Catalytic Production of Hydrogen, Fuels and Chemicals from Biomass- derived Oxygenated Hydrocarbons

Transcription

1 atalytic Production of ydrogen, Fuels and hemicals from Biomass- derived xygenated ydrocarbons James A. Dumesic Department of hemical & Biological Engineering University of Wisconsin Madison, WI 53706

2 Motivation: oil in every day life il is the blood of today s society Polymers Fuels Pharmaceuticals Industrial chemicals Petroleum Agriculture Demand for petroleum products in the United States averaged 19.7 million barrels per day in This represents about 3 gallons of petroleum each day for every person in the country (DE annual report 2004)

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5 U.S. Energy onsumption: End-Use

6 Biomass Potential 1.3 x 10 9 (billion) dry tons per year (U.S.) Equivalent to 3.5 x 10 9 barrels of oil (boe) 1 boe = 5.8 x 10 6 (million) BTU = 6.1 x 10 9 J Equivalent to 20 x (quadrillion) BTU/year U.S. energy consumption = 140 x BTU/year U.S. biomass potential = 15% Global Biomass production = 95 x BTU/year Woody biomass production = 40 x BTU/year Global energy consumption = 315 x BTU/year Global biomass potential = 30%

7 Biomass Transportation Sector Total energy consumed in U.S. = 140 quads Residential = 22 quads (16%) ommercial = 18 quads (13%) Industrial = 32 quads (23%) Transportation = 28 quads (20%) Electric Power = 41 quads (29%) Biomass = 20 quads Biomass potential = 70% of transportation

8 verview of Routes (at UW) for Biomass onversion to ydrogen, Fuels and hemicals

9 UW Routes to 2, Fuels & hemicals 2, 2, 2 Polymers

10 Production of ydrogen from Biomass-derived arbohydrates

11 Reforming Thermodynamics reforming water-gas shift ΔGº/RT (per mole of basis) EG - vapor phase reforming WGS vapor phase 4 - vapor lnp EG phase reforming lnp Glyerol Temperature (K) lnp sor Methane reforming at high temperatures xygenate reforming at low temperatures Favorable Water-gas shift Methanation favorable at low temperatures

12 The hallenge: an we find catalysts that produce 2 versus 4? atalyst? 2

13 (metal) 2 Selectivity hallenges --- * * --- * * cleavage (metal) - cleavage (metal) 2 Dehydration/ ydrogenation (metal,support,solution) Water-gas Shift 2, synthesis (metal) gas --- (alcohols) 2 2, 2 Methanation, Fischer-Tropsch reactions (metal) (metal) Dehydrogenation/ Rearrangement (metal,support,solution) (metal) --- (organic acids) Alkanes 2, 2, 2

14 50 Potential Energy Diagram: Ethanol/Pt(111) 25 0 ΔE [kj/mol] Alcala, Mavrikakis, Dumesic, J. atal. 218, 178 (2003)

15 Reforming of xygenates over Supported Metal atalysts

16 Liquid Phase Kinetics Product Gas BP arrier Gas Pressure maintained above bubblepoint pressure of feed at reaction temperature Differential reactor (verified kinetic control) or high-conversion operation Product analysis via G, PL, T Typical Products: 60-70% 2 30% 2 < 10% alkanes < 1000 ppm Temperature ontroller ooling Water IN ooling Water UT Bench-Scale Aqueous-Phase Reforming Reactor Liquid Drain 2 Selectivity = 2 Produced x 100% 2 that would be produced if all carbon products were from APR Alkane Selectivity = arbon as alkanes x 100% Total carbon in products T ¼ D Stainless Steel Tubular Reactor atalyst Bed Aluminum Block Insulated Furnace Quartz Wool Packing Liquid Feed

17 Aqueous-phase Reforming of xygenates over Pt/Al T= 498 K 1 wt% feed 2 and Alkane Selectivities Alkane Selectivity T= 538 K 2 Selectivity T= 538 K T= 498 K igh onversions lean reaction gas phase products omplete arbon Balance 0 Methanol Ethylene Glycol Glycerol Sorbitol Glucose ortright, Davda, Dumesic, Nature 418, 964 (2002)

18 Demonstration: Biomass to 2 over Pt

19 Non-precious Metal atalysts

20 igh-throughput Reactor A) B) ) Sample Needle oles Bolts Stainless Steel Top Plate Silicone Rubber Septum Gas Products atalyst Aqueous Feed Solution

21 igh-throughput Studies of Raney-NiSn Micromoles of Product conversion onversion (%) Wt. % Sn uber, G.W.; Shabaker, J.W.; and Dumesic. J.A.; Raney Ni-Sn atalyst for 2 from Biomass-Derived ydrocarbons, Science, 300, (2003) 0

