The possibility of regeneration of the catalysts for dehydrogenation С9–С14 paraffins was investigated. The catalysts were prepared on the basis of the active metal (platinum) and promoters supported on Al2O3 or (magnesium) aluminosilicates. The factual data of catalysts runs is used in industrial environments. The stages of coke burning and oxychlorination were investigated using thermogravimetric analysis and a method of mathematical modeling. It is shown that in the way of correct mode of regeneration the lifetime of the catalyst can be extended by 25–30 %. The way of reconstruction of dehydrogenation unit was proposed to allow the regeneration including burning of coke and oxychlorination.

When operating the reforming units with continuous catalyst regeneration there is the problem of optimizing the multiplicity of the catalyst circulation in the reactor-regenerator. This problem can be solved with a combination of natural and computer simulation through a study of the formation of coke on the catalyst surface. Based on the results of TGA of the industrial catalyst Pt-Sn/γ-Al2O3 concluded that amorphous coke is formed on the catalyst surface in reforming process, the whose number of coke at the outlet of the reactor block is 4–6 % depending on the composition of need materials and process parameters. The specific surface area of samples (m2/g): for the original – 152, after regeneration – 140, at the outlet of the reactor – 118, which correlates with the amount of coke on the surface of the samples. Mathematical analysis of processes of coke formation in the reforming reactor, a moving granular bed showed that the multiplicity of the catalyst circulation should be maintained in the range 0,008–0,010 m3/m3 to improve the efficiency of industrial plant. Maintaining the optimum conditions in the reactor and regenerator unit will allow to control the coke formation and to maintain the coke concentration on the minimum possible, and specific surface area of the catalyst at the highest possible level.

A procedure for calculating octane numbers of commercial gasolines with due regard for the intensity of interaction between molecules of blend components, and the mechanism of interaction of interaction of anti-knock additives with hydrocarbons is elaborated. Based on the models developed, a computer program is created for optimization of the process producing high-octane gasoline. The program allows quick and precise determination of the optimum ratio of components, which ensures production of commercial gasolines that meet all the requirements of regulatory documents.

Extending the life of the industrial catalyst is possible by improving the technological conditions of its operation. This will help eliminate possible factors deactivation of the catalyst. Feature of the process of catalytic dehydrogenation of hydrocarbons is unsteady due to the deactivation of the catalysts.The article presents the results of the simulation of industrial process catalytic dehydrogenation of higher alkanes C9–C14 – a key stage in the production of linear alkyl benzene. Described in stages: 1) thermodynamic analysis of the reactions by quantum chemistry methods, 2) estimation of parameters of the kinetic model solution of the inverse kinetic problem, 3) the choice of catalyst deactivation by coke of the equation, 4) development of methods to increase the resources of the dehydrogenation catalyst with time-dependent model based on quantitative records added to the water reactor in the range 470–490 °C. Proposed on the basis of these models, technological system of higher alkanes dehydrogenation allows calculation of the forecast of the reactor under different conditions of water supply. It is shown that when water resource is increasing portions of the catalyst is increased by an average of 20–30 %.

Results of thermodynamic analysis and mathematical simulation of the deactivation of a platinum dehydrogenation catalyst by coke-generating compounds are presented. An approach to increasing the catalyst on-stream time has been proposed, suggesting implementation of a procedure for calculating the optimal flow rate of water fed to the reactor to maintain the conditions of thermodynamic equilibrium of the coke formation reaction and oxidation of intermediate condensation products with water.

The service life of an industrial catalyst can be prolonged by improving the technological conditions of its operation. This allows us to maximally eliminate the catalyst deactivation factors. A specific feature of the catalytic dehydrogenation of hydrocarbons is its nonstationarity produced by the deactivation of catalysts. The results of modeling the industrial catalytic process of C9-C14 paraffin dehydrogenation—the key stage in the production of linear alkylbenzenes—is discussed in this paper. We consider (1) thermodynamic analysis of reactions by means of quantum chemistry, (2) estimation of the kinetic model’s parameters by solving the inverse kinetic problem, (3) selection of an equation that describes the coke deactivation of a catalyst, and (4) development of a method for increasing the service life of a dehydrogenation catalyst using a nonstationary model based on the quantitative consideration of the water added to a reactor within a temperature range of 470–490°C. The higher alkane dehydrogenation flowsheet proposed on the basis of these models allows us to predict the operation of a reactor in different water supply regimes. It is shown that the service life of a catalyst grows by 20–30% on the average, if water is fed by increasing portions.

Исследован процесс низкотемпературного синтеза метанола на Zn-Cu-Al-катализаторе. На основании современных представлений о поверхностном механизме синтеза составлена схема превращения веществ на катализаторе. Разработана математическая модель реактора синтеза метанола, реализованная в виде компьютерной программы. Модель составлена с учетом того, что в реакторе реализуется режим идеального вытеснения, отсутствуют внутридиффузионные осложнения и процесс протекает в кинетической области. С использованием промышленных данных с установки М-750 проведена проверка математической модели на адекватность. Адекватность разработанной модели подтверждается разницей между промышленными и расчетными концентрациями веществ, которая не превышает 0,5 % мольн. Разработанная компьютерная программа универсальна и применима для всех подобных реакторов синтеза метанола различной производительности.

