PyNe -- Innsbruck WP 2A Pyrolysis Biorefinery Doug Elliott September 28, 2005
Presentation Organization Biorefinery basics U.S. Department of Energy program Earlier PyNe efforts Other Biorefinery concepts 2
Important to Note: In both PRESENT and FUTURE biorefineries: Fuels production provides for large economies of scale Bio-based products, while smaller in volume, provide greater rates of return and drive profit 3
The Potential Role of Pyrolysis Part of a sugars-based biorefinery Part of a Petroleum Refinery Stand-alone facilities 4
An Example of a Current Biorefinery Corn Wet Mill corn gluten feed corn gluten meal starch corn oil hydrolysis glucose food & industrial starches food oils feed oils industrial oils glycerol hydrogenation fermentation foodstuffs pharma. sorbitol polyols isosorbide citric acid lysine xanthan gums itaconic acid & other fermentation products lactic acid PLA polymers fuel ethanol High fructose corn syrup Other sweeteners deicers solvents coatings resins & plastics applications polyesters surfactants pharmaceuticals T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005 5
Current Ethanol Process Corn Dry Grind Liquefaction Scarification Fermentation Centrifuge Triple Effect Evaporator Solids Liquids Solids Water Recycle Primary Distillation DDG Dryer 50% EtOH Distillation Rectifier DDG Animal Feed 95% EtOH Molecular Sieves 100% EtOH Ethanol T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005 6
Current Status of Ethanol Dry Mills Economics are difficult Current ethanol facilities are limited to only two products, ethanol and DDG Economics are highly dependent of value of the coproduct DDG Significant energy costs are associated with the drying of DDG Markets for DDG are not always favorable and will deteriorate as additional ethanol facilities come on line T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005 7
Strategies for Creating Additional Value Modify dry mills to include a quick steeping process that allows germ recovery Add an intermediate filtration process to recovery non-starch derived sugars (hemicellulose) Develop new fermentations for utilization of five carbon sugars (itaconic acid, succinic acid, etc) Develop new chemistry to produce value added products from hemi-cellulose (sugar alcohols, polyols) Include an energy component-pyrolyze DDG or modified DDG to produce bio-oil T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005 8
The Holistic Ethanol Facility Germ Corn Quick Steep Separation Scarification Oil Filtration Fiber Starch Fermentation Hydrolysis EtOH Ethanol 95% Recovery EtOH New DDG Animal Feed Molecular Sieves 100% EtOH Ethanol Pyrolysis Fermentation Itaconic Succinic, Etc Fuel/Power Catalytic Conversions EG, PG Glycerol, Etc T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005 9
Integrated Biorefinery Back of the Envelope Economics EtOH,, BDO, Oil, Lignin EtOH BDO Oil Lignin Overall Plant ROI 50 45 40 35 30 25 20 15 10 5 0 0 2122 Tons/Day $30/Dry Ton BDO @ $0.60/lb 7 3 6 11 3 9 15 3 10 22 3 11 29 3 12 37 3 13 44 3 14 % Lignin % Oil % Sugars Percent Feedstock Utilized T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005 10
The Present View of the Biorefinery Lignocellulosic Biomass Products Hydrolysis sugars Fermentation lignin Distillation Ethanol Fuel? D.J. Stevens, PyNe, 2005 11
The Present View of the Biorefinery Lignocellulosic Biomass Products Hydrolysis sugars Fermentation lignin Heat, electricity Distillation Ethanol Fuel Additional Biomass Gasification syngas Mixed Alcohol Synthesis Products (higher alcohols) D.J. Stevens, PyNe, 2005 12
Possible Future Biorefinery Lignocellulosic Biomass Products Hydrolysis sugars Fermentation lignin Heat, electricity Distillation Ethanol Fuel Additional Biomass Pyrolysis bio-oil Upgrading Motor Fuel D.J. Stevens, PyNe, 2005 Products 13
Hydrogenation Pathways with Ruthenium Catalyst H 3 C O CH 2 HO eugenol (propenylguaiacol) guaiacol methyl-guaiacol propyl guaiacol propylmethoxycyclohexanol propylcyclohexanediol methoxycyclohexanol propylcyclohexanol cyclohexanediol methylmethoxycyclohexanol methylcyclohexanediol D.C. Elliott, STCBC, September 2004 methylcyclohexanol HO cyclohexanol 14
