TY - JOUR
T1 - RuSn bimetallic catalysts for selective hydrogenation of levulinic acid to γ-valerolactone
AU - Wettstein, Stephanie G.
AU - Bond, Jesse Q.
AU - Alonso, David Martin
AU - Pham, Hien N.
AU - Datye, Abhaya K.
AU - Dumesic, James A.
N1 - Funding Information:
This work was supported in part by the U.S. Department of Energy Office of Basic Energy Sciences , and by the DOE Great Lakes Bioenergy Research Center ( www.greatlakesbioenergy.org ), which is supported by the U.S. Department of Energy , Office of Science , Office of Biological and Environmental Research , through Cooperative Agreement between The Board of Regents of the University of Wisconsin System and the U.S. Department of Energy. In addition, this work was supported by the Defense Advanced Research Projects Agency (DARPA) and Army Research Lab (ARL) through the Defense Science Office Cooperative Agreement W911NF-09-2-0010/09-005334 B 01 (Surf-Cat: Catalysts for production of JP-8 range molecules from lignocellulosic biomass). The views, opinions, and/or findings contained in this article are those of the authors and should not be interpreted as representing the official views or policies, either expressed or implied, of the Defense Advanced Research Projects Agency or the Department of Defense.
PY - 2012/5/18
Y1 - 2012/5/18
N2 - Carbon-supported ruthenium catalysts containing different amounts of tin were studied for the hydrogenation of levulinic acid (LA) to gamma-valerolactone (GVL) in a 2-sec-butyl-phenol (SBP) solvent. Results from reaction kinetics measurements (453K and 35bar H 2) showed that the Ru/C catalyst was initially more active for hydrogenation of both LA and SBP (i.e., 0.051s -1 for conversion of LA to GVL), followed by continuous deactivation versus time on stream. In contrast, the catalyst containing equal amounts of Ru and Sn had a lower activity for LA to GVL conversion (0.005s -1), but displayed stable activity versus time on stream and showed 100% selectivity for hydrogenation of LA versus the SBP solvent. Increasing the amount of Sn to a 1 to 4 Ru:Sn atomic ratio creates an additional phase, β-Sn, that is not active for hydrogenation, leaches into the SBP solvent, and sinters under reaction conditions. Results from CO and O 2 chemisorption and electron microscopy measurements indicated that the Ru-based metal particles did not leach or sinter at reaction conditions, and that the surfaces of these particles became progressively enriched with Sn as the Sn-loading increases. In addition, Sn did not significantly leach from the catalysts when present as an intermetallic alloy with Ru, such as Ru 2Sn 3 and Ru 3Sn 7. Using LA produced from corn stover, the RuSn 4/C catalyst was stable and demonstrated that it is a promising catalyst to produce valuable chemicals and fuels from real biomass.
AB - Carbon-supported ruthenium catalysts containing different amounts of tin were studied for the hydrogenation of levulinic acid (LA) to gamma-valerolactone (GVL) in a 2-sec-butyl-phenol (SBP) solvent. Results from reaction kinetics measurements (453K and 35bar H 2) showed that the Ru/C catalyst was initially more active for hydrogenation of both LA and SBP (i.e., 0.051s -1 for conversion of LA to GVL), followed by continuous deactivation versus time on stream. In contrast, the catalyst containing equal amounts of Ru and Sn had a lower activity for LA to GVL conversion (0.005s -1), but displayed stable activity versus time on stream and showed 100% selectivity for hydrogenation of LA versus the SBP solvent. Increasing the amount of Sn to a 1 to 4 Ru:Sn atomic ratio creates an additional phase, β-Sn, that is not active for hydrogenation, leaches into the SBP solvent, and sinters under reaction conditions. Results from CO and O 2 chemisorption and electron microscopy measurements indicated that the Ru-based metal particles did not leach or sinter at reaction conditions, and that the surfaces of these particles became progressively enriched with Sn as the Sn-loading increases. In addition, Sn did not significantly leach from the catalysts when present as an intermetallic alloy with Ru, such as Ru 2Sn 3 and Ru 3Sn 7. Using LA produced from corn stover, the RuSn 4/C catalyst was stable and demonstrated that it is a promising catalyst to produce valuable chemicals and fuels from real biomass.
KW - Alkylphenol
KW - Bimetallic
KW - Biomass
KW - Heterogeneous catalysis
KW - Renewable resources
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U2 - 10.1016/j.apcatb.2012.01.033
DO - 10.1016/j.apcatb.2012.01.033
M3 - Article
AN - SCOPUS:84857211696
SN - 0926-3373
VL - 117-118
SP - 321
EP - 329
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
ER -