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.

The paper presents the results of an investigation into the kinetics of catalytic hydrogenation of vacuum residue at temperatures of 380, 400 and 420 °C and different durations, ranging from 30 to 70 min, using a nanocatalyst containing the active metals nickel and titanium supported on chrysotile. It was found that the yield of oils from 30 to 50 wt.% and tars from 12 to 18 wt.% increased with increasing temperatures and reaction times. A slight increase in the proportion of solids in the range of 2.0 to 6.0 wt.% is explained by the activity of the nanocatalyst used. In the study of the kinetics of vacuum residue hydrogenation, using the nanocatalyst developed by the authors, we were able to achieve a low yield of solids with a short contact time as well as a high yield of low-molecular-weight compounds such as oils and tars. To determine the kinetic parameters (rate constants and activation energies), Simpson’s integral method and a random search engine optimization method were used. High values of rate constants are characteristic of reactions in the formation of oils k1, tars k2 and asphaltenes k3 in the temperature range of 380–420 °C. The high values of the rate constants k1, k2 and k3 in the catalytic hydrogenation of the vacuum residue indicate the high reaction rate and activity of the nanocatalyst used. With an increase in temperature from 380 to 420 °C, the rate constant of the formation of gas products from vacuum residue and the conversion of asphaltenes into oils significantly increase, which indicates the accumulation of low-molecular-weight compounds in oils. The activation energy for reactions leading to the formation of oils, tars, asphaltenes, gas and solid products was 75.7, 124.8, 40.7, 205.4 and 57.2 kJ/mol, respectively. These data indicate that the processes of vacuum residue hydrogenation with the formation of oils and asphaltenes require the lowest energy inputs. Reducing the process temperature to increase the selectivity of the vacuum residue hydrogenation process when using the prepared nanocatalyst is recommended. The formation of oils at the initial stage plays a key role in the technology of the heavy hydrocarbon feedstock (HHF) hydrogenation process. Perhaps the resulting oils can serve as an additional solvent for high-molecular-weight products such as asphaltenes, as evidenced by the low activation energy of the process.

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 degrees & Scy; equal to 0.04, process temperature in the range of 420-430 degrees & Scy;, 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 degrees 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 optimal conditions of catalytic hydrogenation of oil sludge (Atasu-Alashankou) and the change in the kinematic viscosity of the fraction to 350℃ from the studied factors using the method of probabilisticdeterministic planning were experimentally determined. During the hydrogenation process of oil sludge, the maximum total yield of light fractions reached 62.1 %, and the kinematic viscosity decreased from 2.2 to 1.2 mm2/s. It was established the initial hydrogen pressure and the amount of added nanocatalyst microsilicate with cobalt (catalyst 1) have the greatest influence on the yield of the middle fraction from oil sludge under experimental conditions. It was shown that catalyst 1 increases the yield of diesel fraction components during the hydrogenation process of oil sludge. For the first time, we established the individual and group chemical composition of the fraction up to 350℃ before and after processing. The use of nanocatalyst 1 in amounts of 1.2–1.5 % led to an increase in the yield of the fraction up to 350℃ and diesel fraction components. This is due to the yield of paraffinic hydrocarbons increasing from 57.6 (initial fraction) to 80.7 %, as well as a decrease in aromatic hydrocarbons from 14.1 to 12.9 % and polycyclic aromatic hydrocarbons from 9.56 to 4.3 %.

The thermokinetic parameters of the thermal decomposition of primary coal tar (PCT) from AO Shubarkol Komir in the Republic of Kazakhstan in the presence of a microsilicate nanocatalyst were experimentally determined. The salts of Group VIII metals (iron, cobalt, and nickel) were preliminarily supported onto the surface of the nanocatalyst. The method of thermogravimetry in an inert atmosphere of nitrogen was applied. The thermokinetic parameters of the decomposition of PCT (activation energy, preexponential factor, and rate constants) found in the absence and presence of the nanocatalyst were calculated using thermogravimetric analysis methods. The experimental results of the kinetics of PCT decomposition can be used to develop a database for the mathematical modeling of the processing of this type of raw materials.

