October, 2006 ESPRI / PBE Energy Outlook Life Goes On After Fossil Depletion Shijie Liu Faculty of Paper and Bioprocess Engineering & Empire State Paper Research Institute SUNY ESF 1 Forestry Drive, Syracuse, New York

From Woody Biomass to Chemicals and Energy ESPRI / PBE Outline n Energy Resources n Biomass Based Energy & Chemicals n Paper Industry –Near-term Application: Hot-water Extraction –Wood Extract Use –Alkaline Pulping & Fiber Quality –Black Liquor Gasification n Conclusion n Life Goes on After Fossil Depletion

From Woody Biomass to Chemicals and Energy ESPRI / PBE Energy Resources n Sun –Hydro, plants n Hydro and Geothermal Energy –Location –Environmental / ecological n Plants –Biomass –Animals n Coal, Petroleum n Nuclear Energy

From Woody Biomass to Chemicals and Energy ESPRI / PBE Energy Consumption : Quadrillion Btu / year YearRenewablesNonrewables U.S.A. World

From Woody Biomass to Chemicals and Energy ESPRI / PBE US Pulp and Paper Industry n Main raw material: forest wood n Accounts for 6.9% Coal, Oil, Gas and Electricity of all manufacturing industries n 1.3% total US fossil energy consumption n 1.1% of all US energy n 0.27% of the world energy diet

From Woody Biomass to Chemicals and Energy ESPRI / PBE Energy Resources ChemicalRecycle Time Algae Agricultural Crops Grasses Shrubs Trees Oil, Gas and Coal 1 Month 3 Months ~ 1 Year 1 Year 1 ~ 5 Years 5 ~ 80 Years 200 million Years

From Woody Biomass to Chemicals and Energy ESPRI / PBE Energy Resources n Availability –Quality –Technology n Reliability –Proximity –Stability n Affordability –Economical –Environmental –Societal Equivalence in energy wood to petroleum: $100 / ton  $34 / Barrel

From Woody Biomass to Chemicals and Energy ESPRI / PBE Environmental Impact USA Government: displacing 10% of the petroleum with biomass derived fuel and products by (DOE Vision for Bioenergy and Biobased Products in the United States, October 2002). Greenhouse gases (GHG) are increasing: in 2000, the atmosphere held about 774 Pg (774 billion metric tonnes) of carbon as CO 2, 369 vppm (Marland & Boden, 2001). The total will double by the end of this century if not controled. To stabilize CO 2 at about 550 vppm, it is necessary to reduce net GHG emissions. USA alone is expected to release 1.8 Pg of carbon in 2010 and 2.1 Pg of carbon in 2020, about 25% of the world total (EIA 2000). Most of current carbon emission is a direct result of the use of fossil fuels. SEEK NEW SUBSTITUTED FUEL derived from biomass Ethanol, butanol, acetone

From Woody Biomass to Chemicals and Energy ESPRI / PBE energy O2O2 CO 2, H 2 O (CH 2 O) n O2O2 Why Biomass?

From Woody Biomass to Chemicals and Energy ESPRI / PBE Pulp and Paper Industry n Unique Position Raw materials Material handling capacity Experience n Question to answer: Can wood be harvested and chipped when fossil energy had been exhausted?

Paper Industry Plant Biomass Volatile Extractives Lignin Hemicelluloses Cellulose Chemicals Energy Sugars Biodegradable Plastics Paper Ethanol Butanol Bio-Diesel

From Woody Biomass to Chemicals and Energy ESPRI / PBE Wood Composition n Inorganic Components K & Ca (400 ~ 1000 ppm); Mg & P (100 ~ 400 ppm) ; and 70 others n Extractives Aliphatic and alicyclic: Terpenes; terpenoids; esters; fatty acids; alcohols; … Phenolic: phenols; stilbenes; lignans; isoflavones; … Others: sugars; cyclitols; tropolones; amino acids, … n Hemicelluloses n Celluloses

From Woody Biomass to Chemicals and Energy ESPRI / PBE (phenols)

From Woody Biomass to Chemicals and Energy ESPRI / PBE Hemicelluloses n Hardwood: –Glucomannan –Glucuronoxylan (Xylan) n Softwood: –Galactoglucomannan –Arabinoglucuronoxylan (Xylan) n Xylan: Polymer of 5-Carbon Sugar

From Woody Biomass to Chemicals and Energy ESPRI / PBE Near-term Applications n Biorefinery n Extraction prior to Pulping n Fractionation of Wood Extracts n Fermentation n Black Liquor Gasification

