The mesoporous aluminosilicates Al-HMS (Si/Al = 10) and Al-MCM-41 (Si/Al = 20) types were synthesized via the neutral templating pathway and used as supports for Ni-Mo sulfide catalysts, prepared by standard incipient wetness co-impregnation technique followed by sulfidation procedure. Ni and Mo content were 7 and 24 wt.% respectively. Both mesoporous aluminosilicates and supported oxide Ni-Mo catalyst precursors were characterized by TEM, solid-state Si-29 and Al-27 MAS NMR, N-2 adsorption/desorption, TPD-NH3, TPR-H-2, ICP-AES techniques. The chemical state and surface composition of freshly sulfided catalysts were revealed by XPS and TEM. The performance of mesoporous Al-HMS and Al-MCM-41 supported Ni-Mo sulfide catalysts in hydro-conversion of 1-methylnaphtalene (1 MN), 2- methylnaphthalene (2 MN) and dibenzothiophene (DBT) was studied in high-pressure batch reactor at T = 320-400 degrees C, P(CO) = 3-5 MPa in the presence of water (20 wt.%) providing in situ hydrogen generation through a water gas shift reaction (WGSR). The results obtained showed that Al-HMS-based catalysts are more active in hydrogenation of aromatics while the higher DBT conversions were obtained over Al-MCM-41 supported catalyst. Mo-containing supported catalysts promoted by Ni were found the most active at T = 380 degrees C, P(CO) = 3 MPa and CO/H2O molar ratio 1.5-2.0.

The activity of unsupported Ni–Mo sulfide catalysts formed during the in situ decomposition of oil-soluble precursors (molybdenum hexacarbonyl, nickel naphthenate) in the hydrogenation of aromatic and naphthene-aromatic compounds is studied. The catalysts are characterized by HRTEM and XPS. Catalytic experiments are conducted at temperatures of 340–380°C and an increased pressure of ?? in the presence of water providing the in situ generation of hydrogen via the water-gas shift reaction. The catalysts exhibit a high activity in the hydrogenation of model substrates (methyl- and dimethyl-substituted naphthalenes and anthracene).

The activity of unsupported Ni–Mo sulfide catalysts is studied in the hydroconversion of benzothiophene and dibenzothiophenes in the temperature range of 340–380°С and at an increased H2 pressure and in the СО/H2О system. The structure of dispersed catalysts formed by the in situ high-temperature decomposition of oil-soluble precursors (molybdenum hexacarbonyl, nickel naphthenate) is investigated by TEM. Effects of СО/H2О molar ratio, water mass content in the system, and CO pressure on the activity of the catalysts and yields of the products are explored. It is shown that, in the СО/H2О system, the highest conversion of benzothiophene and dibenzothiophene is attained at a temperature of 380°С, a СО pressure of 5 MPa, and a СО/H2О molar ratio of 2. The introduction of alkyl substituents into a dibenzothiophene molecule causes a reduction in the rate of reaction that predominantly occurs via the hydrogenation of aromatic rings. The catalyst activities in hydrogenation under H2 pressure and in the СО/H2О system are comparable.