In order to evaluate the possibility of using different catalysts prepared for the hydrogenation process of primary coal tar, the method of differential thermal analysis was used, which allows to determine the kinetic parameters of thermal destruction, such as the rate constant, activation energy, and pre -exponential multiplier. The effect of catalysts on characteristics of mass loss during heating of "Shubarkol Komir" JSC primary coal tar at a constant speed (20 K/min) in a nitrogen medium has been considered. Microsphere, NiO/microsphere, CoO/microsphere, chrysotile and NiCo/chrysotile have been taken as catalytic additives. In the presence of the catalysts, the rate of thermal destruction of primary coal tar increases in the following order: CoO/microsphere < NiO/microsphere < NiCo/chrysotile. While microsphere catalysts extend the range of thermal destruction, chrysotile catalysts lead to the rapid completion of the destruction process. This fact is characterized by the formation of bonds between catalytic additives and primary coal tar. It is important to determine such parameters that affect on the activation energy and macrokinetics of the thermal decomposition process for prediction of catalyst activity during hydrogenation of heavy hydrocarbon raw materials.

Herein, we disclosed a method of preparing a nanocatalyst containing nickel-cobalt by impregnation in a hydrochloric acid medium. Optimal conditions were established for all stages of nanocatalyst preparation using the method of probabilistic–deterministic experiment planning: hydrochloric acid concentration—1 mol/L, ratio of HCl concentration to nickel concentration—20, ratio of HCl concentration to cobalt concentration—20. The method of planning the experiment of preparing a nanocatalyst allows varying all the factors simultaneously and obtaining quantitative estimates of the main effects and effects of interaction, as well as establishing the dominant factors affecting the activity and selectivity of the nanocatalyst during the hydrogenation of benzothiophene. The multifactorial equation was obtained, which allowed us to calculate the optimal manufacturing parameters of the nanocatalyst, providing high activity and selectivity during the hydrogenation of benzothiophene. In the proposed nanocatalyst, a readily available natural chrysotile–asbestos with a nanotube diameter of 60–75 nm was used as a carrier for the benzothiophene hydrogenation process.

Влияние наноразмерного порошка железа на процесс термической деструкции дистиллята каменноугольной смолы было определено методом термогравиметрического анализа. Дистиллят каменноугольной смолы был получен простой перегонкой до 350°C первичной каменноугольной смолы Шубаркульского месторождения. Наноразмерный порошок был получен электрохимическим восстановлением железа из сульфатных электролитов при одновременном воздействии высоковольтных электрических разрядов на катодную зону. Методом сканирующей электронной микроскопии было установлено, что порошок железа состоит из наноразмерных частиц (30-124 нм), образующих агрегаты. С помощью рентгенофазового анализа было установлено, что полученный порошок железа состоит в основном из фаз α-Fe и FeO(OH). Определение среднего размера кристаллитов было произведено с помощью уравнения Шеррера и в результате расчетов средний размер кристаллитов составил 31,7 нм. Полученный порошок железа добавляли к дистилляту каменноугольной смолы в количестве 1% от массы дистиллята и затем эту смесь подвергали термическому разложению при скоростях нагрева 5, 10 и 20°C/мин в инертной атмосфере. Обработка полученных данных проведена с использованием модельного метода Коутса-Редферна. Значения энергии активации были рассчитаны с помощью линейной аппроксимации, построенной в результате обработки термоаналитических данных. Установлено, что при добавлении наноразмерного порошка железа в количестве 1% к дистилляту каменноугольной смолы происходит снижение энергии активации со 153,98 кДж/моль до 84,48 кДж/моль.

Impact of the nanosized iron powder on the process of thermal degradation of coal tar distillate was determined by the thermogravimetric analysis. Coal tar distillate was obtained by simple distillation up to 350°C of primary coal tar from the Shubarkol deposit. Iron powder was obtained by electrochemical reduction of iron from sulfate electrolytes at simultaneous impact of high-voltage electric discharge on cathodic zone. Scanning electron microscopy showed that iron powder consists of nanosized particles (30-124 nm) forming aggregates. X-ray diffraction analysis revealed the presence of α-Fe and FeO(OH) phases. The average crystallite size determination was made using Scherrer equation and amounted to 31.7 nm. Obtained iron powder was added to the coal tar distillate in amount of 1% of distillate weight and this mixture was subjected to thermal degradation at heating rate 5°C/min in an inert atmosphere. Processing of the data obtained was carried out using the model-fitting Coats-Redfern method. The values of activation energy were calculated from the linear approximation constructed as a result of processing thermoanalytical data. It was found that the addition of iron powder in amount of 1% to the coal tar distillate reduces the activation energy from 153.98 kJ/mol to 84.48 kJ/mol.

