Publications
en
en ru
Heterogeneous catalysisMetal complex catalysisElectrochemistry and functional materialsShared Use Center «Nanotechnologies»
Heterogeneous catalysisElectrochemistry and functional materials
Heterogeneous catalysisElectrochemistry and functional materials
Heterogeneous catalysisMetal complex catalysisElectrochemistry and functional materials
Heterogeneous catalysisMetal complex catalysisElectrochemistry and functional materials
Teams
Media
Contacts

Search

Main Departments Heterogeneous catalysis Publications

Heterogeneous catalysis

About department
Developments
Projects
Products
Publications
Engineering

Publications

Investigation of the effect of gas circulation multiplicity on the formation of C5—C18 alkenes in the Fischer—Tropsch synthesis
Zubkov I.N., Denisov O.D., Timokhina M.A., Savostyanov A.P., Yakovenko R.E.
Tuning selectivity in low-temperature Fischer-Tropsch synthesis by applying gas recycle mode
Sergey Mitchenko, Roman Yakovenko, Vitaliy Soromotin, Tatyana Krasnyakova, Roman Svetogorov, Yuri Rusalev
Bifunctional CO catalyst for the synthesis of low-solidification diesel fuel by the Fischer—Tropsch method — from development to implementation. Part 3
Narochny G.B., Zubkov I.N., Savostyanov A.P., Allaguzin I.Kh., Lavrenov S.A., Yakovenko R.E.
OLIGOMERIZATION OF PENT-1-ENE OVER NI-MODIFIED GRANULAR Y ZEOLITE WITH HIERARCHICAL POROSITY
D. V. Serebrennikov, N. G. Grigor’eva, A. N. Khazipova, R. E. Yakovenko, M. R. Agliullin & B. I. Kutepov
ISODEPARAFINIZATION OF DIESEL FRACTION ON GRANULAR PT-CONTAINING MOLECULAR SIEVES SAPO-11 AND SAPO-41
R. E. Yakovenko, M. R. Agliullin, I. N. Zubkov, O. D. Denisov, D. V. Serebrennikov, B. I. Kutepov, A. L. Maksimov
Effects of Ruthenium on the Catalytic Performance of Cobalt-Based Hybrid Catalysts for Synthesis of Hydrocarbons from CO and H2 [ожидает перевода]
S. I. Sulima, V. G. Bakun, I. N. Zubkov, A. P. Savost’yanov, R. E. Yakovenko
Selective Synthesis of a Gasoline Fraction from CO and H2 on a Co-SiO2/ZSM-5/Al2O3 Catalyst
Roman E. Yakovenko, Grigory B. Narochnyi, Ivan N. Zubkov, Ekaterina A. Bozhenko, Yash V. Kataria, Roman D. Svetogorov, Alexander P. Savost’yanov
Crystallization of ALPO-11 aluminophosphate molecular sieve using secondary amines
Agliullin M.R., Yakovenko R.E., Saliev A.N., Zabirov A.R., Pavlova I.N., Sabirov D.Sh.
Ammonia Decomposition over Cobalt-Based Silica-Supported Fischer-Tropsch Synthesis Catalysts
R. E. Yakovenko, T. V. Krasnyakova, A. N. Saliev, M. A. Shilov, A. V. Volik, A. P. Savost’yanov & S. A. Mitchenko
Bifunctional cobalt catalyst for the synthesis of low pour point diesel fuel by the Fischer-Tropsch method — from development to implementation. Part 2
R. E. Yakovenko, V. G. Bakun, I. N. Zubkov, O. P. Papeta, A. N. Saliev, A. P. Savostyanov
Experience in the creation and operation of GTL technology in Russia
A. P. Savostyanov, R. E. Yakovenko
Evaluation of the Efficiency of a Number of Industrial Domestic Catalysts in the Ammonia Decomposition Reaction
R. E. Yakovenko, T. V. Krasnyakova, A. V. Dulnev, A. N. Saliev, M. A. Shilov, A. V. Volik, A. P. Savostyanov, S. A. Mitchenko
Effect of Tail Gas Recirculation Mode on the Activity and Selectivity of the Сo/SiO2 Catalyst for Fischer‒Tropsch Synthesis
V. N. Soromotin, R. E. Yakovenko, T. V. Krasnyakova, R. D. Svetogorov , S. A. Mitchenko
Cobalt Supported and Polyfunctional Hybrid Catalysts for Selective Fischer—Tropsch Synthesis: A Review
R. E. Yakovenko, V. G. Bakun, S. I. Sulima, G. B. Narochnyi, S. A. Mitchenko, I. N. Zubkov & A. P. Savost’yanov
Selective synthesis of olefins on a Co-Al2O3/SiO2 catalyst by the Fischer-Tropsch method
I. N. Zubkov, A. P. Savostyanov, V. N. Soromotin, O. D. Denisov, S. S. Demchenko, R. E. Yakovenko
Effects of Zeolite Type on Integrated Fischer—Tropsch Synthesis and Hydroprocessing
R. E. Yakovenko, V. G. Bakun, M. R. Agliullin, S. I. Sulima, I. N. Zubkov, V. V. Pyatikonova, E. A. Bozhenko & A. P. Savost’yanov
Fischer—Tropsch Synthesis on Bifunctional Cobalt Catalysts with the Use of Hierarchical Zeolite HBeta
R. E. Yakovenko, V. G. Bakun, I. N. Zubkov, O. P. Papeta, A. N. Saliev, M. R. Agliullin & A. P. Savost’yanov
Production of Alcohols and Olefins from CO and H2 on a Cobalt Catalyst at High Pressures and in the Gas Circulation Mode
Zubkov, I.N., Soromotin, V.N., Savost’yanov, A.P., Mitchenko, S.A., Yakovenko, R.E.
Study of the NIAP-06-06 Zinc—Copper Catalyst for the Steam Reforming of Carbon Monoxide in the Synthesis of Methanol
Narochnyi, G.B., Savost’yanov, A.P., Zubkov, I.N., Dul’nev, A.V., Yakovenko, R.E.
Gasification of Biochar Produced by the Hydrothermal Carbonization of Peat
Kulikova, M.V., Krysanova, K.O., Krylova, A.Y., Kulikov, A.B., Muravskii, P.K., Saliev, A.N., Il’in, V.B., Savost’yanov, A.A., Yakovenko, R.E.
Production of mixtures of hydrocarbons from co and H2 in the presence of Co-SiO2 catalysts prepared by the impregnation method
Lapidus, A.L., Savost'yanov, A.P., Taranushich, V.A.
Influence of physiochemical characteristics on properties of Co catalysts for synthesis of hydrocarbons from CO and H2
Lapidus, A. L., Budtsov, V. S., Savost'Yanov, A. P., Krylova, A. Y., Mezhov, V. D., & Bakun, V. G.
The influence of physico-chemical characteristics on the properties of Co catalysts of hydrocarbon synthesis from CO and H2
Lapidus, A. L., Budtsov, V. S., Savost’yanov, A. P., Krylova, A. Y., Mezhov, V. D., & Bakun, V. G.
Mineralogical composition and physicochemical properties of bentonite from Tarasovskoe deposit
Savost'yanov, A. P., Taranushich, V. A., Bakun, V. G., Kononenko, S. A., & Sobchinskii, A. I.
Diffusion effect on hydrocarbon synthesis from CO and H2 with a cobalt catalyst
Savostyanov, A.P., Bakun, V.G., Budtsov, V.S., Taranushich, V.A.
Diffusion in the synthesis of hydrocarbons from CO and H2 on a cobalt catalyst
Savost'yanov, A. P., Bakun, V. G., Budtsov, V. S., & Taranushich, V. A.
Temperature-programmed reduction study of Cu1-xNi xCr2O4 solid solutions
Kirsanova, A. I., Talanov, V. M., Shabel'skaya, N. P., Savost'yanov, A. P., Bakun, V. G., & Semenov, O. A.
Catalytic hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol at atmospheric pressure in the liquid phase
Pyatnitsyna, E. V., El’chaninov, M. M., & Savost’yanov, A. P.
Relationship between the selectivity of the Fischer-Tropsch process and type of pore structure of cobalt catalysts
Savost’yanov, A. P., & Bakun, V. G.
Electrolytic reduction of 2-butyne-1,4-diol as a route to trans-2-butene-1,4-diol
Pyatnitsyna, E. V., El’chaninov, M. M., & Savost’yanov, A. P.
Control over selectivity and rate of hydrocarbon synthesis from carbon monoxide and hydrogen
Savost’yanov, A. P., Budtsov, V. S., Vysochin, N. V., & Lapidus, A. L.
Assessment of the adequacy of a mathematical model for the Fischer-Tropsch synthesis in a fixed-bed tube reactor with a cobalt catalyst
Lapidus, A. L., Budtsov, V. S., Savost’yanov, A. P., & Vysochin, N. V.
Procedures for recovery of crystalline 2-butyne-1,4-diol from industrial aqueous solutions and for its purification
Pyatnitsyna, E. V., El’chaninov, M. M., & Savost’yanov, A. P.
Oxidation products of fused 2-hetarylimidazole derivatives
Aleksandrov, A. A., Savost’yanov, A. P., El’chaninov, M. M., & Salamatina, G. V.
Identification of an admixture in 1,4-butanediol at its production by the roeppe method
Pyatnitsyna, E. V., El’chaninov, M. M., & Savost’yanov, A. P.
Structure and gasification of coal from the Gukovo-Gryaznovskoe deposit
Bakun, V. G., Saliev, A. N., Zemlyakov, N. D., Savost’yanov, A. P., & Lapidus, A. L.
Recent development in heavy paraffin synthesis from CO and H2
Eliseev, O. L., Savost’yanov, A. P., Sulima, S. I., & Lapidus, A. L.
Influence of manganese on formation of active phase of cobalt catalyst of hydrocarbon synthesis
Sulima, S.I., Bakun, V.G., Shabelskaya, N.P., Saliev, A.N., Chistyakova, N.S., Savost'yanov, A.P.
Catalysts in the conversion of coal and shale into synthetic hydrocarbons
Savost’yanov, A. P., Strizhakova, Y. A., Lapidus, A. L., Taranushich, V. A., Bakun, V. G., Budtsov, V. S., ... & Ponomarev, V. V.
