The study of thermal developments of heavy oil feedstock, vacuum residue in particular, is a relevant factor for the development of technologies for the processing and production of petroleum products. This paper investigates the process of thermal decomposition of the vacuum residue in the manufacturing of catalyst and polymer material using thermal analysis methods, including thermogravimetric analysis (TGA) in isothermal and dynamic modes. Particular attention is paid to the measurement of kinetic parameters of thermolysis using model and non-model methods, which allows us to assess the output power and other kinetic characteristics of decomposition. The results obtained can be used for the development of new oil refining technologies for significantly increasing the efficiency and safety of processes. During the course of this study, experimental and theoretical activation energy values were obtained for the vacuum residue without a catalyst (experimentally: 91.54 kJ mol⁻¹/theoretically: 91.35 kJ mol⁻¹) and a sample with the presence of a catalyst (experimentally: 89.68 kJ mol⁻¹/theoretically: 90.87 kJ mol⁻¹). The reduction in activation energy in the presence of the catalyst confirms its catalytic activity and potential for processing heavy hydrocarbon feedstock.

The laws of thermal degradation of the mixture of the heavy fraction of low-temperature coal tar and coal shale were investigated using dynamic thermogravimetry. The kinetic characteristics of the process were determined using various methods, including the Ozawa–Flynn-Wall, Friedman, non-parametric kinetics and Šesták–Berggren methods. It is shown that coal shale initiated changes in the kinetic parameters and decomposition rate of the heavy fraction of coal tar. It was found that a 13% content of coal shale in the mixture led to the maximum rate of weight loss of the heavy fraction of coal tar. A hydrodemetallization kinetic model of the mixture of the heavy fraction of low-temperature coal tar and coal shale is proposed. The kinetic parameters of the hydrodemetallization process were determined; in addition, the rate constants at various temperatures were estimated. The study shows that the distribution of trace elements in the hydrogenate from the initial mixture and in the hydrogenate from the solid residue was characterized by relatively low values of reaction rate constants. The maximum microelement distribution rate was achieved in the hydrogenate solid residue. Energy indicators of activation processes indicated that hydrodemetallization at low temperatures is advantageous from an energy point of view.

This paper presents the results of a study of the catalytic hydrogenation of phenanthrene using catalysts based on chrysotile modified with nickel and titanium (chrysotile/NiTi), as well as coal shale. Complex characterization of catalysts in terms of acid, texture and morphological properties was carried out. Pre-reduction in the catalysts has been found to increase the yield of partially and fully hydrogenated products, including tetrahydronaphthalene, trans-decalin and dihydrophenanthrene. Particular attention is paid to the role of coal shale as a donor source of hydrogen in thermolysis conditions. The results of hydrogenation revealed complex mechanisms of phenanthrene transformations, including partial saturation of aromatic rings, desulfurization and the formation of alkyl-substituted compounds. The obtained data emphasize the prospects of using the studied catalysts in the processes of processing heavy and solid hydrocarbon raw materials, which opens up opportunities for creating new technologies for the production of liquid fuel.

The optimal conditions for demetallization of the heavy fraction of coal tar from Shubarkol Komir JSC were determined by means of full factorial experiment. Optimal conditions for demetallization of the aforementioned fraction were found to be a proportion of “Coal shale” catalytic additive to the heavy fraction of coal tar with boiling point above 300 °С equal to 0.04, process temperature in the range of 420–430 °С, duration from 20 to 30 minutes and initial pressure between 3 and 5 MPa. Experiments conducted under these conditions demonstrated the demetallization rates of 87–89 %. Conversion of the heavy fraction of coal tar in hydrogen medium at pressure of 4.0 MPa and temperature of 420 °C was examined, with and without the use of the “Coal Shale” catalytic additive. The findings demonstrate that the incorporation of the “Coal Shale” catalytic additive is associated with a notable enhancement in the production of liquid hydrogenate, reaching up to 57 %. Atomic emission spectral analysis was used to investigate the content of rare and dispersed elements including Ge, Ga, Y, Yb, Zr, Nb the ash of the heavy fraction of coal tar and the “Coal shale” catalytic additive, as well as in the solid product of demetallization of the heavy fraction of coal tar using the catalytic additive. The results showed that the use of “Coal shale” as the catalytic additive leads to an increase in the content of Ga, Yb, Y elements by 3-3.8 times, and Zr — by 7.5 times compared to the initial heavy fraction of coal tar in the absence of the catalytic additive.

This study investigates the effect of controlled acid demineralization of coal shale from Shubarkol Komir JSC using HCl solutions with concentrations of 9–37% by mass on its structural characteristics, the kinetics of thermal decomposition, and the ability to concentrate rare and dispersed trace elements in the solid residue from the hydrodemetallization of the heavy fraction of coal tar. Analysis of IR spectroscopy, TG/DTG and isoconversional kinetics showed that acid treatment leads to the removal of carbonate and partially iron-containing phases while maintaining the aluminosilicate framework, increasing the structural uniformity of the matrix and moving to a more ordered thermal decomposition mechanism. The activation energy in the range of α = 0.1–0.7 is 83–87 kJ/mol for all modified samples, increasing to 96.20 kJ/mol at α = 0.9 for CS100. It has been established that the ability of coal shale to concentrate rare and dispersed trace elements in the solid residue of hydrodemetallization changes non-monotonically: the total content of trace elements reaches a maximum of 1452.19 g/t with moderate acid treatment (CS50) and sharply decreases to 137.85 g/t with deep demineralization (CS100). It has been shown that the degree of acid treatment acts as a controlled parameter that allows for purposefully regulating the ability of coal shale to concentrate rare and dispersed trace elements in the process of hydrodemetallization of heavy hydrocarbon raw materials.

This study presents an integrated approach to processing the heavy fraction of coal tar (HFCT) using oil shale (OS) from Shubarkol Komir JSC to simultaneously increase the yield of valuable hydrocarbon fractions and extract rare and dispersed trace elements. The lack of data on the effect of shale on the process and the kinetics of multi-component “tar + shale” systems limits the development of effective technologies. TG/DTG analysis was combined with the Friedman, Ozawa–Flynn–Wall, and Šesták–Berggren methods for the first time to evaluate the role of oil shale (OS). It was shown that the addition of 13% OS provides a sustained reduction in activation energy (~85–86 kJ/mol) and optimal conditions for hydrometallization. At 420 °C, an initial H₂ pressure of 4 MPa, and a reaction time of 60 min, the yield of light fractions reaches 62.6%, and the solid residue concentrates Ti, Mo, Ge, and other rare and dispersed elements reach up to 66,000 g/t in total. The possibility of extracting Ge using the Purolite C100 sorbent has also been confirmed. The novelty of the study lies in demonstrating the donor–catalytic effect of shale and the practical prospects of solid residue as a secondary mineral raw materials.