Porous support materials were prepared by assembling primary and secondary ZSM-5 structural units into a well-ordered mesoporous framework. The materials possessed both ZSM-5 microporous building units and mesoporous structure were used as supports for the preparation of hydrodesulfurization (HDS) catalysts. The materials and their corresponding catalysts were characterized by XRD, FTIR, 27Al MAS NMR, TEM, N2 adsorption-desorption, Py-FTIR, H2-TPR, Raman, and HRTEM techniques. The pore structures of the composite materials were modulated by adjusting the molar ratio of butanol/P123 (BuOH/P123) and then, the influences of BuOH/P123 on the catalytic performance in the HDS of dibenzothiophene (DBT) and diesel oil were systematically studied. The results showed that butanol has a big influence on the structure of the micro-mesoporous material, whereby different micro-mesoporous structures, such as the p6mm hexagonal structure or Ia3̄d cubic structure, were formed with different butanol addition amounts. The composite ZK-3 (BuOH/P123 = 100) possessed the best surface area and pore structure. Therefore, the NiMo/ZK-3 catalyst showed the highest catalytic activity in the HDS of DBT with a BP selectivity of 72.1% due to its excellent textural property, moderate MSI, relatively high B/L ratios, and highly dispersed NiMoS active phases. Moreover, the NiMo/AZK-3 catalyst exhibited excellent catalytic performance in the HDS of diesel oil.
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