The generation of hydrogen from unconventional oil is expected to increase significantly during the next decade. It is commonly known that hydrogen is an environmentally friendly alternative fuel, and its production would partially cover the gap in energy market requirements. However, developing new cheap catalysts for its production from crude oil is still a challenging area in the field of petroleum and the petrochemical industry. This study presents a new approach to synthesizing and applying promising catalysts based on Ni, Co, and Ni-Co alloys that are supported by aluminum oxide Al₂O₃ in the production of hydrogen from extra-heavy crude oil in the Tahe Oil Field (China), in the presence of supercritical water (SCW). The obtained catalysts were characterized via scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, transmission electron microscopy (TEM), and, X-ray diffraction analysis (XRD). The obtained XRD data showed 3.22% of Co²⁺ in the Co/Al₂O₄ catalyst, 10.89% of Ni²⁺ in the Ni/Al₂O₄ catalyst, and 1.51% of Co²⁺ and 2.42% of Ni²⁺ in the Ni-CoAl₂O₃ bimetallic catalyst. The BET measurements of the obtained catalysts showed a surface area ranging from 3.04 to 162 m²/g, an average particle size ranging from 0.037 to 0.944 µm, and micropore volumes ranging from 0.000377 to 0.004882 cm³/g. The thermal, SCW, and catalytic upgrading processes of the studied samples were conducted in a discontinuous autoclave reactor for 2 h at a temperature of 420 °C. The obtained results revealed that thermal upgrading yielded 1.059 mol.% of H₂, and SCW led to 6.132 mol.% of H₂; meanwhile, the presence of Ni-CoAl₂O₃ provided the maximal rate of hydrogen generation with 11.783 mol.%. Moreover, Ni-CoAl₂O₃ and NiAl₂O₃ catalysts have been found to possess good affinity and selectivity toward H₂ (11.783 mol.%) and methane CH₄ (40.541 mol.%). According to our results, the presence of SCW increases the yield of upgraded oil (from 34.68 wt.% to 58.83 wt.%) while decreasing the amount of coke (from 51.02 wt.% to 33.64 wt.%) due to the significant amount of hydrogen generation in the reaction zone, which reduces free-radical recombination, and thus, improves oil recovery. Moreover, the combination of SCW and the synthetized catalysts resulted in a significant decrease in asphaltene content in the upgraded oil, from 28% to 2%, as a result of the good redistribution of hydrogen over carbons (H/C) during the upgrading processes, where it increased from 1.39 to 1.41 in the presence of SCW and reached 1.63 in the presence of the Ni-CoAl₂O₃ catalyst. According to the XRD results of the transformed form of catalysts (CoNi₃S₄), after thermal processing, heteroatom removal from extra-heavy crude oil via oxidative and adsorptive desulfurization processes is promoted. These findings contribute to the expanding body of knowledge on hydrogen production from in situ unconventional oil upgrading.

Co-Mo/γ-Al₂O₃ catalysts with different pore shapes were synthesized for the ex situ upgrading of extra heavy oils by hydrodesulfurization (HDS), hydrodemetallization (HDM), and hydrodeasphaltization (HDA). The catalysts were synthesized using aluminum oxides that were prepared by various methods. It was found that using the product obtained by the thermochemical activation of gibbsite leads to the formation of slit-shaped pores in aluminum oxide, while the application of the hydroxide deposition method by the precipitation of sodium aluminate and nitric acid gives cylindrical pores in aluminum oxide. Co-Mo catalysts synthesized using these two types of pores exhibit different catalytic activities. The catalyst synthesized on a carrier with cylindrical pores exhibited a higher catalytic activity in sulfur, heavy metals, and asphaltenes removal reactions that are synthesized on a carrier with slit-like pores. This is because the presence of cylindrical pores leads to a decrease in diffusion restrictions when removing large molecules of asphaltenes and sulfur-containing and metal-containing compounds.

Highly porous cellular material (α-Al₂O₃-HPCM) support was synthesized by the template method. Highly porous support was used for the synthesis of the catalyst. A thin secondary layer with 25–30 μ thick γ-Al₂O₃ and zeolite Y was applied on the α-Al₂O₃-HPCM surface ((γ-Al₂O₃ (85%)-zeolite Y (15%))/α-Al₂O₃-HPCM). The catalyst based on the highly porous support was tested in a process of decreasing oil viscosity. The catalyst in the form of cylindrical granules and a thermal process of decreasing oil viscosity without the catalyst were used as the basis for comparison. α-Al₂O₃-HPCM in the catalyst provides low-quantity pores (d < 10 nm) and a quantity of general acid centers compared with the granular catalyst. On the other hand, it shows a more significant oil viscosity decrease (from 2500 to 41 cPs) and a low rate of gas generation (137 mL/h) for the catalyst with highly porous support. A high oil fraction was observed in the presence of the (γ-Al₂O₃-zeolite Y)/α-Al₂O₃-HPCM compared to the granular catalyst. The presence of large transport cells (pores) 1500–2000 μ for the catalyst based on highly porous support allowed a work period four times longer than that of experiment only with temperature without catalysts.

The effect of the morphological, textural, and acid characteristics of a support prepared from a composite of alumina and a nickel-containing highly porous permeable cellular material (HPCM) on the electronic and geometric properties of supported palladium particles and their activity in the selective hydrogenation of acetylene is studied. It is found that a δ-Al₂O₃/Ni-HPCM support ensures the formation of a more uniform charge state distribution of the active component in comparison with the conventional catalysts supported on pure δ-Al₂O₃, i.e., palladium particles with surface atoms that have a higher electron density on the valence orbitals. This state of the active component is responsible for the high selectivity of the hydrogenation of acetylene to ethylene in the ethane-ethylene fraction when using a Pd/δ-Al₂O₃/Ni-HPCM catalyst; this selectivity is 78.3%, which is 35.7% higher than that of the process using a catalyst based on conventional δ-Al₂O₃.

KGS-3 catalyst is tested in the selective hydrogenation of methylacetylene and propadiene contained in industrial pyrolysis propane-propylene fractions at a pilot installation in two successive adiabatic flow reactors equipped with immobile catalyst beds. The optimum technological conditions for hydrogenation are determined, ensuring a residual content of acetylene and diene admixtures of no more than 5 ppm: pressure in the system, 18 atm; hydrocarbon feedstock hourly space velocity (HSV), 2100 h⁻¹; molar ratio of hydrogen to the sum of methylacetylene and propadiene in the first and second reactors, respectively, 1.1 : 1.0 and 1.6 : 1.0; temperatures, 50 and 55 °C. Under these conditions, KGS-3 catalyst ensures 100% conversion of methylacetylene and propadiene with a propylene selectivity of 76.7%. The expected service life of this catalyst is about 14 months. The catalyst can be used for the purification of hydrocarbon fractions containing up to 5 wt % of acetylene and diene admixtures.