22 EG-Reforming on Raney-NiSn NiSn: Packed-bed APR Reactor atalyst 2 Alkane 2 TF 4 TF 2 Rate Selectivity % Selectivity % min -1 min -1 μmol cm -3 min -1 Raney Ni Raney Ni 270 Sn Raney Ni 14 Sn Pt/Al Addition of Sn: Improves 2 selectivity Decreases 4 selectivity Ni 14 Sn ~ Pt/Al 2 3

23 atalysts for Biomass onversion

24 Virent Energy Systems

25 Vapor-phase phase onversion of Glycerol to : 2 Mixtures

26 Sources of Glycerol By-product waste-stream from biodiesel production, i.e., trans-esterification of triglycerides, leading to ~80 wt% glycerol in water Glucose fermentation, leading to 25 wt% glycerol in water (compared to 5% for ethanol) atalytic hydrogenolysis of xylitol and sorbitol ( 5 and 6 sugar-alcohols)

27 Glycerol onversion to Synthesis Gas at 350 o

28 Glycerol Reactivity (350 o ) onversion to Gas Phase (%) Pt/Mg-Zr Time on stream (h) Pt/ Pt/e 2 -Zr 2 Pt/Al 2 3 Pt/Zr 2 2 TF (min -1 ) Pt/Mg-Zr 2 Pt/Al 2 3 Pt/ Pt/e 2 -Zr Time on stream (h) Pt/Zr 2

29 oupling of Glycerol onversion with Fischer-Tropsch Synthesis

30 Fischer-Tropsch Synthesis igher hydrocarbons from synthesis gas ( 2 :) n + (2n+1) 2 n 2n+2 + n 2 Typical catalysts include: Fe, o, and Ru

31 oupling Gasification & FT Synthesis ( ) ( + ) (+ + ) kcal/mol -81 kcal/mol -10 kcal/mol -7 kcal/mol kcal/mol -354 kcal/mol Δ 1 Δ c (Gly) = 24% Δ 5 Δ c (Gly) = -4%

32 Reforming atalysts Fischer-Tropsch synthesis typically carried out at K (and bar) eat must flow from FT to reforming catalyst (Temperature for FT > T for reforming) Pt/ not active below ~573 K Θ increases as T decreases Additives needed to lower adsorption energy of on Pt Surface alloys may be useful!!

33 d-band shift Nørskov et al., J. atal. 199,, 123 (2001) Pt Ru

34 Adsorption on Near Surface Alloys Greeley & Mavrikakis, atal.. Today 111,, 52 (2006) Pt Pt/Ru Pt/Re

35 Glycerol onversion: Pt-Ru & Pt-Re Glycerol conversion (%) 90 / 2 PtRu:300 o PtRe:250 o PtRu:275 o PtRe 40 2 / PtRe:225 o PtRu Molar ratio Time on stream (h) Time on stream (h) Soares, Simonetti, Dumesic, Angewandte hemie 45, 3982 (2006).

36 FT Data at 275 o & 10 bar onversion and Selectivities (%) X S 5+ S 4 S 2 5+ selectivity Time on stream (h)

37 Dante and the FT product

38 Production of Value-added added hemicals from arbohydrates: MF* from exoses * ydroxymethylfurfural 2

39 Sleeping Giant* MF and its oxidation product 2,5-furandicarboxylic acid are so called sleeping giants in the field of intermediate chemicals from regrowing resources. 2 * M. Bicker, J. irth and. Vogel, Green hemistry, 2003.

40 hemicals from MF 2 6 -sugar MF Furan dicarboxylic acid (FDA) Terephthalic acid FDA

41 MF-derived Polymers Polyethylene terephthalate (PET) Polybutylene terephthalate (PBT) Furan dicarboxylic acid (FDA) N 2 N A polyamide (Nylon) MF 2 2 N 2 2 N A 100 % renewable polyester N 2 2 N 2 2 A polyurethane

42 Dehydration Reaction Pathways Fragmentation Products Additional Dehydration Products Rehydration Products Levulinic Acid Formic Acid D-Fructose β-pyranose Acyclic Intermediates MF aq MForg 2 Reversion Products Fructofuranosyl Intermediates Soluble Polymers and Insoluble umins ondensation Products

43 Approach to Achieve igh Selectivity for MF Extracting solvent, e.g., MIBK, butanol MF Aqueous layer containing promoters (e,g, DMS, NMP) MF Sugar Acid catalyst Dimethylsulfoxide, DMS S N-methylpyrrolidinone,NMP 3 N 3 3

44 MF selectivity vs Extraction Ratio

45 Thank you for your attention! Questions? alkanes sugars acid metal base APD/