Synthesis of high-molecular-weight hydrocarbons from CO and H2 over a cobalt catalyst
Savost’yanov, A. P., Narochnyi, G. B., Yakovenko, R. E., Bakun, V. G., & Zemlyakov, N. D.
Developing a pilot industrial plant for the production of synthetic hydrocarbons from natural gas
Savost’yanov, A. P., Narochnyi, G. B., Yakovenko, R. E., Astakhov, A. V., Zemlyakov, N. D., Merkin, A. A., & Komarov, A. A.
Fischer-Tropsch process for the synthesis of hydrocarbons in flow and flow circulation modes (Short Communication)
Savost’yanov, A. P., Narochnyi, G. B., Yakovenko, R. E., & Lapidus, A. L.
Feasibility of using a tube reactor in high-intensity fischer-tropsch synthesis
Yakovenko, R. E., Narochnyi, G. B., Savost’yanov, A. P., & Kirsanov, V. A.
Effect of the dilution of synthesis gas with nitrogen on the Fischer—Tropsch process for the production of hydrocarbons
Savost’Yanov, A. P., Yakovenko, R. E., Narochnyi, G. B., & Lapidus, A. L.
Experience in introducing a cobalt catalyst technology for the synthesis of hydrocarbons from CO and H2
Narochnyi, G. B., Yakovenko, R. E., Savost’yanov, A. P., & Bakun, V. G.
Industrial catalyst for the selective Fischer—Tropsch synthesis of long-chain hydrocarbons
Savost’yanov, A. P., Yakovenko, R. E., Narochnyi, G. B., Bakun, V. G., Sulima, S. I., Yakuba, E. S., & Mitchenko, S. A.
Unexpected increase in C5 + selectivity at temperature rise in high pressure Fischer-Tropsch synthesis over Co-Al2O3/SiO2 catalyst
Savost'yanov, A. P., Yakovenko, R. E., Narochniy, G. B., Sulima, S. I., Bakun, V. G., Soromotin, V. N., & Mitchenko, S. A.
The impact of Al2O3 promoter on an efficiency of C5+ hydrocarbons formation over Co/SiO2 catalysts via Fischer-Tropsch synthesis
Savost’yanov, A. P., Yakovenko, R. E., Sulima, S. I., Bakun, V. G., Narochnyi, G. B., Chernyshev, V. M., & Mitchenko, S. A.
Synthesis of Low-Pour-Point Diesel Fuel in the Presence of a Composite Cobalt-Containing Catalyst
Savost’Yanov, A. P., Narochnyi, G. B., Yakovenko, R. E., Saliev, A. N., Sulima, S. I., Zubkov, I. N., ... & Mitchenko, S. A.
Enhancement of the Fischer—Tropsch process for producing long-chain hydrocarbons on a cobalt—alumina—silica gel catalyst
Savost’yanov, A. P., Narochnyi, G. B., Yakovenko, R. E., Mitchenko, S. A., & Zubkov, I. N.
Development and industrial approbation of technologies of cobalt catalysts for synthesis of long chain hydrocarbons from synthesis gas
Savostyanov, A. P., Yakovenko, R. E., Narochny, G. B., Bakun, V. G., & Merkin, A. A.
The Microstructure of Cobalt Silica Gel Catalyst in the Presence of Al2O3 Additive
Sulima, S. I., Bakun, V. G., Yakovenko, R. E., Shabel’skaya, N. P., Saliev, A. N., Narochnyi, G. B., & Savost’yanov, A. P.
Supported Bifunctional Cobalt Catalysts for CO and H2 Conversion to Fuel Fractions of Hydrocarbons
Savost’yanov, A. P., Yakovenko, R. E., Saliev, A. N., Narochnyi, G. B., Mitchenko, S. A., Zubkov, I. N., ... & Kirsanov, V. A.
Effect of Diffusion Limitations on the Fischer—Tropsch Synthesis of Long-Chain Hydrocarbons on a Cobalt—Alumina Silica Gel Catalyst
Savost’yanov, A. P., Narochnyi, G. B., Yakovenko, R. E., Soromotin, V. N., & Zubkov, I. N.
Bifunctional Cо/SiО2-Fe-ZSM-5-Al2O3 catalysts for synthesis of hydrocarbons of engine fractions
Savostyanov, A. P., Yakovenko, R. E., Narochny, G. B., Nepomnyashchikh, E. V., & Mitchenko, S. A.
Effect of the Composition of Synthesis Gas on a Combined Process of the Synthesis and Hydrofining of Hydrocarbons from CO and H2
Yakovenko, R. E., Narochnyi, G. B., Zubkov, I. N., Nepomnyashchikh, E. V., & Savost’yanov, A. P.
Thermodynamic Study of Associated Petroleum Gas Reforming to Methane
Ilyin, V. B., Yakovenko, R. E., Belashov, D. M., Zemlyakov, N. D., & Savost’yanov, A. P.
Production of Motor Fuel Hydrocarbon Fractions from Pine Wood (Short Communication)
Yakovenko, R. E., I’lin, V. B., Narochnyi, G. B., Zubenko, A. F., Savost’yanov, A. A., & Lapidus, A. L.
Effect of the Type of the Cobalt-Containing Component of a Composite Catalyst on the One-Stage Synthesis of Liquid Hydrocarbons from СО and Н2
Yakovenko, R. E., Zubkov, I. N., Narochnyi, G. B., Nekroenko, S. V., & Savost’yanov, A. P.
Deactivation of Co-Al2O3/SiO2 Fischer—Trospch Synthesis Catalyst in Industrially Relevant Conditions
Savost’yanov, A. P., Eliseev, O. L., Yakovenko, R. E., Narochniy, G. B., Maslakov, K. I., Zubkov, I., ... & Mitchenko, S. A.
Deactivation of a Commercial Co—Al2O3/SiO2 Catalyst in Fischer—Tropsch Synthesis under High-Pressure and Gas Recycling Conditions
Savost’yanov, A. P., Yakovenko, R. E., Narochnyi, G. B., Zubkov, I. N., Sulima, S. I., Soromotin, V. N., & Mitchenko, S. A.
Effect of Re and Al2O3 Promotion on the Working Stability of Cobalt Catalysts for the Fischer—Tropsch Synthesis
Yakovenko, R. E., Zubkov, I. N., Narochniy, G. B., Papeta, O. P., Denisov, O. D., & Savost’yanov, A. P.
Effect of Gas Circulation on the Synthesis of C35+ Long-Chain Hydrocarbons from CO and H2 at a High Pressure
Yakovenko, R. E., Zubkov, I. N., Narochnyi, G. B., & Savost’yanov, A. P.
Conversion of Liquefied Hydrocarbon Gases on Industrial Nickel Catalysts
Yakovenko, R. E., Il’in, V. B., Savost’yanov, A. P., Zubkov, I. N., Dul’nev, A. V., & Semenov, O. A.
Development of a Highly Productive Supported Bifunctional Catalyst Based on Zeolite ZSM-5 for the Production of Fuel Grade Hydrocarbon Fractions from CO and H2
Savost’yanov, A. P., Yakovenko, R. E., Narochnyi, G. B., Zubkov, I. N., & Nepomnyashchikh, E. V.
Preliminary evaluation of a commercially viable Co-based hybrid catalyst system in Fischer-Tropsch synthesis combined with hydroprocessing
Yakovenko, R. E., Savost'yanov, A. P., Narochniy, G. B., Soromotin, V. N., Zubkov, I. N., Papeta, O. P., ... & Mitchenko, S. A.
Production of Motor-Fuel Hydrocarbon Fractions from Sunflower Husk Biomass
Il’in, V. B., Narochnyi, G. B., Zubenko, A. F., Savost’yanov, A. A., & Yakovenko, R. E.
Hybrid Catalyst for the Selective Synthesis of Fuel Range Hydrocarbons by the Fischer—Tropsch Method
Yakovenko, R. E., Zubkov, I. N., Savost’Yanov, A. P., Soromotin, V. N., Krasnyakova, T. V., Papeta, O. P., & Mitchenko, S. A.
Effect of the Means Used to Synthesize Bifunctional Fischer—Tropsch Catalysts on the Composition and Properties of Synthetic Fuels
Yakovenko, R. E., Bakun, V. G., Zubkov, I. N., Narochnyi, G. B., Papeta, O. P., & Savost’yanov, A. P.
Bifunctional Cobalt-Containing Catalytic Systems Based on SAPO-11 Molecular Sieves in Fischer—Tropsch Synthesis of Fuels
Yakovenko, R. E., Agliullin, M. R., Zubkov, I. N., Papeta, O. P., Khliyan, G. T., & Savostyanov, A. P.
Combined Synthesis and Hydroprocessing of Hydrocarbons over Co/SiO2 + ZSM-5 + Al2O3 Catalysts Promoted by Nickel
Yakovenko, R. E., Zubkov, I. N., Bakun, V. G., & Savost’yanov, A. P.
Bifunctional Cobalt Catalyst for the Synthesis of Waxy Diesel Fuel by the Fischer—Tropsch Method: From Development to Commercialization
Yakovenko, R. E., Zubkov, I. N., Bakun, V. G., Agliullin, M. R., Saliev, A. N., & Savost’yanov, A. P.
Influence of operating conditions on the main characteristics of a cobalt Fischer-Tropsch catalyst
Yakovenko, R. E., Savost’yanov, A. P., Chistyakova, N. S., Bakun, V. G., & Sulima, S. I.
Prospects for Technologies in the Production of Synthetic Base Stocks for Engine Oils (A Review)
Sulima, S. I., Bakun, V. G., Chistyakova, N. S., Larina, M. V., Yakovenko, R. E., & Savost’yanov, A. P.
Reasons for the Rapid Deactivation of a Cobalt Catalyst in the High-Efficiency Fischer—Tropsch Synthesis of C19+ Hydrocarbons
Soromotin, V. N., Yakovenko, R. E., Medvedev, A. V., & Mitchenko, S. A.
Effects of SiO2/Al2O3 Ratio in ZSM-5 Zeolite on the Activity and Selectivity of a Bifunctional Cobalt Catalyst for Synthesis of Low-Pour-Point Diesel Fuels from CO and H2
Yakovenko, R. E., Zubkov, I. N., Bakun, V. G., Papeta, O. P., & Savostyanov, A. P. (2022)
Relation between Morphology and Porous Structure of SAPO-11 Molecular Sieves and Chemical and Phase Composition of Silicoaluminophosphate Gels
Agliullin, M. R., Yakovenko, R. E., Kolyagin, Y. G., Serebrennikov, D. V., Vildanov, F. S., Prosochkina, T. R., & Kutepov, B. I. (2022).

