Conversion of Woody Biomass to Chemicals, Energy and Materials Shijie Liu and Thomas E. Amidon Biorefinery Research Institute Department of Paper and Bioprocess Engineering SUNY College of Environmental Science and Forestry 1
Imagine a renewable world 2
Outline Introduction Hot-Water Extraction Wood Extract Hydrolysis Membrane Separation Fermentation Solid products Conclusion 3
Woody Biomass Chemical components of wood 21% hardwoods 25% softwoods wood Lignin extractives 2-8% carbohydrates 35% hardwoods 25% softwoods hemicellulose cellulose 45% 4
Wood Components: Inorganic Components K & Ca (400 ~ 1000 ppm); Mg & P (100 ~ 400 ppm) ; and 70 others Extractives Aliphatic and alicyclic: Terpenes; terpenoids; esters; fatty acids; alcohols; Phenolic: phenols; stilbenes; lignans; isoflavones; Others: sugars; cyclitols; tropolones; amino acids, Hemicellulose Lignin Cellulose 5
Incremental Deconstruction Maximize value achievable Minimize energy loss Minimize waste byproducts generation Multiple product mix 6
Integrated Biorefinery: Woody Biomass Hot-Water Extraction Residual Woody biomass Co-Gen or CHP Gasification Feedstock Extraction Liquor Unbleached Pulp Alkaline Puling Pulping Chemicals Fuel Pellets Reconstituted Wood Products Electricity and Steam Methanol Acetic Acid Hydrolysis / Separation Food additives: sugar oligomers Sugars Bleached Pulp Paper products or Cellulose products Black Liquor Carbohydrates Separation or Co-Gen Aromatics Plastics Adhesives Solvent Surface agents Xylitol Ethanol Butanol Acetone Hydrogen Lactic Acid PHA 7
ESF Biorefinery: Hot-Water Extraction Hydrolysis Fractionation Acetic Acid Methanol Sugars or monosaccharides Aromatics, Furfurals Polysaccharides Fermentation to Ethanol, Plastics, 8
Hot-Water Extraction 9
Maple Wood Extract Acetic Acid, Methanol Acetyl, Polysaccharides Aromatics, Furfurals Monomeric Sugars Conce entration, mm Methanol, mm 100 10 1 0.1 20 10 0 time, min. 0 50 100 150 200 Acetyl Aromatics Furfurals Starting conditions: 369.20 g OD Maple Woodchips 3024.04 g water, 28 C HOAc MeOH Sugars 0 50 100 150 200 time, min. 40 30 20 10 0 Acetic Acid, mm 10
Hydrolysis Depolymerize macromolecules (of carbohydrates) by inserting water molecules between the monomeric units Enzymatic hydrolysis Using a hydrolytic enzyme as catalyst Substrate specific only working with certain polymer and depolymerize at certain location Acid Hydrolysis Using acid (proton) as catalyst Glycosidic bond breakage, no specificity By-product dehydration reactions 11
Fractionation Solid-liquid separations Aromatics and/or degraded lignin recovery Xylan or xylo-oligomer recovery Catalyst recovery Liquid-liquid separations Membrane separations for Sugar stream purification Recovery of chemicals 12
Nano-Filtration Membrane System 13
Membrane Separation Resistances: Osmotic Pressure Friction Porous Solids Model: µ U p = π + U 1+ k a + U 2 2 bu 14
Flux versus Pressure 500 Permeate Rate, ml/min 400 300 200 100 0 40 60 80 100 120 140 160 Pressure, PSI 15
Osmotic Pressure Change 160 140 120 100 i π, psi 80 60 40 20 0 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 V 0 /V 16
Fractionation of wood extracts Time, minutes 0 60 120 180 240 300 360 15 C, g/l 10 5 Concentrate Stream 0 0.00 Permeate Stream 0.02 0.04 0.06 C, g/l 0.08 0.10 0 60 120 180 240 300 360 Time, Minutes 17
Acetic acid concentrations 0.18 0.16 0.14 0.12 C, mol/ /L 0.10 Concentrate Stream 0.08 0.06 0.04 Permeate Stream 0.02 0.00 0 60 120 180 240 300 360 Time, minutes 18
Separation Efficiency 1.05 1.00 Xylose 0.95 R s 0.90 Aromatic Compounds 0.85 0.80 0 60 120 180 240 300 360 Time, minutes 19
Separation Efficiency 0.5 0.4 0.3 Acetate Methanol Furfural HMF R s 0.2 0.1 0.0-0.1 0 60 120 180 240 300 360 Time, minutes 20
Fermentation Ethanol E. Coli Pichia Stipitis Butanol Clostridium acetobutylicum PHA 21
Residual woody biomass use Pulping paper and fiber products Fiber board reconstituted wood products Wood fuel wood pellets Biomass energy CHP Hydrolysis: cellulose conversion to platform chemicals Lignin conversion to chemicals and/or energy 22
Acknowledgements Christopher D. Wood Raymond Appleby Zhijie (Jeff) Sun Jennifer Putnam Alan Shupe Tingjun Liu Dave Kiemle Houfang Lu Kathryn Gratien Mitchell Graves Ruofei Hu Yang Wang others 23
International Biorefinery Conference October 6-9, 2009 24