HYDRODESULFURIZATION OF THIOPHENE, BENZOTHIOPHENE, DIBENZOTHIOPHENE, AND RELATED COMPOUNDS CATALYZED BY SULFIDED C0O-M0O3-GAMMA-AL2O3 - LOW-PRESSURE REACTIVITY STUDIES

Hydrodesulfurization experiments were carried out with a sulfided CoOMoO3 γ-Al2O3 catalyst in a pulse microreactor operated at atmospheric pressure and temperatures of 350 to 450 °C. The reactants were hydrogen and pure sulfur-containing compounds (or pairs of compounds), including thiophene, benzothiophene, dibenzothiophene, several of their hydrogenated derivatives, and various methyl-substituted benzothiophenes and dibenzothiophenes. The aromatic compounds appeared to react with hydrogen by simple sulfur extrusion; for example, dibenzothiophene gave H2S + biphenyl in the absence of side products. The reactivities of thiophene, benzothiophene, and dibenzothiophene were roughly the same. Each hydrogenated compound (e.g., tetrahydrothiophene) was more reactive than the corresponding aromatic compound (e.g., thiophene). Methyl substituents on benzothiophene had almost no effect on reactivity, whereas methyl substituents on dibenzothiophene located at a distance from the S atom slightly increased the reactivity, and those in the 4-position or in the 4- and 6-positions significantly decreased the reactivity. In contrast to the observation of a near lack of dependence of low-pressure reactivity on the number of rings in the reactant, the literature shows that at high pressures the reactivity decreases with an increased number of rings. The pressure dependence of the structure-reactivity pattern is suggested to be an indication of relatively less surface coverage by the intrinsically more reactive compounds (e.g., thiophene) at low pressures but not at high pressures. The relative reactivities are also suggested to be influenced by differences in the structures of the catalyst at low and high hydrogen partial pressures, which may be related to the concentrations of surface anion vacancies and the nature of the adsorbed intermediates. © 1978.