Hydroisomerization of n-Butane over Platinum-Promoted Cesium Hydrogen Salt of 12-Tungstophosphoric Acid

The hydroisomerization of n-butane was carried out in a fixed-bed gas-flow reactor over Pt-promoted Cs(2.5)H(0.5)PW(12)O(40) (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/Al(2)O(3) and Cs2.5 (denoted as Pt/Al(2)O(3)+Cs2.5), were used for the hydroisomerization. Pt/Al(2)O(3)+Cs2.5 showed a higher stationary activity than Pt/Cs2.5 because the Pt particles supported on Al(2)O(3) were much smaller than those supported on Cs2.5. The initial activity decreased with increasing H(2) pressure over Pt/Al(2)O(3)+Cs2.5. This indicates that the hydroisomerization of n-butane over Pt/Al(2)O(3)+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/Al(2)O(3)+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/Al(2)O(3)+Cs2.5 showed a higher stationary activity than Pt/Al(2)O(3)+H-ZSM-5 and Pt/Al(2)O(3)+SO(4)/ZrO(2) for the hydroisomerization of n-butane at a low H(2) pressure.