Bioenergy Program Department of Forest Biomaterials Faculty in Bioenergy Science and Technology Dimitris Argyropoulos Professor Wood Chemistry Hasan Jameel Professor Process Engineering Orlando Rojas Associate Professor Surface Chemistry Med Byrd Associate Professor Process Development Stephen Kelley Dept Head & Professor Polymer Chemistry Daniel Saloni Assistant Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang John Heitmann Martin Hubbe Professor Professor Professor Forestry Biotechnology Enzyme Biotechnology Surface Chemistry Adrianna Kirkman Professor Process Simulation David Tilotta Associate Professor Wood Chemistry Lucian Lucia Associate Professor Wood Chemistry Richard Venditti Associate Professor Life Cycle Analysis Sunkyu Park Richard Phillips Assistant Professor Executive in Residence Bioenergy Process Bioenergy Economics Bioenergy Projects • Wood-to-Ethanol Research Consortium • Value Prior to Pulping (VPP) • Ethanol from Transgenic Hardwoods • Ethanol from Coastal Bermuda Grass • Enhancing Wood Penetration for More Efficient Hydrolysis and Optimized Saccharification • Opportunities with Dissolved Wood for the Forest Biorefinery • Validation of Therminator Syngas Cleanup • Advanced Technology for Low Cost Ethanol from Engineered Cellulosic Biomass • Economics and Feasibility of North Carolina Biomass Conversion • Producing Ethanol from Biomass by Extracting Value Prior to Extraction • Low Cost Conversion of Industrial Sludges to Ethanol • Integrated Torrefaction-Gasification for the Production of Biofuels • Economic Analysis of Pine Biomass Varieties for Ethanol Production • Life Cycle Analysis for the Production of Transportation Fuels • Fast Pyrolysis of Forestry Biomass Wood to Ethanol Research Consortium (1) • Industry consortium of six companies • Repurposing a kraft pulp mill into a ethanol mill • Develop cost effective process by reusing existing assets Background • Majority of bioethanol in United States is produced from corn, none from wood – – – – Wood is competitive with corn in carbohydrate content with corn Cheaper raw material Capital cost to build large scale plant 2-3 X Corn Plant Increasing controversy over use of corn for fuel vs food • Demand for paper and board declining in United States – > 9 Million tons of capacity have permanently closed in United States since 2000 – Kraft pulp mills can potentially be repurposed to ethanol production 5 Background • Concept inception October 2006 • Ponderosa Consortium – – – – – – – – – 2007 Arborgen BE&K Engineering International Paper Genencor Metso Paper Stone Smurfit Syngenta Weyerhaeuser Xethanol 6 Advantages of Repurposing a Kraft Mill to Ethanol 1. Assets can largely be reused without serious compromise 2. Biomass supply chain in place to grow – harvest – deliver large amounts of wood 3. Low cost harvesting residuals frequently left behind in a kraft mill can be effectively used in ethanol production 4. Equipment in place is commercially proven and needs no additional development 5. Workforce in place, trained, likely motivated to succeed 6. Environmental permitting likely to straightforward 7 Pulp and Paper - Base Case Mill 8 Ponderosa Asset Reuse Lignin To Power Boiler 9 Repurpose Cases Considered • Repurpose A – Same wood volume by species and form as Base Case • Repurpose B1 – Same as Repurpose A + 10% • Repurpose B2 – Same as B1 except 100% Pine – no debarking + 15% Harvesting Residuals • Repurpose B4 – Same as B1 except 100% Hardwood – no debarking + 40% Harvesting Residuals 10 Capital Costs1 in $2009 Ethanol, Liters Repurpose B1 241,015,752 Repurpose B2 240,225,758 Repurpose B4 274,062,729 Repurpose B6 380,216,046 Repurpose B7 169,866,977 Repurpose B8 249,278,852 63,669,622 63,461,129 72,399,939 100,442,766 44,874,248 65,852,711 Ethanol, Gallons $ 1,191,000 5,475,960 $ 3,132,000 $ 1,611,522 $ 5,817,000 $ 3,290,436 $ 5,350,000 $ 172,721,000 $ 109,847,934 $ 155,340,324 17,212,000 $ 30,341,000 $ 12,857,326 $ 17,212,000 $ 3,480,000 $ 3,480,000 $ 3,480,000 $ 3,480,000 220,528,000 $ 225,944,000 $ 246,792,000 $ 136,563,000 $ 185,705,000 3.48 $ 3.12 $ 2.46 $ 3.04 $ 2.82 - $ - $ - 12,478,000 $ Continous Digester Modifications $ 12,296,000 $ 32,564,000 $ 32,564,000 $ 32,564,000 $ Hydrolysate Cleanup $ 1,762,000 $ 1,892,000 $ 1,879,000 $ 1,869,000 Additional Hydrolysis Retention $ 4,769,000 $ 5,178,000 $ 5,350,000 $ Alcohol Plant $ 150,127,000 $ 160,423,000 $ 165,459,000 Lignin Separation and Burning $ 16,100,000 $ 16,991,000 $ Bleach Plant Modifications $ 3,480,000 $ 3,480,000 Total $ 201,012,000 $ Capital Cost per Gallon Ethanol $ 3.16 $ 1 BE&K - $ Batch Digester Modifications $ Estimates based on