The micro-mesoporous materials ZF-x (ZSM-5-FDU-12, x = SiO2/Al2O3) with different molar ratios of SiO2/Al2O3 were synthesized by an in situ nano-assembly method with the ZSM-5 precursor serving as the silica source.

Titanium-modified pure aluminum-based TUD-1 (TiAT) mesoporous material with a highly active three-dimensional was successfully synthesized by using tetraethylene glycol (TEG) as a template through sol–gel method. The series catalysts were characterized by X-ray diffraction (XRD), N2 adsorption–desorption, Raman, pyrolysis-infrared (Py-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) technologies. The characterization results indicated that Ti was incorporated into the TUD-1. In addition, the synthesized materials had large pore size (6.4 nm), high surface area (394.0 m2/g), and large pore volume (0.83 cm3/g). It was shown that Ti acting as an electronic promoter could promote the formation of Mo7O24 6– precursors and more type II NiMoS phases. Furthermore, Ti incorporation could bring more Brønsted and Lewis acids into the catalysts, which were beneficial to improve the hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) reaction processes. Catalytic performances of diffierent catalysts were estimated in a high-pressure hydrotreating microreactor using FCC diesel as feedstock; moreover, the catalyst of NiMo/TiAT-25 exhibit the highest HDS (97.3%) and (HDN) (99.1%) efficiencies of FCC diesel, respectively, and the highest HDS (97.4%) of DBT, since NiMo/TiAT-25 possessed suitable acidity, pore structure, reducibility, and degree of sulfidation.

Post-synthesis methods are a promising technology and have received much attention. In this paper, a series of post-synthesis aluminum modified TUD-1 (PAT) materials with different Al contents were successfully prepared by using aluminum isopropoxide to be Al sources, then the as-synthesized materials were adopted as support additives mixed with commercial γ-Al 2 O 3 to prepare hydrodesulfurization (HDS) catalysts for FCC diesel. The supports and catalysts were analyzed using N 2 adsorption-desorption, XRD, SEM, Py-IR, ICP, 27 Al MAS NMR, UV-vis, H 2 -TPR and HRTEM techniques. The results of Py-IR and 27 Al MAS NMR indicated that the addition of Al species could bring Lewis (L) and Brönsted (B) sites into Si-TUD-1, and that the material of PAT-3 had the highest total acidity sites and Brönsted acid sites among the series PAT composites. The HRTEM technique showed that, compared to the traditional catalyst NiMo/γ-Al 2 O 3 , the sulfided catalyst NiMo/APAT-3 had a relatively short length (3.2 nm) and suitable stacking number (2.5) of MoS 2 slabs. The HDS efficiencies of all the catalysts were tested in a fixed bed micro-reactor with FCC diesel as feedstock. The catalytic results confirmed that the catalyst NiMo/APAT-3 possessed the highest HDS efficiency (97.0%), due to synergistic effects of advantageous properties such as higher acidity, moderate MSI, and relatively short length of the MoS 2 slabs.