Monodisperse dendritic micro-mesoporous composite self-assembled with tiny TS-1 seeds as efficient catalysts for hydrodesulfurization of dibenzothiophenes

Abstract

Novel TS-1/dendritic mesoporous silica nanoparticles (TS-1/DMSNs, TD) micro-mesoporous composites with different morphology were prepared for NiMo catalysts (NiMo/TD-TEA). Series catalysts were tested in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions in a fix-bed reactor. TS-1 were uniformly compounded with mesoporous materials in the form of Si-O-Ti bonds, which did not affect the typical dendritic morphology. The introduction of TEA could inhibit the growth of support particles, and modulate the acidity and the metal-support interaction (MSI) of catalysts. Optimized NiMo/TD-TEA catalyst showed the optimal DBT (98.0 %) and 4,6-DMDBT (92.3 %) desulfurization rate as well as the excellent hydrogenation (HYD) selectivity for DBT and 4,6-DMDBT HDS with the optimal reaction rate constant (12.2 mol·g−1·h−1, 6.7 mol·g−1·h−1) and turnover frequency (2.3 h−1, 1.4 h−1). By correlating to the catalyst acidity–activity and active phase–activity, the activity and selectivity were not only depended on the presence of Brønsted (B) acid and the total acid content but also associated with the dispersion and morphology of MoS2 slabs.