file histories 11 - Manufacturing Cost Enzyme at $0.30 per Gallon Constant Wood +10% Wood 100% Pine + Residuals 100% HWD + Residuals • Hardwood cost per ton higher than softwood but ethanol yield is greater • Higher ethanol yield leads to lower Indirect costs Constant Wood • Cash Cost of Repurpose B4 – 100% Hardwood • $1.90 per Gallon Total Cash Cost • $0.25 per Gallon Energy Cost • $0.30 per Gallon Enzyme Cost • $0.61 per Gallon Biomass Cost +10% Wood 12 100% Pine + Residuals 100% HWD + Residuals Summary • • Repurposing existing Kraft Pulp Mill Promising: – Many practical advantages – Wood – to – Ethanol process with a potential Internal Rate of Return > 20% – Ethanol cash manufacturing cost ~ $1.60 per Gallon ($0.42 per liter) with enzymes at $0.30 per Gallon Requires simplification – Too many people on payroll due to complex process – Higher maintenance cost compared to corn – Distillation and fermentation costs high due to low sugar concentrations 13 WERC Consortium • Used Ponderosa as guidance for second consortium aimed at simplification (currently in progress) – WERC – “Wood Ethanol Research Consortium” 2008 – 2009 •American Process •Arborgen •Andritz •BE&K Engineering •Catchlight Energy/Weyerhaeuser •Evolution Resources •Nippon Paper/JPPRI •NC State Natural Resources Foundation 14 Simplification of Pretreatment • Pretreatment methods in a Repurposed Mill – Autohydrolysis (AH) • Acetic acid prehydrolysis (Hac) – Sodium Carbonate (SC) – Green liquor (GL) • Autohydrolysis/green liquor (AH-GL & HAc-GL) – Sodium Carbonate/Sodium Hydroxide Yongcan Jin Summary Pretreatment Sugar Recovery Autohydrolysis 45% Acetic Acid Autohydrolysis 73% Sodium Carbonate 50% Green Liquor 80% Autohydrolysis Green Liquor 74% Acetic Acid Autohydrolysis- Green Liquor 79% Sodium Carbonate-Sodium Hydroxide 68% Sugars as monomer Sugar Re cov ery Total carbohydra tes in wood Green Liquor Repurpose Case B10 Wood + Forest Residues Woodyard Prehydrolysis Cook Ethanol Product Waste Treatment Beer Column Distillation Dehydration Hydrolysate Cleanup Fermentation Fiber Hydrolysis Lignin Recovery Brownstock Washers Screens PM1 Brownstock Washers Screens PM2 Continuous Digester Lime Kiln Power Sales Sawdust ClO2 Generation Evaporators Causticizing Recovery Boiler Power Generation Power Boiler 17 Natural Gas 18 19 Use of Oxygen and Refining for Softwood • Oxygen delignification and refining can improve enzymatic hydrolysis – Both these unit operations may be available in a repurposed mill Softwood Options in a Repurposed Mill Process Softwood Tot. sugar in pulp (% on wood) 62.8 Sugar recovery (%) Basis on Tot. sugar in wood GL16-25S-170 42.4 GL16-40S-170 45.9 GL16-25S-170-R 58.8 GL16-40S-170-R 64.0 GL16-25S-170-O 62.6 GL16-40S-170-O 68.0 GL16-25S-170-O-R 69.8 GL16-40S-170-O-R 74.4 Hardwood Fiber, Enzyme Costs Critical to success Maintenance and Energy Cost next most critical $1.79 per Gallon 22 Softwood Cash Costs better than Hardwood $1.70 per Gallon 23 Commercialization Status • One consortium member negotiating to acquire 1-3 assets that have been shut down or in the process of being closed – Bastrop, Louisiana: Uncoated free sheet, high HW – Franklin, Virginia: Uncoated free sheet, high HW – Pineville, Louisiana: Linerboard, SW • Engineering studies are being conducted at one location with estimates of capital cost • Propose to start up in 1.5 years 24 Ethanol from Transgenic Hardwoods • Sungrant (DOT) • Evaluate potential for simplifying pretreatments for low/modified lignin hardwoods Samples Lignin S/G – Autohydrolysis – Ozone – Mild alkaline Wildtype TG96 TG141 23 24 11 Figure 1. Effect of lignin content on glucose yield from wildtype and transgenic woods Glucan 2.2 44 6.4 45 2.6 54 Advanced Technology for Low Cost Ethanol from Engineered Cellulosic Biomass • • • • USDA - DOE Demonstrate transgenic tree plantations with fast growing low lignin/high cellulose transgenic trees Demonstrate on a pilot scale the improved processability and economics, including simplified pretreatment strategies Economic evaluation of the different biomass and process options, using standard investment analysis techniques, including all applicable subsidies Economics and Feasibility of North Carolina Biomass Conversion • Indentify the most suitable and profitable scheme to produce ethanol in North Carolina with a complete analysis of the Supply Chain 70,000 Total acres Land investment ($) 70 66,999 60,000 60 50,249 50,000 50 Acres Agriculture biomass 1. Switch grass 2. Myscanthus 3. Coastal bermuda grass 4. Corn stover 5. Sugar beet 6. Arundo donax 7. Sweet sorghum 80 Acres to harvest 40,200 40,000 40 30,000 30 20,000 20 13,400 