Sulfided Mo and CoMo supported on zeolite as hydrodesulfurization catalysts: transformation of dibenzothiophene and 4,6-dimethyldibenzothiophene

The hydrodesulfurization (HDS) of dibenzothiophene (DBT) and of 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out on sulfided Mo and CoMo on HY catalysts, and also on sulfided Mo and CoMo on alumina catalysts (fixed bed reactor, 330°C, 3MPa hydrogen pressure). On all the catalysts, the two reactants transformed through the same parallel pathways: direct desulfurization (DDS) leading to biphenyl-type compounds, and desulfurization after hydrogenation (HYD) leading first to tetrahydrogenated intermediates, then to cyclohexylbenzene-type products. However, additional reactions were observed with the zeolite-supported catalysts, namely methylation of the reactants, cracking of the desulfurized products, and, in the case of 4,6-DMDBT, displacement of the methyl groups and transalkylation. The global activity of Mo/zeolite in DBT or 4,6-DMDBT transformation as well as its activity for the production of desulfurized products (HDS) were much higher than those of Mo/alumina. On the other hand, cobalt exerted a promoting effect on the activity in the transformation of DBT or 4,6-DMDBT of all the molybdenum catalysts. However, this effect was much less significant with the zeolite support than with the alumina support, which indicated that the promoter was not well associated to molybdenum on the zeolite support. Therefore, the activity of CoMo/zeolite in the HDS of DBT was much lower than that of CoMo/alumina. On the contrary, in the case of 4,6-DMDBT CoMo/zeolite was more active in HDS than CoMo/alumina. This increase in HDS activity was attributed to the transformation of 4,6-DMDBT into more reactive isomers through an acid-catalyzed methyl migration. The consequence was that on the zeolite-supported catalyst 4,6-DMDBT was more reactive than DBT.