Helsinki University of Technology Innovative Forest Products Biorefinery Adriaan van Heiningen and Tapani Vuorinen Helsinki University of Technology Department of Forest Products Technology Espoo, Finland III Liekkipaiva Espoo, January 31, 2007
Outline Future of the forest products industry Biorefinery approach Conversion strategy for hemicelluloses Value-added/ODMT wood in biorefineries Projects at HUT Conclusions
Inflation Corrected Price of Northern Bleached Softwood Kraft Pulp
Pulp/Paper Capital Spending in N.A. Facilities are not maintained below 75% expenditures (Kinstrey,R, Pulp and Paper. January 2004)
Pulp and Paper Industry Challenge Due to global competition, pulp and paper prices will continue to decrease. Wood/biomass cost is correlated with energy cost, so feed stock price is increasing Profitability is squeezed from both sides Traditional forest products industry needs more revenue from higher valueadded products besides wood, pulp and paper products
How to Increase Revenue? Maximize pulp production Make ethanol, chemicals and polymers from hemicellulose Make transportation fuel from lignin Use bark and biomass as fuel for pulp mill Forest Biorefinery which produces pulp, paper and chemicals, fuels and polymers
Ultimate Biorefinery for Ligno- Cellulosics Goal: Clean fractionation in cellulose, lignin and hemicellulose, followed by further processing of these components into chemicals and materials Solvent choice: biomass contains water; water removal efficiency of multiple effect evaporation much more efficient than solvent distillation; use aqueous system as solvent Proven and versatile fractionation process for all ligno-cellulosics is kraft pulping. It yields fairly undegraded cellulose; however large fraction of hemicellulose is extensively degraded
Approach for Hemicelluloses Hemicelluloses: - have low fuel value - are valuable in pulp - degrade during pulping - undegraded sugars needed for biofuels and chemicals Extract hemicelluloses before pulping
How to Obtain Undegraded Hemicelluloses? Extraction of hemis as polymers before pulping Extract with water and chemicals which are compatible with the kraft process Minimize the amount of additional water introduced in the pulping process Hardwood and softwood need different approaches because their hemicelluloses are chemically different
Pulping Benefits of Hemicellulose Extraction Decreased alkali consumption Reduced organic + inorganic load to recovery Increased delignification rate Increased pulp production rate
Value of Cellulose Pulp Fibers Maximum theoretical yield of ethanol from cellulose pulp on weight basis is 50% Ethanol price must be at least > $1000/MT ($3.00/gallon) for economical conversion of cellulose ($500/MT) into ethanol Cellulose has high crystallinity, is durable and has unique structural properties Pulp is more valuable than ethanol. Keep pulp as product in paper or structural products
Fuel Costs in Forest Biorefinery Fuel Heating Value (GJ/MT) Fuel Cost (US$/Dry MT) Energy Cost (US$/GJ) Oil 43.5 555 Biomass (20% moisture) Black Liquor (20% moisture) (US$60/barrel) 11.8 15 55 3.7 12.6 75 x 3/4 = 56 (org/inorg = 3/1) Lignin 26.9 75 2.8 Carbohydrates 13.6 75 5.5 4.4 Do not use oil! Obtain energy from biomass and/or black liquor! Minimize use of carbohydrates for energy purposes
Biomass (bark, etc.) Biomass Gasifier Power + Steam IFPR Trees Solid Wood Wood Fiber Wood Modification Wood Composite Legend Wood Extraction Raw Wood Extract Synthesis Gas Diesel Fuel = Existing Products White Liquor (NaOH + AQ) Alkaline Pulping Black Liquor Black Liquor gasification High Pressure Steam Electric Power = Existing Processes = New Processes = Νεω Προδυχτσ Carbon Fibers Oxygen Delignification NaOH Ethanol Pulp Bleaching Wood Extract Conversion Wood Extract Filtrate Sugarbased Polymers Bleached Pulp
Hemicellulose Conversion Strategy Produce oxygen containing products to increase yield, shorten conversion path and competitiveness relative to petroleum-based Thus, produce alcohols, carboxylic acids, lactones, and esters Bio and catalytic conversions must work for both C5 and C6 sugars
