Heavy oil resources are attracting considerable interest in terms of sustaining energy demand. However, the exploitation of such resources requires deeper understanding of the processes occurring during their development. Promising methods currently used for enhancing heavy oil recovery are steam injection methods, which are based on aquathermolysis of heavy oil at higher temperatures. Regardless of its efficiency in the field of in situ upgrading of heavy oil, this technique still suffers from energy consumption and inefficient heat transfer for deeper reservoirs. During this study, we have developed a molybdenum-based catalyst for improving the process of heavy oil upgrading at higher temperature in the presence of water. The obtained catalyst has been characterized by a set of physico-chemical methods and was then applied for heavy oil hydrothermal processing in a high-pressure reactor at 200, 250 and 300 °C. The comparative study between heavy oil hydrothermal upgrading in the presence and absence of the obtained molybdenum-based oil soluble catalysts has pointed toward its potential application for heavy oil in situ upgrading techniques. In other words, the used catalyst was able to reduce heavy oil viscosity by more than 63% at 300 °C. Moreover, our results have demonstrated the efficiency of a molybdenum-based catalyst in improving saturates and light hydrocarbon content in the upgraded oil compared to the same quantity of these fractions in the initial oil and in the non-catalytically upgraded oil at similar temperatures. This has been explained by the significant role played by the used catalyst in destructing asphaltenes and resins as shown by XRD, elemental analysis, and gas chromatography, which confirmed the presence of molybdenum sulfur particles in the reaction medium at higher temperatures, especially at 300 °C. These particles contributed to stimulating hydrodesulphurization, cracking and hydrogenation reactions by breaking down the C-heteroatom bonds and consequently by destructing sphaltenes and resins into smaller fractions, leading to higher mobility and quality of the upgraded oil. Our results add to the growing body of literature on the catalytic upgrading of heavy oil in the presence of transition metal particles.

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.