The activity and selectivity of the bimetallic NiCo/chrysotile catalyst during the hydrogenation of model objects (anthracene and phenanthrene) for 1 hour at an initial hydrogen pressure of 3 MPa and a temperature of 400 °C were studied. The chrysotile mineral used as a substrate for active centers of nickel and cobalt is a waste product of asbestos production at Kostanay Minerals JSC (the Republic of Kazakhstan). The catalyst was characterized by a complex of methods of physical and chemical analysis. The chrysotile mineral consists of nanotubes with an inner diameter of about 10 nm and an outer diameter of about 60 nm. The amount of hydrogenation products is 61.91 %, destruction — 15.08 % and isomerization — 8.37 % during the hydrogenation of anthracene. The amount of hydrogenation products is 26.09 %, and that of destruction is 2.51 % during the hydrogenation of phenanthrene. It was found that the catalyst selectively accelerates the hydrogenation reaction and allows increasing the yields of hydrogenation products. The schemes of the hydrogenation reaction of model objects were drawn up according to the results of gas chromatography-mass spectrometric analysis of hydrogenates.

Currently, there is an interest in effective technologies that cause minimal environmental harm, have low financial costs and allow you to obtain products with high added value. One of the ways to increase the yield of light and medium fractions from oil bottom sediments is to use the electrohydraulic effect. The electrohydraulic phenomenon is a new industrial method of converting electrical energy into mechanical energy, which occurs without the influence of intermediate mechanical links, with high efficiency. Statistical processing of experimental data was carried out with the identification of the optimal mode of the electrohydraulic effect on the destruction of the oil bottom sediment. The influence of various factors is shown (duration of contact, distance between electrodes, amount of added catalyst, capacitance of capacitor and value of applied voltage). The use of the generalized equation made it possible to determine the following optimal conditions for the destruction of the oil bottom sediment using electrohydraulic treatment: duration 7 min, distance 8 mm, amount of added catalyst 1.5 %, capacitance 0.3 μF, applied voltage 14 kV. In terms of the significance of the coefficient (tr), it should be noted that the dominant factors are the distance between the electrodes and the amount of added catalyst. The individual chemical composition of the light and medium fractions of the original oil residue and the processed oil residue was determined. Comparison of the individual chemical composition of fractions up to 200 °С and 200–300 °С, obtained from the oil bottom sediment and from the hydrogenated product, allows to conclude that the electrohydraulic effect has an effective effect on the destruction of the organic mass of the oil bottom sediment. The optimal conditions for electrohydraulic treatment of the oil residue aere established and it is shown that it is possible to utilize the oil bottom sediments

The hydrogen-donor abilities of polymers and the activity of catalysts in the process of thermal destruction of the organic mass of primary coal tar (PCT) are studied by non-isothermal kinetics methods. PCT,magnetic microspheres, nickel-deposited chrysotilechrysotile and Fe3O4nanocatalysts were used as initial raw materials. Рolymers such as polyethylene (PE), polystyrene(PS) and polyethylene glycol (PEG) were selected as a hy-drogen donor. The phases Mg3[OH]4{Si2O5} and NiO were determined by X-ray phase analysis (XRD) in the obtained catalyst (nickel-deposited chrysotile), and the presence of highly dispersed nickel oxide particles on the surface and inside the nanotubes was shown by the transmission electron microscope (TEM). Nickel oxide particles of 8–11 nmand 30–37 nmwere evenly distributed on the surface and inside the chrysotile nanotubes. The kinetic parameters of the thermal destruction of a mixture of PCT, catalyst and polymer material were determined on the basis of thermogravimetric analysis using the integral method and the method for determin-ing the thermokinetic parameters by the inflection point on the thermogravimetric curve(TG). The change in the activation energy, rate constant and pre-exponential factor with an increase in the degree of destruction of the organic mass of the PCT is established. It was shown that the nature of polymers and catalysts significantly affects the value of the rate constant and the activation energy. The calculated activation energies of the thermal destruction of a mixture of coal tar with PS and PE in the presence of a catalyst (nickel-deposited chrysotile) by the first method are 47.6 kJ/mol and 40.4 kJ/mol, and by the second method are 47.3 kJ/mol and 86.5kJ/mol respectively.