Investigation of the effect of gas circulation multiplicity on the formation of C5—C18 alkenes in the Fischer—Tropsch synthesis

The process of obtaining alkenes C5–C18 on a zeolite-containing catalyst Co-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, a volumetric gas velocity of 1000 h–1, a ratio of H2 /CO = 1.70 in the initial gas and circulation multiplicities 4, 8 and 16. It was determined that the process parameters (selectivity and productivity for C5+ hydrocarbons) pass through a maximum at a circulation multiplicity of 8. The use of gas circulation in comparison with the flow mode of synthesis allows you to regulate the composition of products. An increase in the multiplicity of circulation in the range 4-16 leads to an increase in the proportion of C5–C20 alkenes formed from 53.9 to 65.7 wt.%. The use of a zeolite–containing catalyst intensifies the formation of C8-C12 alkenes compared with the Co–Al2O3 /SiO2 catalyst by 3.3 times - their content increases from 13.5 to 44.2 wt.% at similar values of circulation multiplicity, pressure and H2 ratio /CO = 1.70 in the initial gas. It was found that as the circulation multiplicity 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.

More

Tuning selectivity in low-temperature Fischer-Tropsch synthesis by applying gas recycle mode

While hydrocarbons production by Fischer-Tropsch synthesis (FTS) is widely recognized, commercial interest in FTS products is mainly constrained by oil prices. The FTS-derived fuels, although higher quality and greener, cannot currently compete with cheaper fossil fuels, motivating to shift the FTS products distribution to higher value-added chemicals, such as olefins-C5+. The high olefin selectivity in FTS over Co-based catalysts is usually ascribed to Co2C on the catalyst surface with its inherent deficiencies. This study demonstrates a novel approach to alter low-temperature FTS selectivity by applying off-gas recycling. At slow gas recycling rates, C19+ selectivity increases due to re-adsorption and re-incorporation into the growing chain of gaseous olefins from the off-gas. High-intensity gas recycling facilitates C5+ olefin vapors removal from the reactor by enhanced gas flow with their subsequent cut-off in the cold trap, thus reducing residence time of condensed olefins and probability of their secondary reactions.

