All Biorefineries Are Regional Biodiesel Biogasoline BioFuels US: - PowerPoint PPT Presentation

The challenges and Opportunities for Next Generation of Forest Product Biorefineries Arthur J. Ragauskas School of Chemistry and Biochemistry Institute of Paper Science and Technology Georgia Institute of Technology

All Biorefineries Are Regional Biodiesel Biogasoline

BioFuels US: Currently Bioethanol 2% Biodiesel 0.01% 7000 U.S.A. Bioethanol 6000 MM Gal. Annual 5000 4000 3000 2000 1000 0 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2012 OH OH Today Today Amylase Amylase Yeast Yeast O O H 2 H 2 HO HO C C HO HO OH OH H 3 C H 3 C OH OH OH OH Acid Fermentation OH Catalyst O H 2 HO Future Biomass C HO or OH H 3 C OH OH O Enzymes HO HO Others OH OH

LignoCellulosics Bioresource OH OH O OAc O OAc O O OH O OH AcO O HO O O OH AcO O-Xylan HO O O O HO O HO O OAc O O HO O OAc O O O HO O O HO O O OH O HO O OH O HO O OH OH O OH OH HO O OH HO HO O HO OCH 3 Cellulose Cellulose HO O H 3 CO OH OH HO OH HO Polymer of Polymer of OH HO O β -(1,4)-glucan β -(1,4)-glucan OCH 3 DP: ~300 – 15,000 DP: ~300 – 15,000 H 3 CO HO O O OCH 3 HO HO OCH 3 Content: ~ 35 – 50% Content: ~ 35 – 50% HO OCH 3 Content: ~ 15 – 30% Content: ~ 15 – 30% HO O Major Global Major Global Content: ~ 20 - 30% Content: ~ 20 - 30% O HO Biopolymers Biopolymers OCH 3 Hemi Hemi O OCH 3 Lignin Lignin Cellulose Cellulose HO OH O OH OH Polymer Polymer Short chain Short chain H 3 CO O O O OCH 3 Derived from Derived from HO branched,substituted branched,substituted OCH 3 OH HO Coniferyl, Coumaryl, Coniferyl, Coumaryl, polymer of sugars polymer of sugars OH O HO Sinapyl, Alcohol Sinapyl, Alcohol DP: ~ 70 - 200 DP: ~ 70 - 200 OCH 3 HO O OCH 3 O OCH 3 O % ∼ Lignin BioResource Hemicellulose Cellulose Softwood 27 28 39 Hardwood 25 30 40 Corn Stover 18 22 38 Wheat Straw 23 21 38 Fine Paper - 20 80 Switch Grass 18 21 31

LignoCellulosic BioResources DOE

Forest Biorefinery Today’s Industry Situation • U.S. forest products industry is an important and vital segment of the nation’s economy – Is the world’s largest manufacturer of forest products – Directly employs over 1.3 million people – Ranks among the top ten manufacturing employers in 42 states – Estimated payroll of $50 billion. – Sales top $230 billion annually in the U.S. and export markets. • BUT… – Industry has not earned its cost of capital in a decade – Mergers and Acquisitions Forest Products – Return on Equity • Necessary for survival 1990 – 1995 • Won’t solve major problem

Forest Biorefinery Today’s Industry Situation World has Changed – Tropical pulp mills have advantage in the HW market – China is filling their needs Pulp and Paper Forum with modern, high-technology, low-cost mills 2005 – Competition from foreign- made products in the U.S. Techno-Business market is growing Innovation and Transfer • Two choices – Allow production (and supply chains) to migrate offshore – Introduce new line of products to provide significant growth

From Wood to Market Pulp Bleached pulp Wood Cellulose Lignin Cellulose + + Cooking bleaching stages Hemicellulose

Today’s Forest Products BioRefiner Kraft Pulping-Bleaching Products Lignin Thermal Energy -Lignin Cellulose - Carbohydrates Hemicellulose Paper - Carbohydrates Greenfield Mill: $1 – 2 Billion Collects: 650,000 tons of wood/year Generates: 350,000 tons of pulp US: 110 million tons pulpwood/year Lignin

Pulping Wood: Chemically Major Chemical Pulping Processes • Chemical wood pulp fibers are manufactured by chemically dissolving lignin from the wood liberating fibers. • Maximize lignin removal • Maximize carbohydrate retention • Kraft Process - 1879 in Germany • Harsh Conditions Softwood and Hardwood Kraft Pulping Conditions. Softwood Hardwood Active alkali on dry wood 17 - 21 % 14 – 18 % Liquor sulfidity (Na 2 S) 25 % 25 % Max. cooking temperature/ o C 170 170 Total cooking time/min 112 - 174 63 – 95 Kraft cook completed at lignin content 5 % 2 % 48 – 43 Yield 49 – 47

Today- Tomorrow’s Forest Products BioRefiner Energy Value-Added Bark Chemicals Biofuels Wood Wood Debarking Collection Wood Chipping Chemical Chips Markets Wood Extractives Proposed Hemicellulose Extraction Stage Extracted Woodchips Energy Wood Combustion of Pulping Pulping Chemicals Hemicellulose Chemical Pulp Sugars Waste Fermentation Pulp Bleaching Unbleached Pulp Papermaking Bioethanol Papermaking Current Products: Pulp, Tall Oil, Turpentine Future Select Hemicellulose

