The model experiments regarding the conversion of organic matters from carbonate rock samples of Dankov-Lebedyan deposits of Zelenogorskaya area and siliceous-carbonate rocks of Semiluki-Mendym deposits of Berezovskaya area of Domanic formations of Romashkino oil field were carried out. Two types of experiments were carried out: (1) the hydrothermal treatment of rocks at a temperature of 350°C in the presence of carbonic acid and a water content of 30%; (2) pyrolysis at temperatures of 350 and 600°C in the presence of hydrogen. The yield and quality of extracted hydrocarbons from the rocks depending on the mineral composition of rocks, content and composition of organic matter, and thermal stability of kerogen under hydrothermal influences were evaluated. Application of electron paramagnetic resonance in pyrolysis processes revealed the difference in mineral content of rocks (Mn2+, SO3−, and SO2− ions) and free radicals R∗, as well as in vanadyl ion (VO2+) concentration. It is established that an increasing temperature of pyrolysis promotes the formation of new free organic radicals in rock samples: in Domanic rocks of Semiluki-Mendym deposits at 350°С and in carbonate rocks of Dankov-Lebedyan horizon at 600°С. This indicates different ability of oil-generating potential of rocks with hydrothermal and pyrolysis technologies.

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The physical simulation of heavy oil catalytic aquathermolysis with different chemical compositions from deposits located in the Tatarstan Republic, Russia (Ekaterinovsky oil, B 2 type, and Olimpiadovsky oil, A 1 type), was designed. The catalytic aquathermolysis processes were conducted at a temperature of 300 °C in the presence of a rock-forming additivekaolin (the content of montmorillonite was 44%), and catalysts composed of transition metal (Fe, Co, and Cu) carboxylates. The environment of the processes was a mixture of carbon dioxide and water vapor. The distinctive features of hydrothermal-catalytic conversion of various oil types are evaluated by fractional, structural-group, microelement compositions, and H:C ratio changes. These variations are due to initial properties of crude oils and the activation degree of destruction reactions on C−C, C−N, C− O, and C−S bonds leading to different levels of increase of saturated fractions content and decrease of resins and asphaltenes content in the products of experiments. By the thermal analysis method, the assessment of potential content of the oil on a solid sorbent before and after experiments was carried out. The high-molecular-weight components of the naphthene-aromatic B 2 type oil revealed greater adsorption capacity to the rocks, in comparison with the oil of the A 1 type. Therefore, the adsorption of catalyst components on rocks is also greater.

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In this study, the specific features of Ashal’cha heavy oil conversion were revealed. The hydrothermal catalytic experiments were carried out in a CO2 environment and in the presence of oil-soluble carboxylate metals such as Fe, Co, and Cu at the temperature of 300 °C. The results have shown that the catalyst and minerals of reservoir rocks have significant impact on the transformation behavior of group, structural group, and hydrocarbon compositions of oil. The most significant changes in the composition of heavy oil were established after hydrothermal treatment in the presence of a rock-forming additive, clay mineral (kaolin), which are reflected in a significant increase in the content of saturated and aromatic hydrocarbons and a decrease in the content of resins and asphaltenes. Furthermore, the changes in the structure of asphaltenes led to the increase of aromaticity and oxidation degrees. It was found that the catalyst metals mainly concentrate on the asphaltene structures and on the rock-forming reservoir minerals. It has been shown that the concentration of Fe increases up to 5.84% and that of Cu from 0 to 0.25% after catalytic treatment of oil with kaolin. A similar change was observed in the asphaltene content of rock extracts where Fe and Cu concentrations reach 1.38 and 0.31%, respectively, with no Co presence in asphaltene content. The number of catalytically active metals such as Ti, Fe, Cr, Mn, Co, Ni, Cu, Zr, and Ba was found in the rock obtained after the experiment and the extraction of organic matter. Moreover, a slight decrease from 2.27 to 1.93% in Fe concentration included in the catalytic complex has been established with an increase in Co and Cu concentrations, which were practically absent in the original rock, to 0.036 and 0.038%, respectively. It has been established as well that the studied metal complexes (Fe, Co, and Cu) with carboxylate ligands can penetrate not only into the pore space of the rock but also into asphaltenes, thereby allowing them to catalyze the process of heavy oil upgrading under hydrothermal conditions.

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