More

Bifunctional CO catalyst for the synthesis of low-solidification diesel fuel by the Fischer—Tropsch method — from development to implementation. Part 3

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 catalyst powders Co-Al2O3 /SiO2 and HZSM-5 zeolite with a binder - boehmite, under industrial conditions (2 batches of 50 kg each) are summarized. 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, H2 TPR, and DTG, and tested in the synthesis of hydrocarbons from CO and H2 at a temperature of 250 °C, a pressure of 2.0 MPa, and an OSG of 1000 h–1. It has been shown that the implementation of the technology of a bifunctional cobalt catalyst for the production of low-solidification 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 porogen, do not lead to a significant decrease in the productivity of C5+ hydrocarbons. The content of 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 low-temperature properties of diesel fuel were achieved—the cloud point and fluid loss point were minus 16 and minus 24, respectively.

More

OLIGOMERIZATION OF PENT-1-ENE OVER NI-MODIFIED GRANULAR Y ZEOLITE WITH HIERARCHICAL POROSITY

The study investigates the catalytic performance of Ni-modified granular samples of hierarchical porous Yh (FAU) zeolite, some of which were synthesized by ion exchange and others by impregnation. The samples were characterized by X-ray diffraction, X-ray fluorescence, low-temperature nitrogen adsorption/desorption (–196°C), scanning electron microscopy, hydrogen temperature-programmed reduction, and IR spectroscopy of adsorbed pyridine. The samples prepared by ion exchange of Na+ for Ni2+ exhibited high catalytic activity in oligomerization of pentene, specifically 98% monomer conversion and 67% yield of oligomers at 110°C and 10 wt % catalyst. In contrast, the catalysts prepared by impregnation (Ni/Na–Yh) exhibited extremely low activity in pentene oligomerization. The Ni-modified Yh samples showed lower stability in the oligomerization of pentene than H–Yh.

More

ISODEPARAFINIZATION OF DIESEL FRACTION ON GRANULAR PT-CONTAINING MOLECULAR SIEVES SAPO-11 AND SAPO-41

The physicochemical and catalytic properties in the isodewaxing of the hydrotreated diesel fraction of SAPO-11 and SAPO-41 molecular sieves granulated with a binder material and promoted with 0.5 wt.% Pt were studied. It has been shown that the introduction of ~30 wt.% boehmite into the granules, which transforms into aluminum oxide upon calcination, leads to a decrease in the volume of micropores by 50–70% and an increase in the external specific surface area of the material by 6–12% compared to highly dispersed samples of the mentioned molecular sieve It was established that both samples of bifunctional catalysts make it possible to obtain diesel fuel with a pour point of –42 °C and a yield of ~91–92 wt.% at 340 °C, 3 MPa, 2.0 h–1, H2 /feed = 800 m3/m3 .

More

Effects of Ruthenium on the Catalytic Performance of Cobalt-Based Hybrid Catalysts for Synthesis of Hydrocarbons from CO and H2 [ожидает перевода]

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/SiO2 in one sample and Co–Ru/SiO2 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, H2-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, H2/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 C11–C18 (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 (C5–C10 hydrocarbons).

More

Selective Synthesis of a Gasoline Fraction from CO and H2 on a Co-SiO2/ZSM-5/Al2O3 Catalyst

This article reports on a simple method for producing high-octane gasoline from CO and H2 on a Co-Al2O3/SiO2/HZSM-5/Al2O3 hybrid catalyst. In the selected pressure range (0.5, 1.0, and 2.0 MPa), it was found that a decrease in pressure and an increase in temperature contribute to an increase in the content of branched hydrocarbons. The optimal technological parameters of the process were determined to ensure high selectivity and productivity for C5–C10 hydrocarbons: pressure—1.0 MPa, ratio H2/CO = 2, gas space velocity—1000 h−1, temperature—250 °C. The selectivity for the gasoline fraction is 65.2%, and the ratio of branched to linear hydrocarbons (iso/n index) is 2.3. Under the specified technological conditions, an experimental batch of gasoline fraction (1000 cm3) was produced at the pilot plant during 400 h of continuous operation. The main physicochemical and operational parameters of the experimental gasoline fraction of hydrocarbons have been determined. The octane number determined by the research method according to GOST R 52947-2019 is 78.5 units.

More

Crystallization of ALPO-11 aluminophosphate molecular sieve using secondary amines

The effect of the content of secondary amines of various molecular weights (diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine) used as a template on the results of crystallization of the AlPO4 molecular sieve was studied using XRD, SEM, and N2 adsorption-desorption methods. -eleven. It is shown that the content of the template (template/Al2O3) has a significant effect on the phase composition of the crystallization products. It was found that for all the studied templates there is a narrow range of template/Al2O3 ratios, in which the synthesis of AlPO4-11 of high phase purity is possible. The effect of the nature of the template on the morphology and fineness of the AlPO4-11 molecular sieve has been established.

More

Ammonia Decomposition over Cobalt-Based Silica-Supported Fischer-Tropsch Synthesis Catalysts

Decomposition of ammonia over silica-supported cobalt catalysts for Fischer–Tropsch synthesis has been studied at a pressure of 0.1 MPa, a gas hourly space velocity in the range of 1000–6000 h–1, and a temperature in the range of 400–650°C in a tubular fixed bed reactor in a flow-through mode. It was found that silica-supported cobalt catalysts for hydrocarbons synthesis via the Fischer–Tropsch protocol also exhibit high activity in ammonia decomposition. Both the activity and hydrogen performance decrease in the series: Co-Ru/SiO2 > Co-Al2O3/SiO2 > Ru/SiO2 > Co-Al2O3/SiO2(35%)/ZSM-5(30%)/Al2O3(35%). The relatively low values of effective activation energies estimated for all catalysts indicate that the reaction can proceed with high conversion at moderate temperatures.

More

Bifunctional cobalt catalyst for the synthesis of low pour point diesel fuel by the Fischer-Tropsch method — from development to implementation. Part 2

The influence of the content of metal (Co-Al2O3/SiO2 catalyst) and acidic (ZSM-5 zeolite in H-form) components on the properties of a bifunctional catalyst for the integrated synthesis of low-pourness diesel fuel by the Fischer-Tropsch method was studied. The catalysts in the form of a composite mixture with a binder (boehmite) were characterized by XPA, BET, and TPV. The tests were carried out in a flow reactor with a fixed catalyst bed 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 the catalysts and the fractional and hydrocarbon composition of the products were compared depending on the ratio of the components. It has been established that the productivity of the synthesis for C5+ hydrocarbons and the selectivity for the products of the C11–C18 diesel fraction with a high proportion of isomeric products correlate with the ratio of the metal and acid components in the composition of the catalysts. The catalyst recommended for the production of diesel fuel has a composition with a ratio of metal and acid components of 1.17.

More

Experience in the creation and operation of GTL technology in Russia

The paper summarizes the experience of industrial operation of synthetic hydrocarbon technology in Russia at the Novocherkassk Plant of Synthetic Products (NZSP), located in Novocherkassk, Rostov Region. More than 200 types of marketable products for general consumption were produced at NZSP. The article presents information on the production of synthesis gas from natural gas, the synthesis of hydrocarbons and process catalysts.

