The hydrodesulfurization of thiophene using rhodium(III)-13X and -ZSM-5 zeolites has been studied in a pulsed microreader as a function of temperature. Hydrodesulfurization catalysts were prepared by sulfidation with thiophene and with H2S H2. The C4products included butene and butane. Neither tetrahydrothiophene nor butadiene was identified in the product gas stream. Thiophene conversion over Rh(III)-ZSM-5 sulfided at 400 °C with a 10 vol% H2S 90 vol % H2mixture was at least as effective as a commercial cobalt-molybdate catalyst under similar reaction conditions. The effectiveness of the Rh(III)-ZSM-5 catalyst sulfided with the H2S H2mixture at 250 °C and with thiophene at 100 °C was less than the cobalt-molybdate catalyst. The conversion percentage to C4hydrocarbons was greater on the Rh(III)-13X than on CoMo Al2O3. Analysis by X-ray photoelectron spectroscopy (XPS) of the Rh-zeolite catalysts before and after use indicated that the active species is Rh(I). A mechanism for reaction on the Rh-zeolite is proposed where oxidative addition-reductive elimination reactions of Rh(I) Rh(III) are involved in the hydrodesulfurization process. © 1984.
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