glucanase 14 a a e at acts within the chain, breaking it into smaller units and providing more ʺendsʺ for CBH.» Cellobiohydrolase (CBH), acts on the end of the molecule successively cleaving off the disaccharide cellobiose.» Beta glucosidase (or cellobiase) which cleaves cellobiose to two glucose units.

30 Cellulases Binding domain Catalytic domain Endoglucanases (EG) cutting the cellulose chains randomly Cellobiohydrolyses (CBH) cutting cellobiose units of the ends of the cellulose chains

31 Defined as: Fermentation Cellular metabolism under anaerobic conditions for the production of energy and metabolic intermediates Many organisms can ferment (i.e., grow anaerobically) Not all produce ethanol as an end product of fermentation» Butanol» Acetic acid» Propionic acid» Lactic acid

32 Thermoconversion - Basic Definitions Pyrolysis y Thermal conversion (destruction) of organics in the absence of oxygen In the biomass community, this commonly refers to lower temperature thermal processes producing liquids as the primary product Possibility of chemical and food byproducts Gasification Thermal conversion of organic materials at elevated temperature and reducing conditions to produce primarily permanent gases, with char, water, and condensibles as minor products Primary categories are partial oxidation and indirect steam 10/29/

33 Biomass Conversion to Fuels Major Biochemical Conversion Steps Feed Processing and Handling Size Reduction Storage and Handling De-watering Drying Gasification Pyrolysis y Gas Cleanup High T Separation Gas Conditioning Collection/Fractionation Fuel Synthesis Upgrading g Heat & Power Partial xidation Air blown xygen blown Indirect Flash pyrolysis Steam pyrolysis Vacuum pyrolysis Particulate removal Tar reforming Benzene removal S, N, Cl mitigation High T Filtration Alkali removal Methane reforming C 2 removal H 2 /C adjustment Sulfur polishing Aerosol collection Microfiltration Chemical Stabilization Hydrotreating Dehydration C1 chemistry FT liquids MTG Mixed H Upgrading Production Separation 10/29/

34 The distribution ib ti of products depends d on temperature t and residence time Liquid Char Gas FAST PYRLYSIS 75% 12% 13% moderate temperature short residence time GASIFICATIN 5% 10% 85% high temperature long residence time Source: Bridgewater and Czernik 34

35 Primary Energy Source Syngas Step Conversion Technology Products Natural Gas Syngas to Liquids (GTL) Process Fischer Tropsch Upgrading (FT) Diesel Naphtha Lubes Coal Syngas to Chemicals Technologies Syngas (C + H 2 ) Acetic Acid Biomass Methanol Hydrogen Extra Heavy il Mixed Alcohols (e.g. ethanol, propanol) thers (e.g. Triptane, DME, etc) 10/29/ Source: BP

36 Pyrolysis is usually performed at lower temperature to produce a liquid biocrude. Thermal decomposition occurring in the absence of oxygen Is also the first step in combustion and gasification processes Known as a technology for producing charcoal and chemicals for thousands years 10/29/

37 Biocrude is water miscible and is comprised of many oxygenated organic chemicals. Dark brown mobile liquid Combustible Not miscible with hydrocarbons Heating value ~ 17 MJ/kg Density ~ k kg/l Acid, ph ~ 2.5 Pungent odour Ages viscosity increases with time Source: Bridgewater and Czernik 10/29/

38 There are a number of applications for biocrudes Bio-oil Boiler Upgrade Extract Heat Chemicals Electricity Transport fuel Source: Bridgewater and Czernik 10/29/

39 Potential for mobile unit Upgrade biooil at refinery Forest Bioil Residuals Pyrolysis FREST Much cheaper to ship biooil than biomass because of higher energy density 39