The aim of this work is to determine the hydrogen distribution in primary coke oven tar and its fractions. The hydrogen distribution in the primary coke oven tar of «ShubarkolKomir» JSC, its distillate fractions and dis-tillation residue have been determined by the methods of elemental analysis, IR and PMR spectroscopy. The atomic ratio of C: H in the primary coke oven tar is 0.79. All fractions of the tar contain a large amount of al-kyl-substituted aromatic compounds, phenols and other substances with alkyl groups. The initial tarcharac-terized by a high content of hydrogen in the α-and β-positions to the aromatic ring, 29% and 34% respec-tively, which indicates a large number of alkyl substituents in the aromatic rings and near double bonds. The total amount of aliphatic and aromatic hydrogen in the tar is 79% and 21% respectively. Olefinic hydrogen is presented in the initial tar in an amount of 8%. It is possible to make a choice of techniques for further processing (hydrogenation, coking, thermal cracking) to obtain products with high added value on the basis of determination of the elemental composition, quantitative distribution of hydrogen in the primary coke oven tar and its fractions by the using of above mentioned physical and chemical methods.

Experiment planning is the optimal control of an experiment in the context of incomplete information about the process mechanism. Interest in the science of experiment is associated with a wide range of experimental studies and a significant economic effect from the optimal organization of the experiment. An optimal experiment is a way to save time and cash, increase reliability of results. Middle fraction of Kumkol oil (200-300 degrees C) was used to study the cavitation effect on fuel oil. The following catalytic systems were used, namely, modified FeS2, nanocatalysts epsilon-Fe2O3/SiO2, alpha-Fe2O3/SiO2 spherical catalyst, beta-FeOOH, and Fe(OA)(3). By quantifying the individual composition of the middle fraction (200-300 degrees C) of Kumkol oil, a general pattern of the effect of catalytic-cavitation processing on the hydrocarbon composition of the middle fraction (200-300 degrees C) of Kumkol oil was established. The optimal conditions and a number of factors affecting the cavitation processing of the middle oil fraction (200-300 degrees C) in the presence of a FeS2 catalyst were determined. In accordance with the regression equation obtained, the optimal conditions for cavitation processing are the following: tau = 90-120 s, the amount of added catalyst is 0.7-1 g and the amount of added water is 1.5-2 ml.

The results of a study on the hydrogenation of a mixture of anthracene and phenanthrene in the presence of nanocatalysts (Fe 3 O 4 and β-FeOOH) and catalytic additives (microspheres obtained from the ash of coals from the Republic of Kazakhstan and nickel and cobalt additives supported on the microspheres) are presented. The efficiency of a wet mixing method for the preparation of nickel and cobalt oxide catalytic additives on the microspheres in the process of the hydrogenation of a mixture of anthracene and phenanthrene was shown. The hydrogenation process of a mixture of polyaromatic hydrocarbons was represented as a combination of hydrogenation and destruction reactions. The individual chemical composition of the hydrogenation products of a mixture of anthracene and phenanthrene was investigated. The activity and selectivity of the catalysts and catalytic additives in the hydrogenation process of a mixture of polyaromatic hydrocarbons were established.

Experimental results on the kinetics of hydrogenation of a wide fraction of coal tar (bp 230–300°C) in the presence of a Fe 3 O 4 nanocatalyst are presented. The rate constants, overall rate constants, and activation energies were calculated. It was established that the conversion of preasphaltenes into asphaltenes is the rate-limiting stage of the conversion of a wide fraction (230–300°C) of coal tar into reaction products. The process of converting the wide fraction (230–300°C) into products takes place in the kinetic region of a heterogeneous process.

Studies on the thermal destruction of a mixture of vacuum residue (tar) and primary coal tar (PCT) with and without Fe 3 O 4 and β-FeOOH catalytic additives, which were performed using thermogravimetry and differential scanning calorimetry in an inert atmosphere at a heating rate of 10 K/min, are reported. Based on the results of thermogravimetric analysis and the kinetic parameters of the process, activation energies were calculated, and these activation energies can be used in the development of methods for the technological calculation of reactors and the selection of construction materials for their manufacture.

