Stabilization effect of Co for Mo phase in CoMoAl2O3 hydrodesulfurization catalysts studied with X-Ray photoelectron spectroscopy

The promotional effects of Co in $\text{CoMo}\text{Al}{}_2\text{O}{}_3$ hydrodesulfurization (HDS) catalysts were studied by means of X-ray photoelectron spectroscopy. The higher MoO₃-content $\text{Mo}\text{Al}{}_2\text{O}{}_3$ catalysts (10 and 20 wt% MoO₃) contain mobile Mo, which migrates from the pores to the outermost surface layers of the catalysts and segregates to form less active crystalline MoS₂ during the HDS reaction, while in the case of $\text{Mo}\text{Al}{}_2\text{O}{}_3$ (5 wt% MoO₃) catalyst: no migration of Mo was observed. It is revealed that the Co in $\text{CoMo}\text{Al}{}_2\text{O}{}_3$ catalyst inhibits the migration and segregation of Mo and that it keeps Mo effective for the HDS reaction, since no surface enrichment of Mo was observed. It is concluded that stabilization of the Mo monomolecular layer is the main role of Co. The active species of Mo is suggested to have the composition of S/Mo(IV) = 1 on the basis of the sulfur contents of the catalysts under the mild HDS reaction conditions.