BioRefinery: Kraft Mill Opportunities Typical Wood Chemical Distribution for Wood Before and After Kraft Pulping Component Wood Components Kraft Pulp Components Pine Birch Pine Birch As a % of Original Wood Cellulose 38 – 40 40 – 41 35 35 Glucomannan 15 - 20 2 - 5 5 1 Xylan 7 - 10 25 – 30 5 16 Other carbohydrates 0 - 5 0 – 4 - - Lignin 25 - 30 20 – 22 2 – 5 1.5 – 3 Extraneous compounds 4 - 6 2 - 4 0.25 < 0.5 Typical kraft pulp mill will utilize ∼ 630,000 tons of wood/year Approximately 90,000 tons of hemicellulose/year are degraded

BioRefinery: Hemicellulose Extraction Research Background: Kraft pulping selectively degrades hemicelluloses . Carbohydrate Profile for Loblolly Pine Wood and Kraft Pulp. Source Glucose Galactose Mannose Xylanose Arabinose Wood 67.9 3.5 17.7 8.8 2.1 Pulp 84.9 0.3 7.1 7.1 0.5 Potential Process Benefits from Pre-Extracting Hemicelluloses Prior to Kraft Pulping Mayor Chemical Constituents of Wood. • Increased pulp production for recovery furnace limited pulp operations Wood Macromolecules a • Improved pulp properties due to enhanced cooking liquor impregnation in the wood chips Wood Species Cellulose (%) Lignin (%) Hemicelluloses (%) • Improved kraft cooking conditions requiring reduced cooking chemicals Softwoods Picea glauca 41 27 31 Abies balsamea 42 29 27 Pinus strobes 41 29 27 Tsuga Canadensis 41 33 23 Thuja occidentalis 41 31 26 Hardwoods Acer rubrum 45 24 29 Ulmus Americana 51 24 23 Populus tremuloides 48 21 27 Betula papyrifera 42 19 38 Fagus grandifolia 45 22 29 a all samples were analyzed extractives free

BioRefinery: Pre-Extraction Considerations ∼ 1600 post-pulping, ∼ 700 post-bleaching Cellulose DP: α -cellulose content > ∼ 80%, Hemicellulose: a decrease paper sheet strength properties occurs.

BioRefinery: Hemicellulose Extraction Overview of Experimental Plan Southern Loblolly Pine Chips Wood Chip Pre-extraction Control Acidic – Basic Kraft Pulping Pulp Yield Wood Chips Hemi-Extracts Fiber Properties Kraft Pulping Paper Properties Pulp Yield Hemi Yield Fiber Properties Lignin Yield Sheet Properties Hemi Composition

BioRefinery: Hemicellulose Extraction Experimental Pre-Extraction Conditions Loblolly Pine Experimental Alkaline Acidic Steam Parameter Pre-extraction Pre-extraction Pre-extraction Temperature/ o C 100 - 170 130 - 150 130 - 170 Time/h 0.5, 1.0, 1.5 0.5, 1.0 0.5, 1.0, 1.5, 2.0 1.0, 1.5% NaOH 0.0, 0.2, 0.5% H 2 SO 4 53 psi Chemicals/% Ratio of Liquor to 5.0 : 1.0 5.0 : 1.0 4.0 : 1.0 Wood Post Extraction No Yes & No No Washing

BioRefinery: Hemicellulose Extraction Kraft Pulping Steam Pretreated Woodchips: Approach O OAc O OAc O O OH O-Xylan AcO O HO O AcO HO OAcO OAcO O HO O O O O O O O HO O HO HO Steam < 3% Yield OH OH HO O HO HO OH O OH O OH O O OH O-Xylan HO O HO O HO OAcO HO OH O HO O O O O O O O O HO O HO HO OH OH HO O HO + HOAc HO OH

Acidic Pre-Extractions – Kraft Pulping

BioRefinery: Hemicellulose Extraction Acidic Pre-Extracted Woodchips: Monosaccharide Analysis Mass Terminal pH % Hydrolyzed % Recovery 50 Sugars 45 0.5 h 1.0 h 0.5h Pre-Extraction 40 Arabinose 0.0% H 2 SO 4 : 5 3.2 35 Galactose 0.2% H 2 SO 4 : 5 2.7 30 0.5% H 2 SO 4 : 8 2.3 Glucose 25 Xylose 1.0h Pre-Extraction 20 Mannose 15 0.0% H 2 SO 4 : 8 3.7 0.2% H 2 SO 4 : 10 2.4 10 0.5% H 2 SO 4 : 12 2.2 5 1-2 200 0 Fucose 175 Arabinos e 150 0 % 0.2% 0.5% 0 % 0.2% 0.5% Mannos e 125 H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 100 nC Galactos e Xylose 75 Glucos e 50 Yields 10 – 18% 25 0 0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 Minutes

BioRefinery: Hemicellulose Extraction Kraft Pulping Acidic Pre-Extracted Woodchips: Kappa #(Lignin Content 30 25 20 Kappa # 15 10 5 0 ) 4 4 4 4 g 4 4 g 4 g 4 4 n n O O n O O n O O O O O o i i i i h h S S S h S S S S S S t c s s 2 2 s 2 2 2 2 2 2 2 a a a a H H H H H H H H H r w w w t x % % % % % % % % % e t h h u 2 5 2 5 2 5 - t t i 0 i 0 o 0 e W . . W . . . . . 0 0 . 0 0 h . 0 0 r 0 0 0 p t / / i d d W o e e n t t / d ( c c l e a a o r r t r c t t t x x n a e e o r - - t C x e e r r e p p - e r r r h h p 5 0 r . . 0 1 h 0 . 1