Present situation Maximizing Value Product Price ($/ODMT) Yield (%) Value (US$/ODMT wood) Pulp 500 45 225 Wood as fuel 55 55 30 Total 100 255 Value-Added: 255 75 = 180 US$/ODMT wood Future Situation Product Price Wood Yield (%) Conversion (%) Value (US$/ODMT wood) Pulp $500/ODMT 45 100 225 Polymer $3000/MT 10 50 150 PU foam $3000/MT 10 45 135 Diesel $630/MT $2.00/gallon 35 40 88 Total 100 598 Value-Added: 598 75 = 523 US$/ODMT wood
Development Challenges Maintain yield an quality of pulp Selective and economic pre-extraction of hemicellulose polymers Efficient and high yield conversion of extract into ethanol, chemicals and polymers. Efficient and economic purification processes Integration with beneficial effects on pulp production Demonstrate pressurized kraft black liquor gasification at the mill scale
Projects at HUT Extraction Kinetics of Hemicelluloses High Temperature Degradation Kinetics of Black Liquor in the Liquid Phase
Extraction Kinetics of Hemicelluloses Variables: Wood type: ph control: Equipment: Analysis: T, t, ph, ultrasound birch and pine CO 2 /HCO 3- /CO 2-3 buffers Berty type CSTR - on-line UV and RI - off-line TOC, TIC, TN, MeOH, HAc, sugars - extracted wood composition - reducing ends in extracted wood
Berty CSTR Cold Water BFP Heat Exchanger UV spectro. Flow Indicator Needle Valve 280 ml Reactor with a 100 ml basket CO 2 Heating O 2 Gas Liquor tank Computer Domain Controller Controller
Berty Stationary Basket Reactor 2-inch inside diameter and 2-inch height basket Maximum 5800 psig, 343ºC basket volume is 100 ml and the free volume is 280 ml Autoclaveengineers Co.
Setup at UMaine
Collaborations? Antti Grönroos, VTT Jyvaskyla Pertti Koukkari, VTT Espoo Liisa Viikari, University of Helsinki Kari Saviharju, Andritz Oy Others?
Degradation Kinetics of Black Liquor in Liquid Phase Variables: T, t, ph Black liquor: Pine kraft Equipment: Multiple small batch reactors Analysis: - Pressure - Gas composition incl. TRS + NOx - Liquor composition + properties
Collaborations? Pat McKeough, VTT Jyvaskyla Raimo Alen, University of Jyvaskyla Carl-Johan Fogelholm, HUT Miko Hupa, Abo Akademi Kari Saviharju, Andritz Oy Others?
Conclusions Benefits of Forest Biorefinery: Protects the Core: Increases the profits in support of traditional forest products production Ecofriendly: Transportation fuels, power, and bioproducts from a carbon-neutral, renewable resource Low Capital: Use existing pulping equipment and infrastructure for production of new, high value-added products besides traditional wood and paper products Synergy: Full integration of the traditional forest products and new bioproducts will lead to synergies Self-Sufficiency: Replacement of imported fossil fuels by domestic renewable fuel Employment: Preserves and creates jobs in rural forestbased communities
Coproducts Pulp + Transportation Fluids Pulp Production Product Price ($/ODMT) Yield (%) Value (US$/ODMT wood) Pulp 500 45 225 Wood fuel 55 55 30 Total 100 255 Value-Added: 255 75 = 180 US$/ODMT wood Pulp and Transportation Fluids Coproduction Product Price Wood Yield (%) Conversion (%) Value(US$/ODMTwood) Pulp $500/ODMT 45 100 225 Ethanol from hemi Diesel $670/ODMT $2.00/gallon $630/ODMT $2.00/gallon 10 43 29 45 40 113 Total 100 367 Value-Added: 367 75 = 292 US$/ODMT wood
What Products? (Mike Pacheco, NREL)
Examples of Potential Hemicellulose-Derived Chemicals Ethyl levulinate, a diesel additive. Made from esterification of levulinic acid with ethanol 1,3 propane diol, the monomer for Dupont polyester Sonomo made from this diol and phtalic anhydride. Diol is made from HPA. Poly-itaconic acid. Made from sugar monomers by fermentation and then polymerization. Engineered wood products. Use of the new unsaturated polymers in wood composites (for example polypropylene fumarate?) 1,2 propylene glycol. Non toxic anti freeze