Structure-Activity Correlations in Hydrodesulfurization Reactions over Ni-Promoted MoxW(1-x)/Al2O3 Catalysts

In this work, we have investigated the activation process and structure of Ni-promoted MoxW(1-x)S2/Al2O3 hydrodesulfurization (HDS) catalysts. Conversion of Mo and W oxides to the catalytically active MS, (M = Mo, W) phase by sulfidation in gaseous H2S/1-12 proceeded via different pathways, as found by XPS and EXAFS. The slower sulfidation kinetics of W on the alumina support formed NiMoxWo_4 sulfides with a two-dimensional core shell structure. Mo was mostly located in the core and W in the shell, as evidenced by EXAFS. Increasing the H2S/H-2 pressure during sulfidation distributed Mo and W more homogeneously in the metal sulfide particles. This was attributed to the more favorable sulfidation of W under these conditions (i.e., below the temperature of MoS, formation). Catalytic testing was consistent with these findings and demonstrated that a core shell structure is the active phase in thiophene HDS (1 atm), whereas a homogeneously mixed MS, phase catalyzes the HDS of dibenzothiophene at 40 bar. This is the first example of a core shell structure in promoted MoxW(l-x)S, catalysts. Support interactions in the oxidic precursor, which affect the sulfidation kinetics, were determined to play a key role in the formation of these structures.