More

Evaluation of the Efficiency of a Number of Industrial Domestic Catalysts in the Ammonia Decomposition Reaction

Under the conditions of import substitution, the adaptation of domestic industrial catalysts for use in important technological processes, including environmentally friendly production of hydrogen that is not accompanied by COx and NOx emissions, is in demand. Ammonia seems to be the most promising H2 battery due to its high hydrogen density, ease of storage and transportation. The paper shows the possibility of using industrial domestic catalysts NIAP-03-01, NIAP-07-01, NIAP-06-06 and Co-Al2O3 /SiO2 developed by us in the reaction of ammonia dissociation. The degree of conversion and productivity in hydrogen increases in the series NIAP-06-06 - NIAP-03-01 - NIAP-07-01 - Co-Al2O3 /SiO2. At 550°C and OSG 3000 h–1, the conversion of ammonia on Co-Al2O3/SiO2 is close to 100%. The effective activation energies of all catalysts are comparable to those available in the literature for the reaction of ammonia decomposition, which makes their use potentially possible at moderate temperatures.

More

Effect of Tail Gas Recirculation Mode on the Activity and Selectivity of the Сo/SiO2 Catalyst for Fischer‒Tropsch Synthesis

The effect of the gas recirculation mode on the selectivity and deactivation rate of the Co-Al2O3/SiO2 catalyst of the Fischer‒Tropsch synthesis at high pressure (6 MPa) has been studied. The use of recirculation with a gas recycle ratio of up to 2.2 promotes the formation of C19+ hydrocarbons due to the readsorption of gaseous olefins and their involvement in chain propagation. The increased selectivity for C19+ paraffin leads to accelerated deactivation of the catalyst. An increase in the gas recycle ratio to 8 leads to increased selectivity for C5+ olefins and a lower yield of C19+ waxes due to the removal of C5+ olefin vapors from the reaction zone. The latter is associated with a decreased contribution of the readsorption of higher C5+ olefins to the elongation of the carbon chain. At high gas recycle ratios, CoO was reduced to the metal, which partially compensates for catalyst deactivation as a result of the blocking of the active sites of chain propagation by C19+ waxes.

More

Cobalt Supported and Polyfunctional Hybrid Catalysts for Selective Fischer—Tropsch Synthesis: A Review

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.

More

Selective synthesis of olefins on a Co-Al2O3/SiO2 catalyst by the Fischer-Tropsch method

The process of obtaining C5+ hydrocarbons, including unsaturated ones, on a Co-Al2O3/SiO2 catalyst in flow and flow-circulation modes of operation at a pressure of 2.0 MPa, a gas space velocity of 1000 h–1, and H2/CO ratios in the initial gas of 2.0, 1.85, and 1.70, circulation ratios 4–16. It has been determined that the maximum parameters of the process of synthesizing C5+ hydrocarbons from CO and H2 on this catalyst—the degree of CO conversion, selectivity and productivity for C5+ products—are recorded at a circulation ratio of 8 for the entire range of the studied H2/CO ratios in the initial synthesis gas. It has been found that when using a circulation ratio of 8–16, the content of olefins in the synthesis products increases to ~30 wt %. It was found that when the process of obtaining hydrocarbons by the Fischer–Tropsch method in the flow-circulation mode of operation, the rate of catalyst deactivation decreases, which may be a consequence of a decrease in the partial pressure of water in the reaction zone.

More

Effects of Zeolite Type on Integrated Fischer—Tropsch Synthesis and Hydroprocessing

A number of bifunctional composite cobalt-based catalysts were prepared with various types of molecular sieves in the H-form (zeolites ZSM-5, Y, Beta, and Mordernite, and silicoaluminophosphate SAPO-11) as an acid component. The catalytic performance of these catalysts was comparatively assessed in integrated Fischer-Tropsch synthesis of fuels. The catalysts were found to exhibit high activity and high C5+ selectivity at 2.0 MPa, 240–250°C, and a gas hourly space velocity (WHSV) of 1000 h–1. With the CO conversion reaching 80.9–93.7%, the productivity was in the range of 146.4 kg/(m3cat h). The study further revealed the effects of the crystalline and porous structures of the molecular sieves on the hydrocarbon and fractional compositions of the fuel products and on the selectivity towards branched hydrocarbons. It was shown that catalysts based on HZSM-5 and HBeta zeolites are preferable for high-performance and selective synthesis of fuels. In the presence of the HZSM-5-based catalyst, an effect atypical of Fischer–Tropsch synthesis was observed for the first time: an elevation of the process temperature leads to an enhancement of C5+ selectivity.

More

Fischer—Tropsch Synthesis on Bifunctional Cobalt Catalysts with the Use of Hierarchical Zeolite HBeta

The production of fuel components in the integrated Fischer–Tropsch synthesis on bifunctional cobalt catalysts in the form of a mixture of the cobalt catalyst Co–Al2O3/SiO2 and hierarchical zeolite HBeta samples with a binder was studied. The conditions for the preparation of HBeta samples with a developed mesoporous structure by alkaline modification using a solution of NaOH were determined. The effect of the structure and acidic properties of HBeta on the activity of the catalysts in the Fischer–Tropsch synthesis and the hydrocarbon and fractional composition of the resulting products were studied. The studies were carried out in a flow reactor with a fixed catalyst bed at a pressure of 2 MPa, a gas space velocity of 1000 h–1, and a temperature of 240°C. The process parameters for the bifunctional catalysts and the composition of fuel components correlated with the structure and surface condition of the HBeta zeolite samples.

More

Production of Alcohols and Olefins from CO and H2 on a Cobalt Catalyst at High Pressures and in the Gas Circulation Mode

The results of a study of the synthesis of products from CO and H2 on a supported industrial Co–Al2O3/SiO2 catalyst under medium and high pressures in the gas circulation mode are presented. It was found that an increase in pressure from 2.0 to 8.0 MPa led to an increase in the amount of formed alcohols and synthesis olefins by factors of 10.5 and 2.0, respectively. It was determined that alcohols obtained in the synthesis were not the products of olefin hydration. The effect of an increase in selectivity for C5+ products with temperature at a high pressure in the gas recirculation mode, which is atypical for the Fischer–Tropsch synthesis, was confirmed. 

More

Study of the NIAP-06-06 Zinc—Copper Catalyst for the Steam Reforming of Carbon Monoxide in the Synthesis of Methanol

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/(mcat3 h) in the circulation mode. 

More

Gasification of Biochar Produced by the Hydrothermal Carbonization of Peat

The influence of the thermophysical characteristics of biochars obtained by hydrothermal carbonization of peat on the yield and composition of producer gas in the course of its steam–air gasification was studied. It was established that an increase in the temperature of hydrothermal treatment of peat facilitated not only an increase in the yield of gas but also an increase in its qualitative characteristics, namely, calorific values. Long-term processing of peat raw materials (50 h) during hydrothermal carbonization led to too deep deoxygenation of the raw materials and adversely affected the quality of the resulting producer gas. 

More

Production of mixtures of hydrocarbons from co and H2 in the presence of Co-SiO2 catalysts prepared by the impregnation method

It has been established that silica gel supports with structures of different porosities can be used for obtaining effective Co catalysts for the synthesis of hydrocarbons from CO and H2. The influence of the addition of Al2O3 on the activity and selectivity of the catalysts has been investigated. It has been shown that Al2O3 has a promoting action on the selectivity of Co-SiO2 catalysts with respect to liquid and solid hydrocarbons.

