Nanostructured Catalysts for Green Gasoline 2010 NSF Nanoscale Science and Engineering Grantees Conference

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2 Nanostructured Catalysts for Green Gasoline 2010 NSF Nanoscale Science and Engineering Grantees Conference Prof. John R. Regalbuto Dept. of Chemical Engineering U. Illinois at Chicago December 6 th, 2010

3 Outline The sea change in federal funding for biofuels research catalyzed by NSF bioethanol to green gasoline the key role of catalysis and biocatalysis A simple, scientific method to prepare highly active supported metal catalysts strong electrostatic adsorption (SEA) single metal, promoted, bimetallic catalysts

4 Biomass R&D Board National Action Plan 2006 version

5 Biofuel Production Alternatives Sugar/Starch corn grain starch saccharification sugarcane sugar fermentation Ethanol Lipids thermal routes catalytic routes soy beans transesterfication Biodiesel biological routes synthetic biology

6 forest waste lignocellulose Biofuel Production Alternatives Jet Fuel corn stover switchgrass dissolution Sugar/Starch corn grain starch Lipids sugarcane soy beans saccharification sugar hydrotreating transesterfication lignin fermentation Biodiesel Heat/Power Ethanol butanol thermal routes catalytic routes biological routes synthetic biology

7 forest waste corn stover lignocellulose Biofuel Production Alternatives gasification to syngas (CO + H 2 ) pyrolysis, fast or slow gases Fischer-Tropsch methanol Jet Fuel switchgrass dissolution bio-oil Diesel Sugar/Starch corn grain starch Lipids sugarcane soy beans saccharification sugar hydrotreating transesterfication lignin fermentation Biodiesel Heat/Power Ethanol butanol thermal routes catalytic routes biological routes synthetic biology

8 Roadmap for Hydrocarbon Production 2007 NSF/ENG and DOE/EERE Cosponsored Workshop in June, 2007 Workshop participants: 71 invited participants 27 academics from 24 universities 19 companies, small and large 13 representatives from 5 national labs 10 program managers (NSF, DOE, USDA) Workshops Goals: Articulate the role of chemistry and catalysis in the mass production of green gasoline, diesel and jet fuel from lignocellulose. Understand the key chemical and engineering challenges. Develop a roadmap for the mass production of next generation hydrocarbon biofuels. Final Report Released April 1, Input for Interagency Working Group on Biomass Conversion

9 forest waste corn stover lignocellulose Biofuel Production Alternatives gasification to syngas (CO + H 2 ) pyrolysis, fast or slow gases Fischer-Tropsch methanol Jet Fuel switchgrass dissolution bio-oil Diesel alga Sugar/Starch corn grain starch Lipids sugarcane soy beans saccharification liquid phase processing sugar hydrotreating transesterfication lignin fermentation Biodiesel Heat/Power Gasoline Ethanol butanol thermal routes catalytic routes biological routes synthetic biology

10 Potential advantages of hydrocarbons Self-separate; remove great expense of distillation 30-50% higher energy density; won t suffer a commensurate loss of gas mileage Reduction of water use Green gasoline/diesel/jet fuel fit into current infrastructure; no need for engine modifications or new distribution systems

11 Hybrid Petrochemical/Biofuel Refineries Petroleum-Derived Feedstocks Vacuum-Gas Oil Light Cycle Oil Diesel Fuel LPG Hybrid Refinery Catalytic Cracker Hydrotreating Hydrocracking Biomass-Derived Feedstocks Bio-oils Aqueous Sugar Streams Vegetable Oils Glycerol Lignin Olefins Gasoline Diesel Jet Fuel Huber, G. W.; and Corma, A.; Synergies between bio- and oil- refineries for the production of fuels from biomass, Angewandte Chemie International Edition, 2007, 46, 2-20.

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14 December 2007 Biomass R&D Board Meeting Dr. Bement proposed: Interagency working group on Hydrocarbon biofuels: Biomass Conversion Interagency Working Group Revision of National Action Plan to include next generation hydrocarbon biofuels Research DOE/SC NSF Development USDA DOE/EERE USDA

15 National Action Plan 1 st major revision 6.x Conversion research and technology (Lead: NSF/DOE)... 6.x.1 Optimization of oxygenated fuel production... 6.x.2 Next generation hydrocarbon biofuels...

