The work investigated the process of oxidative oligomerization of Fischer-Tropsch synthesis products - a fraction of C10-C15 hydrocarbons with a total content of alkenes (mainly β- and γ-alkenes) of 64.7 wt. % using zirconium octoate as a catalyst. The hydrocarbon fraction was obtained on a zeolite-containing catalyst at a pressure of 2.0 MPa, a temperature of 250 °C, H2/CO ratio at the reactor inlet of 1.70, a gas space velocity of 1000 h-1 and circulation mode ratio range 0-16. It was found that at a temperature of 160 °C the catalyst content is 5.0 wt. %, process duration 6 hours and pressure (air) - 2.5 MPa, target fraction yield - 52.7 %. It was found that the oligomerization product has a low pour point of minus 31 °C. It was proposed to improve the viscosity characteristics of the oligomerization product by introducing additives into its composition, for example, polymethacrylates or polyisobutylene.

A way of producing high-octane gasoline from associated petroleum gas (APG) by combining APG aromatization with Fischer–Tropsch (FT) synthesis is proposed. APG aromatization is studied experimentally in a flow setup at a pressure of 0.1 MPa and temperatures of 450–600°C on ZnO/ZSM-5/Al2O3 catalyst. It is shown that the conversion of С3+ hydrocarbons is greatest in the 550–600°C range of temperatures to reach 22.7–27.8

The synthesis of C5–C18 alkenes in the presence of a zeolite-containing Co–Al2O3/SiO2/ZSM-5/Al2O3 catalyst in flow and recycle flow operation modes at a temperature of 250°C, a pressure of 2.0 MPa, a gas hourly space velocity (GHSV) of 1000 h−1, an H2/CO ratio of 1.70 in the feed gas, and recycle ratios of 4, 8, and 16 has been studied. It has been found that the process parameters (selectivity and productivity with respect to C5+ hydrocarbons) pass through a maximum at a recycle ratio of 8. The use of gas recycling, unlike the flow synthesis mode, makes it possible to control the product composition. An increase in the recycle ratio in a range of 4–16 leads to an increase in the content of synthesized C5–C20 alkenes from 53.9 to 65.7 wt

The process of producing C5+ hydrocarbons, including unsaturated ones, on a zeolite-containing catalyst Сo-Al2O3 /SiO2 /ZSM-5/Al2O3 in flow and flow-circulation modes of operation at a temperature of 250 °C, a pressure of 2.0 MPa, GHSV 1000 h–1 has been studied , H2 /CO ratio = 1.70 in the source gas and circulation ratios of 4, 8 and 16. It was determined that the process indicators (selectivity and productivity for C5+ products) pass through a maximum at a circulation ratio of 8. The use of gas circulation in comparison with flow synthesis mode allows you to regulate the composition of products. An increase in the circulation ratio in the range of 4–16 leads to an increase in the proportion of formed olefins with a hydrocarbon chain length containing 5–20 carbon atoms, from 53.9 wt.% up to 65.7 wt.%. The use of a zeolite-containing catalyst intensifies the formation of C8–C12 alkenes in comparison with the Co-Al2O3 /SiO2 catalyst by 3,3 times – the content increases from 13,5 wt.% up to 44.2 wt.% at similar values of circulation ratio, pressure and H2 /CO ratio = 1.70 in the source gas. It was found that as the circulation ratio increases, the rate of deactivation of the zeolite-containing catalyst decreases, which may be caused by a decrease in the partial pressure of water in the reaction volume.

