Catalytic activities of Co(Ni)Mo/TiO2-Al2O3 catalysts in gasoil and thiophene HDS and pyridine HDN:: effect of the TiO2-Al2O3 composition

The effect of the TiO2-Al2O3 mixed oxide support composition on the hydrodesulfurization (HDS) of gasoil and the simultaneous I-IDS and hydrodenitrogenation (HDN) of gasoil+pyridine was studied over two series of CoMo and NiMo catalysts. The intrinsic activities for gasoil HDS and pyridine HDN were significantly increased by increasing the amount of TiO2 into the support, and particularly over rich- and pure-TiO2-based catalysts. It is suggested that the increase in activity be due to an improvement in reducing and sulfiding of molybdena over TiO2. The inhibiting effect of pyridine on gasoil HDS was found to be similar for all the catalysts, i.e., was independent of the support composition. The ranking of the catalysts for the gasoil I-IDS test differed from that obtained for the thiophene test at different hydrogen pressures. In the case of gasoil HDS, the activity increases with TiO2 content and large differences are observed between the catalysts supported on pure Al2O3 and pure TiO2. In contrast, in the case of the thiophene test, the pure Al2O3-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also, in the thiophene test the difference in intrinsic activity between the pure Al2O3-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also in the thiophene test, the difference in intrinsic activity between the pure Al2O3- and pure TiO2-based catalysts is relatively small and dependent on the H-2 pressure used. Such differences in activity trend among the gasoil and the thiophene tests are due to a different sensitivity of the catalysts (by different support or promoter) to the experimental conditions used. The results of the effect of the H-2 partial pressure on the thiophene HDS, and on the effect of H2S concentration on gasoil HDS demonstrate the importance of these parameters, in addition to the nature of the reactant, to perform an adequate catalyst ranking. (C) 1999 Elsevier Science B.V. All rights reserved.