Chemical Engineering Journal Advances (Aug 2022)
Role of the solvent evaporating temperature on the NiMo/TiO2-Al2O3 catalyst and the hydrodesulfurization performance for 4,6-dimenthyldibenzothiophehe
Abstract
Binary TiO2-Al2O3 serial composites(TA-x) and the NiMo supported catalysts(NiMo/TA-x) were successfully synthesized at different solvent evaporation temperatures,. The materials were characterized by several advanced characterization techniques, and the catalytic hydrodesulfurization (HDS) performances were evaluated. The results revealed that the synthesized TA-x serial composites are amorphous mixtures of TiO2 and Al2O3 with highly ordered two-dimensional hexagonal mesopores. Both the mesostructures and the acidities of the synthesized TA-x composites changed at different evaporation temperature of the solvent. The metal-support interaction(MSI), the existence states and the coordination states of the Mo precursors can be modulated by the changes in the physicochemical property of the TA-x composites caused by the solvent evaporating temperature. A moderate solvent evaporation temperature is favorable for the doping of Ni species into the MoS2 slab and Mo sulfidation degree, thus enhancing the proportion of the NiMoS active phases. Catalyst NiMo/TA-60 exhibits superior activity and the highest direct desulfurization(DDS) pathway selectivity due to the excellent acidity and pore structure property, the highest dispersion and the highest Mo sulfidation degree, a moderate MSI, the highest efficiency in the formation of NiMoS phase and the highest proportion of corner Mo atoms. Moreover, the rate constants of the specific HDS pathways can be correlated with the specific types of active sites: the DDS pathway (kDDS) is closely related to the proportion of corner active sites and the hydrogenation desulfurization pathway (kHYDS) is closely related to the proportion of brim sites. The activity of a single corner active site is found to be approximately 100 times that of a single edge active site. These findings are promising in the design of HDS catalysts for inferior distillates.