More

Influence of physiochemical characteristics on properties of Co catalysts for synthesis of hydrocarbons from CO and H2

A study has been made of the influence of the porous structure of precipitated cobalt catalysts on their activity in the synthesis of hydrocarbons from CO and H2. The dependence of activity in relation to ceresin on the structural characteristics of the catalyst has been determined. It has been established that Co catalysts containing supports with a developed surface (over 200 m2/g) and a polydispersed pore distribution, with which, besides pores of small radii, there is a considerable proportion of wide transport pores with radii of up to 2000 nm, are preferable for the synthesis of high-molecular weight hydrocarbons from CO and H2.

More

The influence of physico-chemical characteristics on the properties of Co catalysts of hydrocarbon synthesis from CO and H2

The influence of cobalt catalyst porous structure on their activity in hydrocarbon synthesis from CO and H2 has been studied. The dependence of certain activity from catalyst structural characteristics has been determined. It has been established that Co-catalysts containing supports with developed surface and polydispersive pores distribution are the best for high molecular hydrocarbon synthesis from CO and hydrogen.

More

Mineralogical composition and physicochemical properties of bentonite from Tarasovskoe deposit

Samples enriched with montmorillonite and treated with sodium carbonate and sulfuric acid are prepared from alkaline-earth bentonite from the Tarasovskoe deposit. The influence of the enrichment and treatment on the mineralogical composition of bentonite is evaluated. The specific surface area, degrees of absorption of organic dye, plasticity index, and mechanical compression strength of the samples are determined.

More

Diffusion effect on hydrocarbon synthesis from CO and H2 with a cobalt catalyst

The synthesis of hydrocarbons from carbon monoxide and hydrogen (products of coal gasification) at 0.9 MPa on a cobalt catalyst was studied. It is established that the synthesis of C5-C60 hydrocarbons proceeds in the external diffusion region, whereas the synthesis of ceresine (C60+) takes place in the internal diffusion region. It is suggested that the process selectivity can be controlled by the pore size distribution in the catalyst support.

More

Diffusion in the synthesis of hydrocarbons from CO and H2 on a cobalt catalyst

We studied the synthesis of hydrocarbons from CO and H2 - the products of coal gasification at a pressure of 0.9 MPa on a cobalt catalyst with a granule size of 3-4 mm. We found that the synthesis of C5-C 60 hydrocarbons proceeds in the external, and of ceresine (C 60+) in the internal diffusion region. It is presumed that the selectivity of the process can be controlled by regulating the distribution of the pore radiuses of the support.

More

Temperature-programmed reduction study of Cu1-xNi xCr2O4 solid solutions

Cu1-xNixCr2O4 solid solutions are studied by temperature-programmed reduction (TPR). This method is demonstrated to be sensitive to changes in the structure and composition of the solid solutions. The Cu1-xNixCr2O4 solid solutions whose compositions are near the multicritical point take up the greatest amounts of hydrogen at 910 to 950°C. The TPR method proved to be applicable to structural studies of solid solutions.

More

Catalytic hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol at atmospheric pressure in the liquid phase

Selective hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol on suspended palladium and Raney nickel catalysts at atmospheric pressure was studied. The optimal parameters of this reaction were determined. Samples containing 90% 2-butene-1,4-diol were prepared.

More

Relationship between the selectivity of the Fischer-Tropsch process and type of pore structure of cobalt catalysts

The dependence of the selectivity and output capacity of the Fischer Tropsch process with respect to liquid and solid hydrocarbons on pore structure parameters of a catalyst was determined for the example of a cobalt catalyst produced by impregnation of a preformed aluminosilicate support. The results obtained are analyzed in terms of the diffusion-kinetic theory.

More

Electrolytic reduction of 2-butyne-1,4-diol as a route to trans-2-butene-1,4-diol

The effect of the cathode material on the electrochemical transformations of 2-butyne-1,4-diol at atmospheric pressure was studied by chromatographic analysis. The optimal parameters of the selective synthesis of trans-2-butene-1,4-diol were determined.

More

Control over selectivity and rate of hydrocarbon synthesis from carbon monoxide and hydrogen

A mathematical model was developed for hydrocarbon synthesis from CO and H2 in a tubular fixed-bed reactor over a cobalt catalyst. On the basis of the model, optimal conditions for the process in the cases when the desired products are C7H16 and C17H 36 are recommended.

More

Assessment of the adequacy of a mathematical model for the Fischer-Tropsch synthesis in a fixed-bed tube reactor with a cobalt catalyst

The adequacy of a model developed for the synthesis of hydrocarbons from CO and H2 was assessed. It was found that the results calculated based on this model correspond to experimentally obtained data with a high degree of accuracy (the squared coefficient of correlation was higher than 0.97).

More

Procedures for recovery of crystalline 2-butyne-1,4-diol from industrial aqueous solutions and for its purification

Four procedures for recovery of crystalline 2-butyne-1,4-diol from aqueous solutions and for its purification were examined. Samples of crystalline 2-butyne-1,4-diol containing 98.5 to 99.9 wt % target product were obtained.

More

Oxidation products of fused 2-hetarylimidazole derivatives

Oxidation of 5-(1-methyl-1H-benzimidazol-2-yl)thiophene-, and -selenophene-2-carbaldehydes with potassium dichromate in 20% aqueous sulfuric acid afforded the corresponding carboxylic acids. Analogous reaction with 5-(1-methyl-1H-benzimidazol-2-yl)furan-2-carbaldehyde led to the formation of 1- methyl-1H-benzimidazole as a result of decarboxylation of the primary oxidation product and subsequent decomposition of the furan ring. Probable factors responsible for instability of 5-(1H-benzimidazol-2-yl)- hetarene-2-carboxylic acids were considered. The oxidation of 2-furylnaphtho[2,3-d]- and 2-hetarylphenanthro- [9,10-d]imidazoles gave, respectively, an anthraquinone analog and 6,7-quinones. ?-Electron-rich heterocycles in 2-furyl- and 2-pyrrolylphenanthro[9,10-d]imidazoles were oxidized completely, being replaced by hydrogen.

More

Identification of an admixture in 1,4-butanediol at its production by the roeppe method

A possibility was studied for the isolation of a prebutanediol admixture contained in a marketable product and in raw butanediol by the rectification method with the purity necessary for the subsequent identification. The independent method of obtaining the required admixture was found. Its structure was determined by physicochemical methods and elemental analysis.

More

Structure and gasification of coal from the Gukovo-Gryaznovskoe deposit

The structural elements of the organic matter and the composition of an anthracite sample from the Gukovo-Gryaznovskoe deposit in Rostov oblast were considered. The process of layer coal gasification was studied at atmospheric and elevated pressures.

More

Recent development in heavy paraffin synthesis from CO and H2

A review of recent studies on the Fischer–Tropsch synthesis of heavy paraffins is presented. The effects of temperature, pressure, feed composition, active metal, promoters and carriers on the formation of heavy products are discussed. New approaches to wax-selective processes such as the application of metallic carriers and supercritical fluids are also described.