In this work, new bifunctional cobalt catalysts for Fischer-Tropsch synthesis were synthesized in the form of a composite mixture: a metal component- the Co-Al2O3/SiO2 catalyst, an acid component- HBeta zeolite and a boehmite binder- AlO(OH). In HBeta zeolite (with SiO2/Al2O3 molar ratios of 40.5) in protic form, the porous structure has been optimized with an alkaline treatment (molar NaOH concentration: 0.1, 0.15, 0.25, 0.3 and 0.5) to ensure the production of branched paraffins and olefins in fuel hydrocarbons. The catalysts are characterized by X-ray diffraction (XRD), low-temperature N2 adsorption-desorption and temperature-programmed hydrogen reduction (TPR H-2), zeolite-energy dispersive surface microanalysis (EDM), thermogravimetry (TGA), scanning microscopy (SEM) and adsorption-desorption of N-2. The effectiveness of treatment with NaOH solution to increase the mesoporosity of the HBeta structure was assessed. Research on Fischer-Tropsch synthesis was carried out with a stationary catalyst bed at a pressure of 2 MPa, a temperature of 240 - 250 degrees C and a gas velocity of 1000 h(-1) . Balance experiments were carried out for 70-80 - 80 h, analyzing the composition and amount of gas at the outlet. It has been shown that increasing the synthesis temperature from 240 to 250 degrees C intensifies the synthesis process- the degree of conversion of CO catalysts increases by 9-12%. The composition of the FischerTropsch synthesis products was analyzed. It has been established that selectivity of the formation of hydrocarbons in fuel fractions, with a high degree of isomerization and catalyst productivity, determines with the use of HBeta, a modified by NaOH solution with a concentration of 0.25 and 0.5 M.

In this paper, the physicochemical and catalytic properties of SAPO-11 and SAPO-41 molecular sieves granulated with a binder material and promoted with 0.5 wt

The work summarizes the results of testing the technology for preparing a bifunctional cobalt catalyst for the synthesis of hydrocarbons from CO and H2, obtained by extruding a mixture of Co-Al2O3 /SiO2 catalyst powders and HZSM-5 zeolite with a binder – boehmite in industrial conditions (2 batches of 50 kg each were prepared). The catalyst technology was implemented on the equipment of Ishimbay Specialized Chemical Catalyst Plant LLC. The obtained industrial samples of the catalyst were characterized by XRF, TPR H2, DTG, and tested in the synthesis of hydrocarbons from CO and H2 at a temperature of 250 °C, a pressure of 2.0 MPa, GHSV 1000 h–1. It has been shown that the implementation of the technology of a bifunctional cobalt catalyst for the production of low pour point diesel fuel in industrial conditions makes it possible to reproduce the characteristics of the catalyst obtained in laboratory conditions. The technology for producing the catalyst can be recommended for the production of industrial batches. It was determined that changes in the heat treatment conditions of the catalyst, as well as the presence/absence of a peptizer and pore former do not lead to a significant decrease in the productivity of C5+ hydrocarbons. The contentof the diesel fraction in C5+ products obtained from industrial samples of the catalyst remains at the level of the value obtained from the laboratory sample of the catalyst. At the same time, the low-temperature properties of diesel fuel obtained using all catalyst samples have similar values. Using an industrial sample synthesized without the use of a peptizing agent and a pore-forming component, the best lowtemperature properties of diesel fuel were achieved – the cloud point and fluid loss point were minus 16 and minus 24, respectively.

New bifunctional composite catalysts for the Fischer—Tropsch synthesis were developed on the basis of a mixture of the Co—Al2O3/SiO2 catalyst, meso-HZSM-5 hierarchical mesoporous zeolite, and boehmite binder. The mesoporous zeolite was obtained by alkaline treatment of the industrial HZSM-5 zeolite. The developed catalysts are suitable for one-pot conversion of syngas into linear C5+ hydrocarbons, which then undergo cracking and isomerization reactions. The effect of the concentration of NaOH solution on the porosity and catalytic efficiency of the obtained meso-HZSM-5 zeolite was studied. The performances of the bifunctional catalysts obtained from alkali-treated and pristine HZSM-5 in the conversion of syngas were compared. In the presence of the catalyst based on the alkali-treated zeolite, the total productivity to C5+ hydrocarbons somewhat decreases. However, the increase in the total yield of branched and unsaturated hydrocarbons provides the formation of motor fuels with high anti-knock properties.

