Theoretical Insights into the Catalytic Effect of Transition-Metal Ions on the Aquathermal Degradation of Sulfur-Containing Heavy Oil: A DFT Study of Cyclohexyl Phenyl Sulfide Cleavage

[Image: see text] Steam injection is the most widely used technique for effectively reducing the viscosity of heavy oil in heavy oil production, in which in situ upgrading of heavy oil by aquathermolysis plays an important role. Earlier, transition-metal catalysts have been used for improving the efficiency of steam injection by catalytic aquathermolysis and achieving a higher degree of in situ oil upgrading. However, the unclear mechanism of aquathermolysis makes it difficult to choose efficient catalysts for different types of heavy oil. This theoretical study is aimed at deeply understanding the mechanism of in situ upgrading of sulfur-containing heavy oil and its catalysis. For this purpose, cyclohexyl phenyl sulfide (CPS) is selected as a model compound of sulfur-containing oil components, and, for the first time, a catalytic effect of transition metals on the thermochemistry and kinetics of its aquathermolysis is investigated by the density functional theory (DFT) methods with the use of the Becke three-parameter Lee–Yang–Parr (B3LYP), ωB97X-D, and M06-2X functionals. Calculation results show that the hydrolysis of CPS is characterized by fairly high energy barriers in comparison with other possible reaction routes leading to the cleavage of C–S bonds, while the heterolysis of C–S bonds in the presence of protons has a substantially lower kinetic barrier. According to the theoretical analysis, transition-metal ions significantly reduce the kinetic barrier of heterolysis. The Cu(2+) ion outperforms the other investigated metal ions and the hydrogen ion in the calculated rate constant by 5–6 (depending on the metal) and 7 orders of magnitude, respectively. The catalytic activity of the investigated transition-metal ions is arranged in the following sequence, depending on the used DFT functional: Cu(2+) ≫ Co(2+) ≈ Ni(2+) > Fe(2+). It is theoretically confirmed that transition-metal ions, especially Cu(2+), can serve as effective catalysts in aquathermolysis reactions. The proposed quantum-chemical approach for studying the catalytic aquathermolysis provides a new supplementary theoretical tool that can be used in the development of catalysts for different chemical transformations of heavy oil components in reservoirs due to hydrothermal treatment.