The object of research is the process of thermal degradation of oil sludge in the presence of heterogeneous catalysts. The creation of efficient technological processes for processing the organic part of oil sludge into motor fuels, raw materials for petrochemicals and the disposal of microsilicate is an important urgent task, the solution of which will allow to obtain a significant economic and environmental effect. The problem to be solved is to establish the general kinetic laws of the process of thermal degradation of oil sludge in the presence of microsilicate with deposited metals. The advantage of the Ozawa– Flynn–Wall method is that it is possible to determine the kinetic parameters for each value of oil sludge conversion, that is, for different stages of thermal degradation. The activation energy of oil sludge 67.1 kJ/mol, and with a catalyst 59 kJ/mol are calculated for each degree of conversion (α), respectively. The value of the correlation coefficient was (R2≥0.997) provides good convergence with experimental results. Compared with other methods of thermal processing of oil sludge, catalytic thermal degradation has a number of advantages: relatively low process temperatures (400–650 °C), low sensitivity to the composition of raw materials and the processing process, which meets all modern requirements of chemical production. Regularities of thermokinetic parameters of thermal decomposition of oil sludge were studied using raw materials obtained during the process of oil transportation, in the presence of catalyst with applied metal (nickel, iron, cobalt) to microsilicate. Obtained results of oil sludge decomposition kinetics can be used in creating a database for mathematical modeling of process of heavy hydrocarbon raw materials processing

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.

The calculated thermodynamic functions of a primary coal tar fraction with a final boiling point of 300°C were presented for the modeling of hydrogenation products using an additive method. Based on model reactions of the hydrogenation of o -cresol, it was demonstrated that the hydrogenation of an aromatic ring is more likely than the hydrogenolysis of the bonds of methyl and hydroxyl groups with the aromatic ring in a temperature range of 700 K. The heat capacity, enthalpy, entropy, and Gibbs energy were calculated for the total composition of coal tar with a final boiling point of 300°C taking into account the additivity of thermodynamic functions in a temperature range of 298–1000 K. It was shown that these data can be used in the process modeling of the hydrogenation conversion of the primary coal tar fraction.

The paper provides experimentally determined thermokinetics of the thermal decomposition of high-viscosity oil (HVO) from the Karazhanbas field, the Republic of Kazakhstan, in the presence of a Fe3O4 nanocatalyst, catalytic additives (nickel catalytic additives in microspheres prepared from coal ash), and polymers (such as polyethylene glycol and polystyrene) as hydrogen donors. The HVO decomposition thermokinetics (activation energy, pre-exponential factor, and rate constants), depending on the presence of nanocatalysts, catalytic additives, and/or polymers, were estimated by thermogravimetry methods in an inert nitrogen atmosphere. The experimental data (including HVO weight loss and weight loss rate vs. temperature) and the estimated thermokinetics of HVO decomposition can be used to create a database appropriate for mathematical modeling of the processing of HVO and heavy oil residues.

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.

The kinetics of coal hydrogenation from the Shenghua deposit (People's Republic of China) has been studied. To calculate the kinetic parameters, experimental data on the hydrogenation of coal from the Shenghua field have been used. The hydrogenation process was carried out at a pressure of 5 MPa, at temperatures from 350 to 440 0C using a batch reactor. Tetrahydronaphthalene was used as a solvent and donor in the process of coal hydrogenation. The rate constants were calculated using the random search optimization method and the integral Simpson method. It was found that the previously calculated rate constants of the hydrogenation of Shenghua coal (Runge-Kutt method) differ from our data by one order of magnitude. It is supposed that our calculated values of the rate constants are more reliable and adequate than those obtained by the Runge-Kutt method. The limiting rate of coal hydrogenation is observed for the stage of coal conversion into a mixture of gas and oil.

The kinetics of an intermediate fraction of coal tar with a boiling point of 230–300°C in the presence of a Fe3O4 nanocatalyst was studied. The rate constants of cavitation processing of coal tar were calculated using the Simpson method with a random search optimization, and the apparent activation energy of the cavitation process with the intermediate fraction of coal tar was determined. The effects of temperature, processing time, and the Fe3O4 nanocatalyst on the yield of polyaromatic hydrocarbons were shown.

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.

This paper shows the effectiveness of the synthesized catalytic additives in the process of hydrogenation of phenanthrene in the presence of ethanol as a hydrogen donor. Ferrosphere, NiO/SiO2 covered the surface of ferrosphere and Fe2O3/SiO2 covered the surface of ferrosphere were used as catalytic additives. Ferrosphere was extracted from energy ashes of Karaganda thermal power plant. NiO/SiO2 and Fe2O3/SiO2 covered the ferrosphere were prepared by the method of "wet mixing". The phase composition, surface morphology, average size and distribution of particles of ferrospheres and nanocatalytic additives NiO/SiO2 and Fe2O3/SiO2 covered the ferrospheres were determined. The composition of the reaction products was determined by the method of chromato-mass spectrometry on the gas chromatograph of Agilent Technologies 7890A with mass spectrometric detector 5975C. Identification of the substances was carried out using the NIST 98 mass-spectral database. A synergistic effect of nanocatalytic additives NiO/SiO2 and Fe2O3/SiO2 covered the ferrospheres was established. The high degree of phenanthrene conversion is observed on the hydrogenation in the presence nickel and iron catalytic additives on the ferrosphere. According to the results of hydrogenation of phenanthrene efficiency range of the catalytic additives was built: NiO/SiO2 on the ferrosphere > > Fe2O3/SiO2 on the ferrosphere > NiO/SiO2 > Fe2O3/SiO2 > ferrosphere.

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.