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Ancatalysis EFRC Funded Center by for the Energy U.S AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Presented by Dion Vlachos, Director Lead Institution: University of Delaware www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences CCEI’s Par tners Consists of 22 faculty researchers from 9 academic institutions UD team: 9 faculty Non-UD team: 13 faculty from 8 affiliated institutions 3 NAE members, 1 NAS member, 11 named professors, 4 junior faculty www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences CCEI Facu lty Mem bers Dion Vlachos, Stan Sandler Director Univ. of Delaware Univ. of Delaware Scott Auerbach George Huber Mark Snyder Paul Dauenhauer Univ. of Univ. of Lehigh University Univ. of Massachusetts Massachusetts Massachusetts Mark Barteau Mark Davis Bruce Koel Michael Tsapatsis Univ. of Delaware California Institute Lehigh University Univ. of Minnesota of Technology Aditya Bhan Doug Doren Jochen Lauterbach John Vohs Univ. of Minnesota Univ. of Delaware Univ. of Delaware Univ. of Pennsylvania HiHai Wang Douglas Buttrey Anatoly Frenkel Kelvin Lee Univ. of Southern Univ. of Delaware Brookhaven Univ. of Delaware National Lab California Jingguang Chen Raymond Gorte RlLbRaul Lobo Phillip Univ. of Delaware Univ. of Pennsylvania Univ. of Delaware Westmoreland Univ. of North Carolina www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences CCEI’s Mission the enabling science leading to improved or radically new heterogeneous catalytic technologies for viable and economic operation of biorefineries from various lignocell ul osi c bi omass f eed stock s the workforce needed to further develop and implement these new technologies techlhnology trans fer strategi illically via mul liti- institutional collaborations and joint ventures with industrial partners www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Major Research Goals biomass an d/or its d eri vati ves i nt o val uabl e chemicals, fuels and electricity through a fundamental understandinggyyp of the chemistry and catalyst performance novel hierarchical multiscale materials with nanoscale resolution suitable for processing derivatives from complex, multiphase media of biomass to ensure efficient, highly selective and benign processes cataldilyst design and dhl technology ad vancement through novel theoretical and multiscale simulation ppglatforms and cutting-edge characterization tools www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences GdChllGrand Challenges ¾ Lignocellulosic biomass decomposition (e.g., pyrolysis) leads to coking andthd the process is slow ¾ Complex feedstock renders fundamental studies difficult ¾ Biomass and its derivatives are over-functionalized molecules Selectivity is critical Chemical transformations require fundamental understanding of chemistry and catalyst performance (currently lacking) ¾ Processing of biomass derivatives occurs in a complex environment Low volatilityyyq and thermal stability require solution chemistry 9Typical supports (e.g., Al2O3, SiO2) dissolve in water 9Acid-based chemistry (e.g., HCl) is environmentally harsh 9MdldModels do not ex ist www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Research Thrusts Crosscutting Hierarchical Multiscale Characterization Research Multiscale Modeling Techniques Thrust Materials Reforming Technological H Platform 2 Furans Biomass Degradation/ Direct Carbon FCs Oil Upgrade CO+2H2/FT Chemicals Fuels Electricity Science Reaction Pathways, Kinetics, Structure-Property Relationships Processing Process Innovation, Optimization www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences CCEI First-Year Highlights ¾ Novel catalyst for the single pot conversion of glucose to HMF ¾ Computational engine for model-based bimetallic catalyst discovery applied to reforming technologies ¾ Defined surrogates of bio-oil ¾ Molten metal electrolyte-based fuel cells for the direct conversion of carbon to electricity www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences CCEI First-Year Highlights ¾ Novel catalyst for the single pot conversion of glucose to HMF ¾ Computational engine for model-based bimetallic catalyst discovery applied to reforming technologies ¾ Defined surrogates of bio-oil ¾ Molten metal electrolyte-based fuel cells for the direct conversion of carbon to electricity www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Chemicals: Objectives Develop technologies for production of chemicals and hydrogen or syngas from biomass derivatives (e.g ., sugars, glycerol, ethylene glycol, etc. ) Understand the reaction mechanisms Design active, selective, stable, and inexpensive catalysts that will enable effective and selective transformation of oxygenates to desirable products www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Chem ica ls: Su b-thrus ts ¾ Furans: Selective transformation of sugars to value-added chemicals, while retaining or increasing the number of carbon atoms e.ggg., isomerization of glucose to fructose; conversion of sugars to valuable chemicals, such as HMF, EMF, etc. Selective deoxygenation(mainly C-O bond scission; e.g., dehydration) and possibly hydrogenation Acid and base catalytic functional groups ¾ Reforming: H2 and syngas production Selective C-C bond scission (followed by dehydrogenation) Metal catalysis for hydrogenation and reforming www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Biomass Contains a lot of Glucose 100 90 80 70 60 Ash Uronic Acids 50 Extractives Lignin Hemicellulose 40 Cellulose / Algin 30 20 10 0 Corn Grain Corn Stover Cane Cane Pine Aspen Bagasse www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Tin-Containing Zeolite Beta for Sugar Isomerizations in Water by Manuel Moliner, Yuriy Roman-Leshkov, Eranda Nikolla & Mark Davis Chemical Engineering California Institute of Technology Pasadena, CA 91125 M. Moliner, Y. Roman-Leshkov, M.E. Davis, Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water. Proc. Natl. Acad. Sci., Vol. 107 ()(2010) 6164-6168. www.efrc.udel.edu AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Isomerization of Glucose to Fructose: Intermediate Step to Fuels and Chemicals Glucose isomerization is a crucial step in the efficient production of valuable chemical intermediates, such as 5-hydroxymethylfurfural (HMF) HYDROLYSIS ISOMERIZATION DEHYDRATION Starch HMF Glucose Fructose Combination of Acid Enzymes enzymes or acid treatment treatment Juben N. Chheda, George W. Huber, & James A. Dumesic, AngewandteChemie Int. Ed., 46 2007 A heterogeneous iiilisomerization catalyst thlhat can easily integrate glucose isomerization with the transformations of starting polymers of www.efrc.udel.edusugars and of fructose into fuels intermediates is lacking AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Isomerization of Glucose into Fructose by Immobilized Enzymes Isomerizationof glucose into fructose is the largest immobilized biocatalytic process worldwide for the production of high-fructose corn syrup (HFCS, 8 × 106 tons/year) Reaction slightly endothermic (ΔH=3 kJ/mol) and reversible (Keq ~ 1 at 298 K) Equilibrium mixture of 42% (wt/wt) fructose, 50% (wt/wt) glucose, and 8% (wt/wt) other saccharides using OH xyloseisomerase. H HO OH O H O H OH HO Products HO H H OH H OH HO H H OH Glucose (α-pyranose form) Fructose (α-furanose form) Starch-Starke. 2002.54, 75 H OH OH O HO HO H H H H OH www.efrc.udel.edu Mannose (α-pyranose form) AnCatalysis EFRC funded Center by for the Energy U.S. Department Innovation of Catalysis Center for Energy Innovation Energy Office of Basic Energy Sciences Isom eriz ati on of GGucoselucose into Fructose by Immobilized Enzymes Drawbacks 1) Pre-reaction purification processes to remove impurities that inhibit enzyme activity 2) Use of buffered solutions to maintain pH~7-8 (Na2CO3) and to activate the enzyme (MgSO4), requires post-reaction ion-exchange 3) Optimal
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