price cost volume sales uses Cyclohexanol Market $0.81-0.83/lb from benzene ~$0.35/lb w/25% ROI 852 million lb (1972 est. U.S.) 6,400 million lb world (incl cyclohexanone)1992 20 million lb (incl cyclohexanone)1992 (most is used internally for adipic acid) adipic acid for nylon, esters for plasticizers, cyclohexanone for caprolactam, cyclohexylamine for emulsion stabilizer D.C. Elliott, STCBC, September 2004 15
The Potential Role of Pyrolysis Part of a Petroleum Refinery Biomass first would be converted to bio-oil, possibly at distributed locations at small scale Bio-oil can be partially upgraded by catalytic hydrotreatment at larger scale in proximity of a petroleum refinery Upgraded bio-oil then would be co-fed with petroleum feedstocks through a catalytic process to produce conventional refinery product slate The global petroleum industry is showing more interest From the Department of Energy perspective, this is a medium-term approach 16
Pyrolysis/Petroleum Biorefinery Lignocellulosic Biomass Fast Pyrolysis Products bio-oil Upgrading and Refining with Petroleum Motor Fuel 17
The Potential Role of Pyrolysis Stand-alone facilities Small size makes economics of fuel production difficult May be more appropriate for heat and power applications High-value specialty chemicals may provide the economic driver Unlikely to gain strong support from DOE in the U.S. because of current focus on petroleum displacement 18
Concept of a Biorefinery Fuel Gas Biomass Pyrolyzer Char Converter Bio-oil Anhydrosugars NH 3 lime alcohol water Hydrolysis & Fermentation Reaction Reaction Reaction Separation Ethanol Slow Release Fertilizers (N, Ca, Zn, Fe...) Noxolene (NOx reduction) BioLime (NOx/SOx reduction) Fuel Enhancers Flavor Chemicals Chemicals Flavors Adhesives Ash Activated carbon D. Radlein, Fast Pyrolysis Handbook, 1999 Separation Catalytic Reforming Diesel/boiler Fuel Specialty Synthesis Gas Hydrogen 19
Other Chemicals Produced from Bio-oil oil Wood Preservative (Ensyn patent) Road deicers (Waterloo patent) Resin formulations (many patents) Levoglucosan and Levoglucosenone Czernik & Bridgwater, Fast Pyrolysis Handbook 3, 2005 20
Integrated Pyrolysis Combined Cycle gas recycle char Biomass chemicals Bio-oil R.C. Brown et al. Iowa State University International Journal of Power & Energy Systems 24 (3) 2004 electricity gas and steam turbines 21
Forschungszentrum Karlsruhe in der Helmholtz-Gemeinschaft BACKBONE OF A BIOMASS REFINERY fossil other coal fuel:... starch, biomass: oil... Different biomass and carbon feedstock lignocellulosic biomass: wood, straw, hay... biomass preparation organic waste: paper, plastics, dung... special chemicals fast pyrolysis bio-oil/char -slurry rail transport from many pyrolysis plants to large, central plant for syngas generation and use pulverised coal coal/water slurry synthesis products: synfuel, chemicals, H 2 FW FW entrained flow gasification ~ 1200 C, 60 bar, τ 2-3 s gas cleaning with heat recovery liquid fuel synthesis single pass operation electricity generation CC turbine, engine, FC electricity low T heat co-generation of a marketable product mix O 2 CO 2 ITC-CPV HE
Industrial emitter of greenhouse gases The University of Georgia Biorefinery/Carbon Cycling Program NH 3 and CO 2 scrubbing media Hydrogen and Fischer-Tropsch Diesel Biorefinery Bio-Oil Biomass Stack emissions are converted to carbon based fertilizer vanillic acid acetic acid guaiacol phenol... carbon fertilizer back into fields E.D. Threadgill / P. Harrell, U. Georgia website 23
Summary Numerous opportunities involving: incorporation into sugar biorefinery incorporation into a petroleum refinery stand-alone with chemical, fuel, and power production incorporation into a gasification and synthesis plant Pyrolysis demonstration will lead to biorefinery Product separation and recovery is a major hurdle Finding the right niche is key 24