40 Yields & Carbon Utilization Cellulosic Ethanol (BC) Cellulosic Ethanol (TC) Steam Cellulosic Ethanol (TC) PX Ethanol Corn Dry Mill Ethanol Sugar Cane Pyrolysis Fuel il Intermediate Methanol Intermediate Yield gal/ton biomass gal Ethanol eq/ton biomass By-Product type -- C 3+ H C 3+ H DDGS Sugar gal Ethanol eq/ton biomass wt% 5.7 wt% Electricity, kwh/ton External Fuel Nat Gas, MMBtu/dry ton 3.11 Process Efficency, HHV verall (Prod + Byprod) % Product % Carbon Utilization (basis - feed carbon) Product % By-Product % Acid Gas/Fermentation C2 % Combustion Flue Gas C2 % ther % Type char NG Flue Gas %

41 Plant Gate Prices 100 MMGPY EtH Production, $2005$ 10/29/

42 Novozymes Biochemical Various (Davis, CA) Genencor Biochemical Various (Palo Alto, CA) Ceres, Inc Various (Thousand aks, CA) Major DE Biofuels Project Locations Geographic, Feedstock, and Technology Diversity Pacific Ethanol Biochemical Wheat Straw, Stover, Poplar Residues (Boardman, R) DE Joint Bioenergy Institute (Berkeley, CA) Verenium Corp Biochemical Various (San Diego, CA) Emery Energy Thermochemical Corn Stover (Salt Lake City, UT) BlueFire Ethanol Biochemical Municipal Solid Waste (Mecca, CA) Nine Small-Scale Biorefinery Projects Montana State University Bozeman, (MT) Lignol Biochemical Woody Biomass- Ag Residues (Grand Junction, C) Abengoa Biochemica Agricultural Residue (Hugoton, KS) Cargill Inc Biochemical Various (Minneapolis, MN) Poet Biochemical Corn Cob/Corn Fiber (Emmetsburg, IA) Regents of the University of Minnesota Various Mascoma (Minneapolis, MN) Biochemical Mascoma Flambeau River Hardwoods Thermochemical (Upper Peninsula, MI) Forest Residues/Wood Waste Biochemical Various (Lebanon, NH) (Park Falls, WI) NewPage Cornell University Thermochemical DE Great Lakes (Ithaca, NY) Woody Biomass Mill Residues (Wisconsin Rapids, WI) Iowa State (3) University (Ames, IA) Bioenergy Research Center (Madison, WI) University of Maine (rono, ME) Gas Technology Institute (Des Plaines, IL) Stevens Institute of Purdue University Technology UP, LLC (West Lafayette, IN) (Hoboken NJ) Thermochemical Univeristy of (Des Plaines, IL) Toledo (Toldeo, H) Alltech Purdue University Biochemical Virginia Tech Biochemical Corn Cobs/Corn Fiber (Blacksburg, VA) (West Lafayette, IN) (Washington County, KY) ICM Biochemical Switchgrass, Forage Sorghum, Stover (St. Joseph, M) Southern Research Institute Thermochemical Various (Birmingham, AL) Georgia Tech (Atlanta, GA) DE Bioenergy Science Center (ak Ridge, TN) University of Georgia (Athens, GA) Range Fuels Thermochemical Woody Waste (Soperton, GA) RSE Pulp & Chemical, LLC Biochemical i Woody Biomass- Mill Residues (ld Town, ME) University of Massachusetts Amhers (Amherst, MA) GE Global Research (Niskayuna, NY) DSM Innovation Center Biochemical Various (Parsippany, NJ) Dupont Biochemical Various (Wilmington, DE) Research Triangle Institute (2) Thermochemical Woody Biomass (Research Triangle Park, NC) Four Commercial-Scale Biorefinery Projects Four Improved Enzyme Projects Five Projects for Fermentation rganisms Verenium Biofuels Corp. Biochemical Process Energy Cane and Bagasse (Jennings, LA) Five Thermochemical Syngas Projects Regional Partnerships Three ffice of Science Bioenergy Centers South Dakota State Univ., Brookings, SD DE Joint Solicitation Biomass Projects Cornell University, Ithaca, NY Univ. of Tennessee, Knoxville, TN Five Thermochemical Bio-il Projects klahoma State Univ., Stillwater, K regon State Univ., Corvallis, R Six University Projects Modified 10/1/2008