16 Current Status of Hydrocarbon Biofuels in U.S. Sea change in biofuels funding Biomass Conversion Interagency WG 10 Year RD&D Plan Federal Funding: DOE/SC $20 MM EFRCs; 3 or 4 on hydrocarbon fuels DOE/EERE/OBP: $800 MM, $480MM demonstration projects, $85 MM algae (NAABB) and thermochem. (NABC) consortia NSF: Hydrocarbons from Biomass FY 09 EFRI topic, $16 MM USDA, DOD, etc. No EtOH targets at DOE/OBP past 2012

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19 Virent Shell: 100 MM GPY, Envergent (UOP/Ensyn): 100 MM GPY, 2011 for license (major oils interested) KiOR : 100 MM GPY, 2011 Amyris - Crystalsev:?? MM GPY, 2011 Choren:?? MM GPY (FTS) Sapphire Oil (Algae): 100 MM GPY, 2016, 1 B GPY, 2022

20 Virent Energy Systems Overview Founded in 2002 by Dr. Randy Cortright and Professor Jim Dumesic from the Department of Chemical Engineering of the University of Wisconsin

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22 Cane Sugar to Green Gasoline

23 Catalysts: Heart of Petroleum Refineries Fuels, Chemicals, Materials (Textiles)

24 The Catalyst: Heart of a Catalytic Converter NO + CO N 2 + CO 2 N N O Rh O C Pt Pt/Rh/Al 2 O 3 catalyst washcoat

25 Motivation What s the best way to make small, stable metal catalyst particles over oxide and carbon supports? Hypothesis: strong adsorption of metal precursor will lead to high dispersion of reduced (finished) catalyst: 1) adsorption of [PtCl 6 ] -2 precursors 2) reduction of [PtCl 6 ] -2 to Pt 0 25

26 Electrostatic Adsorption ph<pzc OH 2 + K ads [PtCl 6 ] -2 K 1 PZC OH [H] + (ph shifts) K 2 ph>pzc O - K ads [(NH 3 ) 4 Pt] +2 26

27 ph Final Method of Strong Electrostatic Adsorption (SEA) ph<pzc OH + 2 K ads [PtCl 6 ] Uptake ph survey K 1 3. Reduce to retain high dispersion PZC OH [H] + (ph shifts) H 2 K 2 ph>pzc O - K ads [(NH 3 ) 4 Pt] PZC determination L90 M-7D EH-5 VN-3S FK300 Model ph Initial PTA/SiO 2 M. Schreier, J. R. Regalbuto, J. Catal., 225 (2004) 190.

28 Catalyst Preparation (SEA vs. DI) NM and base metal ammines

29 Pd, Co, Ru uptake (mmol/m 2 ) Cu uptake (mmol/m 2 ) Co, Ru, Pd, Ni ammines on silica 1000 m 2 /liter Vn3s silica, 200 ppm 1.8 Tetraammine Pd Hexaammine Co Hexaammine Ru(II) Hexaammine Ru(III) Hexaammine Ni(II) Self-prepared tetraammine Cu Purchased tetraammine Cu ph final

30 ph 11 DI Cu 2.8 wt% 31 ± 8 Å 140 ± 170 Å Pd 2.2 wt% 16 ± 4 Å 55 ± 34 Å

31 ph 11 DI Ru 3.0 wt% 12 ± 2 Å 130 ± 47 Å Ni 1.6 wt% 17 ± 4 Å 32 ± 17 Å

32 Pt/SiO 2 - STEM images (SEA vs. DI Pt%=9.2%) 9.2% Pt SEA 160 C reduc 1.8 ±.45 nm 9.2% Pt DI 13 ± 6.2 nm

33 Pd/SiO 2 - STEM images (SEA vs. DI Pd%=8.7%) 8.7% Pd SEA 200 C reduc 1.3 ±.4 nm 8.7% Pd DI 11 ± 5.2 nm

34 [Au(en) 2 ] +3 3Cl - First production Block et. al 1951 Current groups using Precursor Catherine Louis Titania Other Groups Silica/Carbon

