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.

The study investigates the effect of catalytic additives containing iron and titanium, derived from converter shop slag of Qarmet JSC, on the thermal destruction of a model mixture. A polymeric material, polyethylene, was used as a hydrogen donor. The thermal decomposition of a mixture consisting of phenanthrene and benzothiophene, in the presence of polyethylene and iron- and titanium-based catalytic additives, was examined using thermogravimetric analysis. It is shown that the decomposition of these organic systems, modeled using the Coats–Redfern method, reliably reflects their thermokinetic behavior and provides consistent results under statistical processing of experimental data. Catalytic additives exert a significant influence on the kinetics of thermal decomposition and degradation processes in the studied systems. It is demonstrated that the titanium-containing catalyst promotes a noticeable reduction in the reaction energy barrier and activation energy, whereas the iron-containing catalyst ensures high reproducibility and stability of the kinetic parameters. The applicability of the D3 model (three-dimensional diffusion) for the accurate description of the thermodestruction process has been established, and the reliability of the Monte Carlo method has been confirmed when accounting for experimental fluctuations. Additionally, it has been established that the introduction of catalysts substantially alters the degradation kinetics: the titanium-containing catalyst leads to a decrease in activation energy, while the iron-containing catalyst ensures maximum reproducibility of the determined kinetic parameters across a series of independent experiments.

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.