The process of CO2 conversion into synthetic hydrocarbons including the stages of synthesis gas production on the catalyst NIAP 06-06 and hydrocarbon synthesis by the Fischer-Tropsch method on a bifunctional zeolite-containing catalyst has been investigated. Experimental studies of the process of catalytic conversion of CO2 into synthesis gas were carried out in order to obtain gas with the ratio of H2/CO close to the required ratio for Fischer-Tropsch synthesis. The possibility of obtaining gasoline and diesel fractions of hydrocarbons with a high content of isomeric structures that increase the performance characteristics of motor fuels has been shown. The yield of hydrocarbons C5+ with 1 m3 of initial CO2 and H2 at the synthesis temperature of 220 °C is found to be 44.5 g.

This study investigates the chemical and phase compositions, acidic properties, and porous structure characteristics of an acidic support for a bifunctional catalyst. This catalyst was a high-crystallinity granulated hierarchical H-ZSM-5 molecular sieve promoted with 0.5 wt

The synthesis of C5+ hydrocarbons, including unsaturated ones, on the Co-Al2O3/SiO2 catalyst was studied in flow and flow-circulation operation modes at a pressure of 2.0 MPa, a gas space velocity of 1000 h–1, H2/CO ratios in the initial gas of 2.0, 1.85, and 1.70, circulation rate of 4–16. It was determined that the maximum parameters of the synthesizing C5+ hydrocarbons from CO and H2 on this catalyst—CO conversion, selectivity, and performance for C5+ products—are detected at a circulation rate of 8 over a whole range of the studied H2/CO ratios in the initial syngas. The content of olefins in the synthesis products was found to increase to 30 wt

A review of modern approaches to the development of cobalt catalyst technology used in most known ways of synthesizing hydrocarbons from CO and H2 using the Fischer–Tropsch is presented. The development of efficient catalysts solves the problem of replacing fossil fuels with ultra-clean alternative fuels and reduces their negative impact on the environment. An analysis of results from scientific and technological research, including ones obtained recently by the authors, shows current lines in developing the technology of high-performance catalysts for the Fischer–Tropsch synthesis of hydrocarbons using classical and integrated GTL technology, including the creation of new types of polyfunctional systems. The review mainly describes the catalytic characteristics of supported cobalt catalysts synthesized via impregnation and polyfunctional hybrid catalysts obtained on their basis for the selective synthesis of fuel fraction hydrocarbons. Problems of controlling selectivity, productivity, and changes in the activity and physicochemical properties of catalysts during long-term operation are considered.

Results of a study of the synthesis of hydrocarbons (HC) from CO and H2 in the presence of a commercial Co–Al2O3/SiO2 catalyst at 6.0 MPa and a reaction gas recycle ratio of 2.2–6.0 for 1000 h have been described. Under these conditions, the catalyst deactivation rate depends on the selectivity for synthetic C35+ long-chain HCs (SLCHCs). An increase in the SLCHC content in the products from 27.6 to 39.8% leads to a threefold increase in the catalyst deactivation rate. With an increase in the recycle ratio from 2.2 to 6.0 at a pressure of 6.0 MPa, the olefin content in the synthesis products increases. An increase in temperature leads to a shift of the selectivity toward HCs with a shorter chain. The viscosity of LCHCs condensed in the pores decreases owing to their dilution with lighter HCs, which contributes to an increase in the number of accessible active sites of the catalyst and facilitates catalyst regeneration.

The effect of the content of metallic (Co–Al 2 O 3 /SiO 2 catalyst) and acidic components (ZSM-5 zeolite in H-form) on the properties of a bifunctional catalyst for the integrated synthesis of low-pour-point diesel fuel by the Fischer–Tropsch method has been studied. The catalysts in the form of a composite mixture with a binder (boehmite) have been characterized by XRD, BET, and TPR methods. The tests are conducted in a fixed-bed flow reactor at a pressure of 2.0 MPa, a temperature of 240°C, and a gas space velocity of 1000 h –1 . The activity and selectivity of catalysts and the fractional and hydrocarbon compositions of products as a function of the ratio of components have been compared. It has been found that the synthesis productivity with respect to С 5+ hydrocarbons and selectivity to products of the С 11 –C 18 diesel fraction with a high content of isomeric products correlate with the ratio of metallic and acidic components in the catalyst composition. The catalyst recommended for use in diesel fuel production has a composition with a ratio of metallic and acidic components of 1.17.

