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Hydroisomerization of n-Butane over Platinum-Promoted Cesium Hydrogen Salt of 12-Tungstophosphoric Acid
Biomass Technology Research Center, National Institute of Advanced Industrial Science and Technology, AIST Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
Professor Emeritus, University of Tokyo, Bunkyu-ku, Tokyo 113-8656, Japan
* Author to whom correspondence should be addressed.
Received: 13 November 2009; in revised form: 4 December 2009 / Accepted: 14 December 2009 / Published: 14 December 2009
Abstract: The hydroisomerization of n-butane was carried out in a fixed-bed gas-flow reactor over Pt-promoted Cs2.5H0.5PW12O40 (denoted as Cs2.5). Two kinds of catalysts, a direct impregnation of Pt on Cs2.5 (denoted as Pt/Cs2.5), as well as a mechanical mixture of Pt/Al2O3 and Cs2.5 (denoted as Pt/Al2O3+Cs2.5), were used for the hydroisomerization. Pt/Al2O3+Cs2.5 showed a higher stationary activity than Pt/Cs2.5 because the Pt particles supported on Al2O3 were much smaller than those supported on Cs2.5. The initial activity decreased with increasing H2 pressure over Pt/Al2O3+Cs2.5. This indicates that the hydroisomerization of n-butane over Pt/Al2O3+Cs2.5 proceeded through a bifunctional mechanism, in which n-butane was hydrogenated/dehydrogenated on Pt sites and was isomerized on acid sites of Cs2.5. For the hydroisomerization of n-butane over Pt/Al2O3+Cs2.5 the hydrogenation/dehydrogenation on Pt sites is a limiting step at a low Pt loading and the isomerization on solid acid sites is a limiting step at a high Pt loading. During the reaction, hydrogen molecules were dissociated to active hydrogen atoms on Pt sites, and then the formed active hydrogen atoms moved to the solid acid sites of Cs2.5 (spillover effect) to eliminate the carbonaceous deposits and suppress the catalyst deactivation. Because Cs2.5 has suitably strong and uniformly-distributed solid acid sites, Pt/Al2O3+Cs2.5 showed a higher stationary activity than Pt/Al2O3+H-ZSM-5 and Pt/Al2O3+SO4/ZrO2 for the hydroisomerization of n-butane at a low H2 pressure.
Keywords: hydroisomerization; n-butane; platinum; heteropolyacid; bifunctional catalyst
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Liu, Y.; Misono, M. Hydroisomerization of n-Butane over Platinum-Promoted Cesium Hydrogen Salt of 12-Tungstophosphoric Acid. Materials 2009, 2, 2319-2336.
Liu Y, Misono M. Hydroisomerization of n-Butane over Platinum-Promoted Cesium Hydrogen Salt of 12-Tungstophosphoric Acid. Materials. 2009; 2(4):2319-2336.
Liu, Yanyong; Misono, Makoto. 2009. "Hydroisomerization of n-Butane over Platinum-Promoted Cesium Hydrogen Salt of 12-Tungstophosphoric Acid." Materials 2, no. 4: 2319-2336.