Hierarchically Porous β/SBA-16 Composites: Tuning Pore Structure and Acidity for Enhanced Isomerization Performance in Hydrodesulfurization of Dibenzothiophene and 4,6-Dimethyldibenzothiophene

β/SBA-16 (BS) materials were fabricated using β-nanoclusters through self-assembly hydrothermal crystallization approach; subsequently, the corresponding NiMo/BS catalysts were synthesized. The influence of HCl concentration on the physicochemical properties of the composite support and the corresponding catalyst was investigated by a series of characterization methods. The hydrodesulfurization (HDS) performances were evaluated under the conditions of T = 340 °C, P H2 = 4 MPa, and H2/oil (v/v) = 200 by adopting dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) as probe reactants. The results indicated that NiMo/BS-1.5 prepared under the HCl concentration of 1.5 mol L–1 exhibited the superior HDS performance due to its well-ordered shape and pore channel, high sulfidation degree, moderate acidity, and suitable metal–support interaction (MSI). In addition, the potential HDS reaction networks for DBT and 4,6-DMDBT of series NiMo/BS were presented.