The hydrocarbon feedstock consists of condensed aromatic hydrocarbons and other high-molecular compounds are a complex mixture of organic and mineral substances. In such systems it is quite difficult to describe the mechanism of the process of the activity and selectivity of selected catalysts. Model compounds (anthracene, phenanthrene, pyrene, naphthalene, and others.) facilitate the process of learning, depending on the reactivity of the chemical structure of substances as the organic fragments may represent a primary weight of coal tar and its fractions. The results of the hydrogenation polyaromatic hydrocarbon compound, and the calculations of kinetic and thermodynamic parameters of the process. The method of equilibrium-kinetic analysis allows you to link the equilibrium and kinetic characteristics and additional information from the usual array of experimental data, thus to intensify chemical research. Defined and calculated the forward and reverse constant velocity, the equilibrium constant, activation energy, and the thermal effects of the hydrogenation reaction pyrenein the presence of iron-containing catalyst in the temperature range 623-698 K, with an initial hydrogen pressure of 4MPa. References [1] Akhmetkarimova Zh.S. // Chemical Journal of Kazakhstan, 2014, 4. 121-127 (in Rus.). [2] Akhmetkarimova Zh.S., Baikenov M.I., Meiramov M.G., Ordabaeva A.T., Khrupov V.A., Muldakhmetov Zh.H. // Chemical Journal of Kazakhstan, 2015, 3. 202-206 (in Rus.). [3] Malyshev V.P., Shkodin V.G. The equilibrium-kinetic analysis of chemical processes. M.: Gylym, 1990. 112 p. (in Rus.). [4] Baikenov M.I., Baikenova G.G., Akhmetkarimova Zh.S. and other // Solid Fuel Chemistry, 2015, 3, 22-28 (in Rus.). [5] Ordabaeva A.T., Akhmetkarimova Zh.S., Meiramov M.G., Khrupov V.A., Muldakhmetov Zh.H., Dyusekenov A.M., Ma Feng Yun. // Bulletin of the Karaganda university. Chemistry series, 2017, 3(87). 126-130 (in Rus.). [6] Gudun K.A., Akhmetkarimova Zh.S., Feng-Yung Ma, Baikenov M.I. // Bulletin of the University. 2013. 1(69), 44-48 (in Rus.). [7] Gagarin S.G., Kirilina T.A., Krichko A.A. // Solid Fuel Chemistry. 1987, 3, 110-114 (in Rus.). [8] Baikenov M.I., Fengyun Ma, Akhmetkarimova Zh.S. // European Applied Sciences, 2013, 3, 71-73 (n Eng.). [9] Akhmetkarimova Zh.S., Fengyun Ma, Baikenov M.I. // Reports of NAS of RK, 2014, 1, 70-77 (in Rus.). [10] Dyusekenov A.M., Baikenov M.I., Akhmetkarimova Zh.S. and other // Bulletin of the University, 2016, 1(69), 40-44 (in Eng). [11] Malyshev V.P., Karimov L.M., Zhumashev K.Zh. // CUMR, 2011, 1(274), 61-70 (in Rus.). [12] Malyshev V.P. Probabilistic and deterministic mapping. Almaty: Gylym, 1994. 374 p. (in Rus.). [13] Malyshev V.P. // CUMR, 2009, 4(264), 61-71 (in Rus.). [14] Akhmetkarimova Zh.S., Muldakhmetov Zh.H., Baikenov M.I., Dyusekenov A.M. // Chemical Journal of Kazakhstan, 2016, 1. 331-336 (in Eng.). [15] Akhmetkarimova Zh.S., Muldakhmetov Z.M., Baikenov M.I. and other // News of NAS RK, 2016, 2, 23-29 (in Kaz.). [16] Lipovich V.G., Kalabin G.A., Kalechits I.V. Chemistry and processing of coal. M.: Chemistry, 1988, 336 p. (in Rus.). [17] Borah D., Barua M., Baruah M. K. // Fuel Process. Technol, 2005, 86.977–993 (in Eng.). [18] Karimova L., Karimov R. Equilibrium-kinetic analysis. M.: Lap Lambert Academic Publishing, 2014, 65 p. (in Rus.). [19] Ctromberg A.G., Semchenko D.P. Physical chemistry. M.: Higher School, 1988, 315 p. (in Rus.). [20] Zamanov V.V., Krichko A.A., Ozerenko A.A., Frosin S.B. // Solid fuel chemistry, 2005, 42, 67-70 (in Rus.).