10,050 10,000 8,040 0 10 0 7.5 BDT/acre/year 10 BDT/acre/year 12.5 BDT/acre/year Land investment (Millions $) Forest biomass 1. Hardwoods: Eucalyptus, poplar, mixed hardwood 2. Pine 80,000 3. Forest residues Ethanol from Coastal Bermuda Grass • Develop simplified pretreatments for the conversion of coastal Bermuda grass to ethanol – – – – – – Autohydrolysis Sodium Carbonate Ozone Ammonia Explosion Microwave/NaOH Lime Pretreatment Bio-ethanol Coastal Bermuda Grass Bales Untreated AFEX treated Economic Analysis of Pine Biomass Varieties as Feedstock for the Production of Ethanol • • • • Characterize 178 pine varieties to identify those with varying lignin and cellulose content Select 20 varieties with different wood properties, and perform chemical and physical characterization of the wood properties Measure fermentable sugar yield using three pretreatments (dilute-acid, weak alkaline, organosolv) Compare feedstock value of different pine and poplar and recommend ideal loblolly pine feedstock Low Cost Conversion of Industrial Sludges to Ethanol • Biofuels Center of North Carolina • Demonstrate an effective technology to convert industrial papermaking sludge as a cost effective feedstock for the efficient biochemical biomass conversion to ethanol Negative feedstock cost Contains CaCO3 and inorganics Papermaking Sludges Value Prior to Pulping • DOE and Consortium of Companies and various research organizations and universities • Extract hemicelluloses prior to pulping and convert to ethanol and chemicals PULP & PAPER WOOD CHIPS DIGESTER CHEMICALS FERMENTATION ETHANOL 31 Producing Ethanol from Biomass by Extracting Value Prior to Combustion • Develop a process for hot water treatment of wood to extract the hemicelluloses. • Following extraction, the wood residue is sent to a boiler and burned as conventionally practiced Woody Biomass Hot Water Extraction Combustion Ethanol – Acetic Acid Opportunities with Dissolved Wood for the Forest Biorefinery Certain Ionic Liquids Can Completely Dissolve Wood Time recycling of IL’s Lignin Based Comodity Chemicals / Phenolics New Value –Added Materials Kraft Lignin Oxidative Dealkylation Wood Modification Fully Dissolved Wood & Components Wood Based Comodity & Speciality Chemicals/ Furanoids Component Fractionation Biofuels Liquid Wood Novel Exruded Wood Products Hemicellulose Cellulose Dimitris S. Argyropoulos Cellulose Fibers Enhancing Wood Penetration for More Efficient Hydrolysis and Optimized Saccharification 2+ H2O Ir OH2 Ir NO3 NO3 H2O Morphology of a microemulsion represented by a random bicontinuous structure or a Schwartz surface. = surfactant The metal (IrCp*)-cellulase complex is later recovered and the SOW (Surfactant Oil-Water) micro-emulsion may also be recycled Life Cycle Analysis for the Production of Transportation Fuels • Perform detailed material and energy balances on a set of biofuel manufacturing processes and feedstocks • Develop equipment and facility engineering plans for the processes/feedstocks • Perform a life cycle analysis on the processes/feedstocks and report the relative impacts of the different processes/feedstocks Raw Materials Energy Production Waste Energy Transportation Waste Emissions to air and water Energy Use Waste Emissions to air and water Emissions to air and water CORRIM Consortium for Research on Renewable Industrial Material Energy Disposal Waste Emissions to air and water Validation of Therminator Syngas Cleanup • US Department of Energy • Validate syngas cleanup technology (“Therminator”, RTI International) and syngas conversion unit operation • Integrate into the gasification process at the University of Utah • A fixed bed or slurry bubble column reactor will be integrated downstream of the “Therminator” to produce FT waxes from RTI’s proprietary iron-based catalyst 36 Integrated Torrefaction-Gasification for the Production of Biofuels • Turn woodchips into a substitute for coal by using a process called torrefaction that is greener, cleaner and more efficient than traditional coal burning. • Quantify relationship between time and temperature to produce torrefied wood • Use of torrefied wood for gasification • Scale up process to pilot plant evaluation • Economic and life cycle analysis of combine process Fast Pyrolysis Bio-oil from Forest Resources • • • • NSF I/UCRC (Industry/University Cooperative Research) 43mm fluidized bed reactor for fast pyrolysis Assess the quality of bio-oils produced from forest resources including forest residue, small diameter wood, and deconstruction materials Investigate statistical relationships between feedstock lignin content and specific bio-oil properties