More

Influence of manganese on formation of active phase of cobalt catalyst of hydrocarbon synthesis

The active phase and catalytic properties of cobalt catalysts of Fischer-Tropsch synthesis promoted with manganese and prepared by impregnation were studied. KSKG silica gel having a monodisperse structure with an average pore diameter of 12-16 nm was used as a support. The cobalt content in the obtained samples was 20.8-21.8 wt. %, manganese content was 0.5-2 wt. %. The structural characteristics of the catalysts were investigated by X-ray diffraction, transmission electron microscopy, temperature-programmed reduction and temperature-programmed hydro-gen desorption. The catalytic activity and selectivity of the samples in the process of hydrocarbon synthesis were researched in the flow mode at a pressure of 0.1 MPa, at a Gas Hourly Space Ve-locity (GHSV) of 100 h-1, at the temperatures of 150-220 °C and a ratio of CO to hydrogen in synthesis gas of 2:1. Preliminary reduction of catalysts was carried out with hydrogen at a tem-perature of 400 °C. In the composition of the studied samples with manganese the formation of solid solutions of metals such as xCo3O4-(1-x)Mn3O4 was confirmed. It is shown that the reduc-tion process of Co3O4 is determined by the composition and structure of solid solutions of compo-nents that are hard-to-recover compounds. The features of the promoting action of manganese depending on the concentration are determined. The introduction of 0.5-2 wt. % manganese al-lows to regulate the composition and microstructure of cobalt oxide compounds, the properties of metallic Co, increases the catalytic characteristics: activity, selectivity for C5+ and reduces the yield of methane. It is shown how, depending on the content of the metal additive, the manifesta-tions of the structural (at a concentration of 0-1 wt. %) or electronic (at a concentration of 2 wt. %) promoting action of manganese increase. The optimum concentration of manganese is 1 wt. %. The catalyst is characterized by the minimum average size of crystallites, the highest val-ue of the specific surface of cobalt metal and the maximum catalytic indicators. © 2020, Ivanovo State University of Chemistry and Technology.

More

Catalysts in the conversion of coal and shale into synthetic hydrocarbons

The preparation and use of Co catalysts for the synthesis of hydrocarbons from CO and H2 mix- tures-coal and oil shale gasification products-were considered. Problems related to increasing the activity and selectivity of the catalytic test systems were reported.

More

Synthesis of high-molecular-weight hydrocarbons from CO and H2 over a cobalt catalyst

Hydrocarbon synthesis from CO and H2 over a cobalt catalyst has been carried out, and the dependence of the selectivity and productivity of the process on process parameters, namely, temperature, pressure, GHSV, and synthesis gas composition has been investigated. Raising the temperature by 17°C decreases the high-molecular-weight hydrocarbon (C35+) selectivity of the process by 24% at GHSV = 60 h-1 and by 69% at GHSV = 100 h-1. Raising the pressure from 0.1 to 2.0 MPa improves these characteristics of the process, and increasing the GHSV from 60 to 300 h-1 diminishes them. Concentrated synthesis gas mixtures should be used to obtain C35+ hydrocarbons (ceresin). The actual composition of the resulting hydrocarbon mixture differs from the theoretical composition calculated using the Anderson-Schulz-Flory molar mass distribution equation, suggesting that, under real synthesis conditions, the molar mass distribution is described by more complicated relationships. This study is an applied one, and its results are planned to be used in the design of a pilot plant for ceresin (brand 100) production.

More

Developing a pilot industrial plant for the production of synthetic hydrocarbons from natural gas

Basic engineering solutions for a pilot industrial plant for the production of synthetic hydrocarbons from natural gas by a three-stage scheme that includes the synthesis of syngas, the synthesis of a wide fraction of hydrocarbons, and the separation and purification of ceresin are developed. The partial oxidation of methane (natural gas) with air for the synthesis of syngas is validated. The area of stable operation for tubular reactors based on a cobalt catalyst using diluted syngas is determined for the synthesis of a wide fraction of hydrocarbons: T ≤ 230°C, P ≤ 2.0 MPa, gas hourly space velocity (GHSV) ≤ 1500 h-1. Target synthesis products that include Ceresin 100 are separated via stagewise fractionation at atmospheric and low (below 10 mmHg) pressures and T ≤ 360°C. The proposed solutions ensure the flexibility and reliability of the pilot industrial plant and the possibility of refining its operational regimes within a wide range of process parameters.

More

Fischer-Tropsch process for the synthesis of hydrocarbons in flow and flow circulation modes (Short Communication)

The results obtained in the synthesis of hydrocarbons from CO and H2 in flow and flow circulation modes are compared. It is established that the latter mode has a number of advantages.

More

Feasibility of using a tube reactor in high-intensity fischer-tropsch synthesis

This article considers some of the problems associated with the use of a tube reactor in high-intensity Fischer-Tropsch (FT) synthesis with heavy loads of processed syngas (3000-5000 h−1). The main factor preventing the development of highly efficient FT synthesis is removal of the heat released. Intensification of the heat-exchange process may be possible by accelerating the convective heat-exchange component by increasing the linear speed of the gas flow from 0.1 to 10 m/sec. Required values of the heat-exchange coefficient, and the fictitious linear velocities of the gas flow at which maximum degree of CO processing is attained without disruption of the stable operating temperature regime of the reactor have been calculated. The expediency of reactive-gas circulation in FT synthesis is demonstrated.

More

Effect of the dilution of synthesis gas with nitrogen on the Fischer—Tropsch process for the production of hydrocarbons

The process of the production of hydrocarbons from synthesis gas diluted with nitrogen according to the Fischer–Tropsch method was investigated. It was experimentally established that inert-ballasted synthesis gas facilitated an increase in selectivity for C5+ and C35+ hydrocarbons and a decrease in selectivity for C1–C4 hydrocarbons. The dilution of synthesis gas improved heat exchange conditions in the reaction zone and decreased the synthesis temperature and a temperature gradient across the catalyst bed. A loss of process efficiency upon the dilution of synthesis gas can be compensated due to an increase in the gas space velocity. The applicability of diluted synthesis gas to the production of the high-molecular-weight C35+ hydrocarbons was demonstrated.

More

Experience in introducing a cobalt catalyst technology for the synthesis of hydrocarbons from CO and H2

The experience in introducing the technology of for the production of a silica-supported cobalt catalyst under industrial conditions is summarized. The catalyst is designed for the selective synthesis of С5+ hydrocarbons from СО and Н2, including macromolecular hydrocarbons С35+. The technology has been implemented at ZAO Samara Catalyst Factory. Parameters of the technological process are adjusted to allow for the features of existing equipment in preparing an experimental industrial lot of catalysts. The optimum technological mode of support preparation (evacuation to avoid granule cracking), its impregnation (at 80°С over 30 min), and the thermal treatment of the catalyst (in programmed mode at a maximum temperature of 400°С over a total of 9 h) are determined. The catalysts of an experimental industrial lot of 1 m3 conform to the new technical conditions in their physicochemical and catalytic properties.

More

Industrial catalyst for the selective Fischer—Tropsch synthesis of long-chain hydrocarbons

The results of development of an industrial supported cobalt–silica gel catalyst for the Fischer–Tropsch synthesis are reported. The studies included the selection of a support and the determination of an optimum active component content, a calcination temperature, and the effect of doping with aluminum oxide on the physicochemical and catalytic properties of the Co–SiO2 system. The catalyst samples were characterized by a set of physicochemical methods. The on-stream stability of the supported cobalt–silica gel catalyst was tested in the continuous mode for 1000 h. In the course of the entire test cycle, the catalyst exhibited stable operation under varied synthesis temperature and gas space velocity, and it can be recommended for industrial applications. The experimental results were used for the preparation of a pilot batch of the catalyst.

More

Unexpected increase in C5 + selectivity at temperature rise in high pressure Fischer-Tropsch synthesis over Co-Al2O3/SiO2 catalyst

The effect of process variables on selectivity of Fischer-Tropsch synthesis (FTS) over Co/SiO2 catalyst was studied in a fixed-bed reactor operating in gas recycle mode. The unusual increase in C5 + selectivity with temperature was found in FTS at 6 MPa. Whereas at a moderate pressure (2 MPa) the catalyst response on temperature was typical for FTS, i.e. increase in activity concurrent with decrease of C5 + selectivity, at high pressure the C5 + selectivity grew up in parallel with catalyst activity. Selectivity to C35 + hydrocarbons was in order of magnitude greater in the FTS at 6 MPa compared to 2 MPa.

