1. Bioenergy Program Department of Forest Biomaterials

2. Faculty in Bioenergy Science and Technology Dimitris Argyropoulos Professor Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor Forestry Biotechnology Martin Hubbe Professor Surface Chemistry Stephen Kelley Dept Head & Professor Polymer Chemistry Adrianna Kirkman Professor Process Simulation Lucian Lucia Associate Professor Wood Chemistry Sunkyu Park Assistant Professor Bioenergy Process Richard Phillips Executive in Residence Bioenergy Economics Orlando Rojas Associate Professor Surface Chemistry Daniel Saloni Assistant Professor Process Development David Tilotta Associate Professor Wood Chemistry Richard Venditti Associate Professor Life Cycle Analysis Hasan Jameel Professor Process Engineering John Heitmann Professor Enzyme Biotechnology

3. 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

4. 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

5. 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

6. Background Concept inception October 2006 Ponderosa Consortium 2007 –Arborgen –BE&K Engineering –International Paper –Genencor –Metso Paper –Stone Smurfit –Syngenta –Weyerhaeuser –Xethanol 6

7. 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

8. Pulp and Paper - Base Case Mill 8

9. Ponderosa Asset Reuse 9 Lignin To Power Boiler

10. 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

11. Capital Costs 1 in $2009 11 1 BE&K Estimates based on file histories

12. Manufacturing Cost Enzyme at $0.30 per Gallon 12 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 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 Constant Wood +10% Wood 100% Pine + Residuals 100% HWD + Residuals

13. 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

14. WERC Consortium Used Ponderosa as guidance for second consortium aimed at simplification (currently in progress) –WERC – “Wood Ethanol Research Consortium” 14 2008 – 2009 American Process Arborgen Andritz BE&K Engineering Catchlight Energy/Weyerhaeuser Evolution Resources Nippon Paper/JPPRI NC State Natural Resources Foundation

15. 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 Simplification of Pretreatment

16. Summary PretreatmentSugar Recovery Autohydrolysis45% Acetic Acid Autohydrolysis73% Sodium Carbonate50% Green Liquor80% Autohydrolysis Green Liquor74% Acetic Acid Autohydrolysis- Green Liquor 79% Sodium Carbonate-Sodium Hydroxide68%

17. 17 Green Liquor Repurpose Case B10 Recovery Boiler Waste Treatment PM2 Sawdust Woodyard Brownstock Washers Screens PM1 Brownstock Washers Screens Evaporators Power Boiler Natural Gas Distillation Beer Column Fermentation Fiber Hydrolysis Prehydrolysis Cook Dehydration Ethanol Product Hydrolysate Cleanup ClO2 Generation Wood + Forest Residues Power Sales Lignin Recovery Lime Kiln Power Generation Causticizing Continuous Digester

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20. 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

21. Softwood Options in a Repurposed Mill Process Tot. sugar in pulp (% on wood) Sugar recovery (%) Softwood62.8 Basis on Tot. sugar in wood GL16-25S-17042.4 GL16-40S-17045.9 GL16-25S-170-R58.8 GL16-40S-170-R64.0 GL16-25S-170-O62.6 GL16-40S-170-O68.0 GL16-25S-170-O-R69.8 GL16-40S-170-O-R74.4

22. Hardwood Fiber, Enzyme Costs Critical to success Maintenance and Energy Cost next most critical 22 $1.79 per Gallon

23. Softwood Cash Costs better than Hardwood 23 $1.70 per Gallon

24. 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

25. Ethanol from Transgenic Hardwoods Sungrant (DOT) Evaluate potential for simplifying pretreatments for low/modified lignin hardwoods –Autohydrolysis –Ozone –Mild alkaline Figure 1. Effect of lignin content on glucose yield from wildtype and transgenic woods

26. 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

27. 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 Forest biomass 1.Hardwoods: Eucalyptus, poplar, mixed hardwood 2.Pine 3.Forest residues Agriculture biomass 1.Switch grass 2.Myscanthus 3.Coastal bermuda grass 4.Corn stover 5.Sugar beet 6.Arundo donax 7.Sweet sorghum

28. 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 Untreated AFEX treated Coastal Bermuda Grass Bales Bio-ethanol Pretreatment

29. 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

30. 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 Papermaking Sludges Negative feedstock cost Contains CaCO 3 and inorganics

31. 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 31 ETHANOL FERMENTATION WOOD CHIPS PULP & PAPER DIGESTER CHEMICALS

32. 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 CombustionWoody Biomass Hot Water Extraction Ethanol – Acetic Acid

33. Certain Ionic Liquids Can Completely Dissolve Wood Time Opportunities with Dissolved Wood for the Forest Biorefinery

34. Enhancing Wood Penetration for More Efficient Hydrolysis and Optimized Saccharification The metal (IrCp*)-cellulase complex is later recovered and the SOW (Surfactant Oil-Water) micro-emulsion may also be recycled Morphology of a microemulsion represented by a random bicontinuous structure or a Schwartz surface. = surfactant

35. 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 ProductionTransportationUseDisposal Raw Materials Energy Waste Emissions to air and water CORRIM Consortium for Research on Renewable Industrial Material

36. Validation of Therminator Syngas Cleanup 36 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

37. 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

38. 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