From Woody Biomass to Chemicals and Energy ESPRI / PBE Wood harvesting Debarking Wood chipping Wood chips Pulping Extraction Hemicellulose Bioethanol Bleaching Papermaking Degraded Lignin and carbohydrates Bark Value-added chemicals Energy Butanol Lactic acid Biodegradable polymer Near-term Application

From Woody Biomass to Chemicals and Energy ESPRI / PBE Hot-Water Extraction n Abundant n Safety, Environmental, Reuse n Catalyst Use n Product Value n Product Separation

From Woody Biomass to Chemicals and Energy ESPRI / PBE Hot-Water Extraction Aspen Wood Glucan: 44.5% Xylan: 17.7% Galactan: 1.3% Arabinan: 0.5% Mannan: 1.7% Klason Lignin: 21.1% Others: 13.2% Residual Wood: 81.8% 44.7% Glucan 8.8% Xylan 0.0% Galactan 0.0% Arabinan 1.2% Manan 20.9% Klason Lignin 6.2% Others Wood Extracts: 18.2% 0.7% Glucan 9.1% Xylan 0.8% Galactan 0.4% Arabinan 0.6% Manan 1.1% Klason Lignin 5.5% Others Autocatalytic Extraction 150  C, 4.5h Data from: U. Tschirner, et al. (2006)

From Woody Biomass to Chemicals and Energy ESPRI / PBE Fractionation n Acetic Acid n Acetates n Hexoses, Pentoses n Oligomers n Methanol n Aromatics n Furfurals n Catalyst

From Woody Biomass to Chemicals and Energy ESPRI / PBE Ethanol Production n Anaerobic Fermentation: Sugar is Sugar C 6 H 12 O 6  2 C 2 H 5 OH + 2 CO 2 3C 5 H 10 O 5  5 C 2 H 5 OH + 5 CO 2 Theoretical yield: 51.14% (lb-ethanol/lb-sugar) n “Poly-glucose”: (Cellulose, glucomannan, …) HO(C 6 H 10 O 5 ) n H + (n–1)H 2 O  2nC 2 H 5 OH + 2nCO 2 Contribution of water adds to 56.82% n “Poly-xylose”: (Xylan) 3HO(C 5 H 8 O 4 ) n H + 3(n–1)H 2 O  5nC 2 H 5 OH + 5nCO 2 Contribution of water adds to 58.12%

From Woody Biomass to Chemicals and Energy ESPRI / PBE Effect of Hot-Water Extraction n Hemicelluloses removal –Uronic acid –Acetyl groups –Carboxyl groups –Metal ions n Lignin –Lignin-hemicellulose bonds –Active chemical agent access to lignin sites

From Woody Biomass to Chemicals and Energy ESPRI / PBE Alkaline Pulping & Fiber Quality n Mild cooking / bleaching conditions n Sulfur-free if desired –Environmental –Black Liquor Gasification n TCF ? n Low Hemicelluloses content –High Freeness for the same other indices –High SEC to reduce freeness n Fiber-Fiber bonding n Bulk

From Woody Biomass to Chemicals and Energy ESPRI / PBE Advantages n Bottom Line improvement n Environmental benign modification to existing processes enabling –Sulfur use on the way out –Chlorine, Chlorine Dioxide, on the way out –Value-added chemical and energy byproducts n Kraft Process?

From Woody Biomass to Chemicals and Energy ESPRI / PBE Conclusions n Biorefinery: a strategic direction to Energy and Chemicals n ESF Biorefinery: water-based technology n Pulp and Paper Industry Adaptation: Extraction; Fractionation; Fermentation; Pulping; Bleaching; Papermaking; Black Liquor Gasification

From Woody Biomass to Chemicals and Energy ESPRI / PBE Conclusions n Future depends on renewable energy and chemicals n Pulp and Paper Industry potential to play as a leader n Life will go on when fossil energy is depleted

From Woody Biomass to Chemicals and Energy ESPRI / PBE Life After Fossil Depletion n Automobiles Butanol; Propanol; Ethanol; Hydrogen n Airplane Butanol; Propanol; Hydrogen n Tractors, Combines, … Butanol; Ethanol; Bio-diesel n Cooking, Heating and Lighting Green power; Bio-gas; Bio-diesel; Bio-oil

From Woody Biomass to Chemicals and Energy ESPRI / PBE Acknowledgements n T.E. Amidon n G.M. Scott n R.C. Francis n B.V. Ramarao n Y.Z. Lai ESPRI SPPF PBE Staff ESF Colleagues, Students, and Research Fellows

ESPRI / PBE Thank You!