35 Representative STEM Images SBA-15 Mesoporous Silica SEA DI 50 nm 50 nm D avg : nm D avg : nm

36 SEA: CPA/Al 2 O 3 surface coverage mmol/m ppmCPA model 2days aged / Gamma-277 2days aged / Gamma ph 3.1 wt% Pt/Al 2 O 3 (277 m 2 /gm), d av = 1.3 nm

37 Carbon Name Abbreviation SA (m 2 /g) Pretreatment Total Pore Volume (ml/g) PZC Activated carbon Darco s-51 S Acid washed, steam activation of lignite coal Norit SX 2 SX2 800 Acid washed steam activated Norit SX 4 SX4 650 Acid washed steam activated 7.9 Norit SX ULTRA SXU 1200 Acid washed steam activated Norit CA-1 CA 1400 Chemically activated by phosphoric acid Darco KB-B KB 1500 chemical activation of hardwood Graphite Asbury Grade 4827 ASBURY 115 Heated, ground natural graphite Timcal TIMREX HSAG 300 Carbon Black Degussa A N754 TIMREX 280 Heated, ground petroleum coke N pyrolysis Ensaco 250 Powder E pyrolysis Ensaco 350 Powder E pyrolysis Vulcan XC 72 VXC 254 pyrolysis

38 ppm Pt adsorbed CPA, PTA uptake vs. ph, varying carbon type CPA/high PZC PTA/mid PZC ppm Pt adsorbed ph SX4 1Hr pzc=7.5 SX 1Hr pzc=8.0 SX2 1Hr pzc=8.5 Vulcan 1Hr pzc=8.6 Ensaco 250 1Hr pzc=8.8 ensaco 350 1Hr pzc= Darco s51 pzc=4.8 TIMREX pzc=4.8 KB pzc=5.0 Asubury pzc= ph finals - narrower volcano curves w.r.t alumina, silica - pore exclusion of PTA from small pore carbons at high ph

39 STEM of PTA/Timrex after 200 C Reduction dry impregnation SEA, ph 10 - average size 8-10 nm - average size 1.5 nm

40 Comparison of Platinum Particle size on High Surface Area Carbon Black (BP2000, 1500 m 2 /gm) SEA, 500 m 2 /l, ph 2.9, 200 C reduc. DI (pore filling, ph init 0.5), 200 C reduc. o Good dispersion and small particle size (1-2 nm) o Also good dispersion and small(er?) particle size (1-2 nm)

41 Mn onto Co 3 O 4 of Co 3 O 4 /TiO 2 EDXS Results T. Feltes and J. Regalbuto, J. Catal. 2010

42 Mn onto Co 3 O 4 of Co 3 O 4 /TiO 2 EDXS Results PZC measurements Uptake ph survey 42

43 Mn onto Co 3 O 4 of Co 3 O 4 /TiO 2 EDXS Results XPS; Co is covered by Mn Selectivity increases, activity decreases 43

44 Mn onto Co 3 O 4 of Co 3 O 4 /TiO 2 EDXS Results Z contrast T. Feltes, Y Zha, R. Klie and J. Regalbuto, ChemCatChem 2010 b) EELS map 5 n m 2 n m

45 Bimetallic Catalyst Synthesis 45

46 TEM image of the Core-shell structure made by Sequential Impregnation Image on the left shows a larger particle with diameter around 35nm. From the TEM image we can see clearly that there is a grey shell around the dark core. The thickness of the shell is around 4.5nm. The diameter of the core is around 24nm. 46

47 Sequential Impregnation sample Small particles (diameter smaller than 10nm) also show the core-shell structure with a CoO x core and Pd shell. L. D Souza and J. Regalbuto, 47 in preparation

48 Concluding Remarks Peak oil is real; our country s energy infrastructure must be reinvented Biofuels: hydrocarbons High energy density Infrastructure Compatible Long range vision: Electric/plug in hybrid for light vehicles Diesel and jet fuel for the heavies (trucks, planes, ships, tanks) Use biomass for these; energy independence in 2 decades!? Catalysis will play a central role in the development of this new infrastructure Bio- and solar fuels and chemicals Fuel cells and artificial photosynthesis Clean coal: CCS, CO 2 activation