Physicochemical and catalytic properties of molecular sieves SAPO-11 and SAPO-41, which were granulated with a binder and promoted with 0.5 wt.% Pt, were studied in isodeparaffinization of hydrotreated diesel fraction. It was shown that the introduction of ca. 30 wt.% boehmite, which turns into alumina upon calcination, into the granules leads to a 50– 70 % decrease in the micropore volume and a 6–12 % growth of the external specific surface area of the material in comparison with highly dispersed samples of the indicated molecular sieves. Both samples of bifunctional catalysts make it possible to produce diesel fuel with the pour point of –42 °С and the yield of ca. 91–92 wt.% at 340 °С, 3 MPa, 2.0 h–1, and H2 /feedstock = 800 m3/m3.

A number of catalysts were synthesized from a composite mixture consisting of a metal component (specifically, a Co–Al2O3/SiO2 catalyst in an amount of 20–40

The effect exerted by the content of metallic (Co-Al2O3/SiO2 catalyst) and acidic (ZSM-5 zeolite in the H-form) components on the properties of bifunctional catalyst for the integrated synthesis of waxy diesel fuel by the Fischer–Tropsch method was studied. Catalysts represented by a composite mixture with a boehmite binder were characterized by XRD, BET and TPR methods. The testing was performed in a flow reactor with a fixed catalyst bed at a pressure of 2.0 MPa, temperature 240 °С and gas hourly space velocity 1000 h–1. Activity and selectivity of the catalysts as well as the fractional and hydrocarbon composition of the products were investigated in dependence on the ratio of components. It was found that productivity of the synthesis for С5+ hydrocarbons and selectivity for the С11–С18 diesel fraction products with a high content of isomeric products correlated with the ratio of metallic and acidic components in the catalysts. The composition of the catalyst recommended for the diesel fuel production has the 1.17 ratio of metallic and acidic components.

The study investigated a number of cobalt-based hybrid catalysts (prepared as composite mixtures) for integrated Fischer–Tropsch (FT) synthesis and hydroprocessing. The metal component was a Co-based catalyst for FT synthesis prepared by impregnation (Co–Al/SiO 2 in one sample and Co–Ru/SiO 2 in another); the acid component was a ZSM-5 zeolite in the H-form that additionally contained Ru (incorporated by impregnation in one sample and by ion exchange in another); and the binder was boehmite. The catalysts were characterized by XRD, low-temperature argon adsorption/desorption, EDX, SEM, TEM, H 2 -TPD, and TPR. The promoter incorporation method was shown to affect the particle size and cobalt reduction conditions. The catalysts were tested in FT synthesis at 2.0 MPa, 240°C, H 2 /CO = 2, and GHSV 1000 h –1 . The method for loading Ru as a hydrogenating agent was found to govern the catalytic activity as well as the group and fractional compositions of the reaction products. It was further shown that co-loading Co and Ru intensifies the hydrogenation and synthesis of hydrocarbons—including C 11 –C 18 (diesel fuel) and in particular iso -alkanes—and minimizes the content of unsaturated hydrocarbons. Incorporating Ru into the acid component favors the isomerization activity of the catalyst. Using impregnation for this purpose maximizes the gasoline productivity (C 5 –C 10 hydrocarbons).

A study is performed by using a zinc–copper catalyst for the steam reforming of CO NIAP-06-06 in the synthesis of methanol. The catalyst is characterized via the TPV of N2, XRF, and SEM. It is tested in the synthesis of methanol in flow and circulation modes at a pressure of 5.0 MPa, GHSV of 3000 h−1, and the 220–260°C range of temperatures. It is shown that the catalyst has high activity and selectivity in synthesizing methanol from gas obtained in the ratio H2 : CO = 3.9 via the steam reforming of methane. Using a series of tubular catalytic reactors in the technological mode of a flow circle allows more than 70% of the CO to be processed and raw methanol to be obtained with a concentration of 95%. The performance of the catalyst for methanol is 427.7 kg/( $${\text{m}}_{{{\text{cat}}}}^{3}$$ h) in the circulation mode.