During the operation of continuous catalyst regeneration reformers, the problem of optimizing the catalyst circulation ratio in the reactor-regenerator system arises. This problem is solved by a combination of real and computational experiments to investigate the regularities of coking on a catalyst’s surface. Based on TGA results for industrial Pt-Sn/γ-Al 2 O 3 catalyst, it is concluded that amorphous coke is formed on the catalyst’s surface during reforming, its quantity at the reactor block outlet being 4–6%, depending on the feed composition and technological parameters of the process. The specific surface of samples is 152 m 2 /g for the fresh catalyst, 140 m 2 /g after regeneration, and 118 m 2 /g at the reactor outlet, which correlates with the quantity of coke on the surface of samples. Mathematical analysis of the coking processes in a reformer with a moving bed show that the catalyst circulation ratio must be maintained in the range of 0.008–0.010 m 3 /m 3 to increase the operating efficiency of an industrial unit. Maintaining optimal conditions enables us to control the coking process, keeping coke concentration as low as possible and the catalyst specific surface as high as possible.

The research of the superfi cial mechanism of synthesis of methanol on the low-temperature Zn–Cu–Al-catalyst was explored. The mathematical model of process, that allows reactions, proceeding on a catalyst surface is made. The mathematicalmodel is basedon the assumptionthat theprocess proceedsin the kinetic sphereand the reactoroperates inplug fl ow.With use of the developed mathematical model, the assessment of effi ciency of modernization of the technological scheme of the M-750 installation, based on introduction in the technological scheme of the reactor of a precatalysis is created. It is shown that the optimum volume of the catalyst in the reactor of a precatalysis equals 30 m 3 , the productivity of installation of synthesis increases up to 9,8 %. It is shown thatdue to changes inthe regimeof the fi rstregimentsof the catalystwill not cometoa prematuredeactivation.

A mathematical model of the catalytic reforming of gasolines in a reactor with continuous catalyst regeneration is proposed. The model takes into account the motion of the catalyst, changes in its activity along the bed height, and the dependence of its activity on the circulation ratio. The kinetic parameters of the Pt-Sn catalyst are determined under operational conditions by solving the inverse kinetic problem. The composition of the reformate component as calculated by the model coincides with the experimental data within the accuracy of chromatographic analysis. The proposed model is invariant to the composition of raw materials and can be used for predictive calculations.

In this article, we present the main results on the modeling of the industrial process of catalytic C 9 –C 14 n -paraffin dehydrogenation, which is one of the technological stages in the production of linear alkyl benzenes used for the synthesis of synthetic detergents. The application of the developed mathematical model for evaluating the influence of the raw material composition on the target product yield is considered. The calculation results on the optimal technological modes for different dehydrogenation Pt catalysts and also on the prediction their lifetime are given.

The deactivation of catalysts by coke-forming structures in the dehydrogenation of higher n-paraffins is discussed. The patterns of coke formation on a catalyst subject to process conditions are presented. A mathematical model of the process is described to show its adequacy. A calculation algorithm for the optimum mode of operation of a dehydrogenation catalyst is constructed, and the calculation results are given. Dehydrogenation catalysts of different brands are compared with respect to several parameters (coke formation on catalysts, the yield of the reaction by-product, and the dynamics of temperature rise in the reactor). The model can be used to estimate the efficiencies of catalysts in a cycle and to compare them.

In this work, we considered the results on the modeling of the industrial catalytic alkylation process, one of the terminal stages in the production of linear alkyl benzene sulfonates (LAS) used as the basis for the synthesis of synthetic detergents. Taking into account the experimental data obtained under regular operational conditions of alkylation unit at the Linear Alkyl Benzene and Linear Alkyl Benzene Sulfonates (LAB-LAS) Plant of OOO Kirishinefteorgsintez (OOO KINEF), we developed a scheme of chemical reactions for the purpose of creating the kinetic model for the alkylation process. The kinetic parameters of this model were identified by solving the inverse kinetic problem under the lack of necessary experimental data, so we had to reduce the number of estimated kinetic parameters with the use of thermodynamic data. The software model of this process permitted us to calculate quite precisely the material and heat balances of the reactor and also to study the influence of changes in different technological parameters on the effectiveness of the process.

Based on mathematical approach method, computer modeling system was applied to dienes hydrogenation process optimization. Use of the system allows quantitative determination of sulfur consumption required for hydrogenation on nickel-containing catalyst. Research showed that the system might help to prolong catalyst life saving the desired quality of target products.

A methodology of constructing nonstationary kinetic models of multicomponent catalytic processes of hydrocarbon conversion on platinum-containing catalysts was developed. Their kinetic and technological parameters in industrial catalytic reforming were estimated. The simulation system in gasoline production allows for the testing and choosing of an optimum catalyst depending on the composition of the processed hydrocarbon raw materials. The developed testing technique is based on the processing of the results of the commercial operation of platinum-containing reforming catalysts using the computer simulation system. It allows the estimation of kinetic parameters, the prediction of selectivity, and raw cycle duration after catalyst regeneration under conditions of commercial operation, taking into account the reactivity of hydrocarbons.