More

The impact of Al2O3 promoter on an efficiency of C5+ hydrocarbons formation over Co/SiO2 catalysts via Fischer-Tropsch synthesis

The influence of doping of Co/SiO2 catalysts with alumina on a performance of Fischer-Tropsch synthesis (FTS) was studied by extended FTS trials in a fixed-bed tubular pilot-scaled reactor. The addition of small amount of Al2O3 causes apparent promotional effect on the catalysts activity and C5+ hydrocarbons selectivity. The largest promotion effect was observed for the catalysts with 1 wt.% of alumina loading. The modification of the catalyst with alumina (1 wt.%) changes molecular weight distribution of the resultant C5+ paraffins with increasing the fraction of C8–C25 and decreasing the fraction of longer chain hydrocarbons. The addition of a proper amount of alumina into Co/SiO2 catalyst alters Co° particle size distribution making it narrower with the maximum at 8 nm and the same mean value for Co° particle size. A volcano-like dependence of CO chemisorption on alumina loadings with a maximum at 1 wt.% was observed. Relatively high CO chemisorption at the proper amount of alumina decreases the ratio of surface hydrogen to carbon monoxide and in such a way promotes formation of C5+ hydrocarbons.

More

Synthesis of Low-Pour-Point Diesel Fuel in the Presence of a Composite Cobalt-Containing Catalyst

Production of synthetic diesel fuel by the Fischer–Tropsch (FT) method in the presence of a composite catalyst prepared by mechanically mixing 35 wt % Co/SiO2, 30 wt % HZSM-5, and 30 wt % Al2O3 has been studied. The catalyst has been characterized by the H2 TPR, H2 TPD, NH3 TPD, XRD, SEM, and TEM methods. Catalytic properties have been studied in a fixed-bed flow reactor at 2 MPa and a GHSV of 1000 h–1 in the temperature range of 230–250°C. The highest efficiency and C5+ HC selectivity values of 130 kg/(m3 h) and 72.5%, respectively, are achieved at 250°C. The low-temperature properties of the synthetic diesel fuel meet the requirements for winter diesel.

More

Enhancement of the Fischer—Tropsch process for producing long-chain hydrocarbons on a cobalt—alumina—silica gel catalyst

The effects of the H2/CO ratio, pressure, temperature, and the reaction-gas recycle ratio on the selectivity for hydrocarbons (HCs), including long-chain C35+ HCs, in the Fischer–Tropsch synthesis over a supported industrial cobalt–silica gel catalyst have been studied. The synthesis parameters have been as follows: a pressure of 2.0 or 6.0 MPa, an H2/CO ratio of 1–5, a recycle ratio of 2–6, a temperature of 150–240°C, and a gas hourly space velocity of 1000 h−1. It has been shown that gas recycling provides thermal stability in the catalyst bed, significantly increases the yield of C35+ HCs, and makes it possible to control the group and fractional composition of the synthesis products.

More

Development and industrial approbation of technologies of cobalt catalysts for synthesis of long chain hydrocarbons from synthesis gas

The compositions, methods of preparation and specific technological parameters of the production processes of cobalt catalysts for the synthesis of long chain hydrocarbons from syn-thesis gas were justified. To obtain C35+ selective catalysts by coprecipitation of active compo-nents, the carrier must provide a polydisperse distribution of the pore volume along the radii. This is achieved by hydrothermal treatment of the aluminosilicate carrier. To increase the strength of catalysts, it is possible to incorporate natural bentonites and diatomite of Roctov region deposits into the composition of coprecipitated catalysts. Effective catalytic systems are impregnated cata-lysts on Al2O3 and SiO2 supports with aluminum oxide promotion. The insertion of 5% - Al2O3 of cobalt metal mass allows to form crystallites of Co-CoO system with a size of 8 nm on the SiO2 surface, which provides high activity and selectivity for ceresin. Aluminum oxide is stabilized with Co3O4 in a structure with a high degree of ordering, without hindering its reduction, with the formation of cobalt predominantly with the crystalline structure of hexagonal close packing. Cat-alyst technologies are implemented in industry. The catalysts underwent continuous continuous testing (1000 h) in laboratory and industrial conditions, showed high stability of operation. Dur-ing the entire operation, the yield of C5+ hydrocarbons was 159-171 g/Nm3 based on the processed synthesis gas. The long-chain hydrocarbons C35+ (ceresin) obtained are of high quality: the drop-ping point was 114-116 °C (37-40% ceresin content). Operation during the year of two industrial reactors at the Novocherkassk plant of synthetic products with a total volume of catalyst loading of 18 m3 confirmed the results of laboratory tests.

More

The Microstructure of Cobalt Silica Gel Catalyst in the Presence of Al2O3 Additive

The physico-chemical characteristics and microstructure of cobalt silica gel catalysts with an Al2O3 additive (up to 10%) for the synthesis of hydrocarbons by the Fischer–Tropsch method are studied using a set of methods including X-ray diffraction, BET, IR spectroscopy, and temperature-programmed reduction of H2, as well as scanning and transmission electron microscopy. Phases with a spinel structure, Со3О4, CoAl2O4, and solid solutions on their basis are identified in the samples. The addition of Al2O3 changes the degree of heterogeneity and the orientation of the cobalt crystallites in the oxide and reduced forms of the catalysts. Addition of 1% Al2O3 stabilizes Со3О4 in the spinel form with a structure close to the normal one and promotes the formation of cobalt with a unimodal distribution of particles with an average size of 8 nm. The catalyst is characterized by maximum activity and selectivity with respect to C5+ carbons.

More

Supported Bifunctional Cobalt Catalysts for CO and H2 Conversion to Fuel Fractions of Hydrocarbons

of Supported bifunctional cobalt catalysts for the direct conversion of synthesis gas to liquid fuelfraction hydrocarbons (HCs) have been studied. The effect of ZSM-5 zeolite in the structure of the support preformed using a boehmite binder on the catalytic and physicochemical properties of the catalysts has been examined. The synthesized catalysts exhibit high mechanical strength; therefore, they can be used in tubular Fischer–Tropsch (FT) synthesis reactors. The efficiency of the supported bifunctional Со/(Аl2O3–ZSM-5) catalysts is determined by the number of active metal cobalt sites, the degree of dispersion of the cobalt crystallites, and the total surface acidity. An increase in the catalyst acidity leads to an increase in the fuel fraction selectivity owing to long-chain HCs. At the same time, the activity of the catalysts decreases; therefore, a decrease in their efficiency is observed. It is assumed that this finding is attributed to the diffusion limitations between the HC synthesis and hydrotreating sites.

More

Effect of Diffusion Limitations on the Fischer—Tropsch Synthesis of Long-Chain Hydrocarbons on a Cobalt—Alumina Silica Gel Catalyst

The effect of diffusion limitations on the Fischer–Tropsch synthesis of long-chain hydrocarbons on a cobalt–alumina–silica gel catalyst are analyzed at pressures of 1.5 and 2.0 MPa, depending on the particle size distribution (0.4–6.0 mm), gas hourly space velocity (100–1000 h−1), and composition of the synthesis gas (H2 : CO = 1, 2, and 5). It is shown that mass limitations increase the selectivity and productivity of C35+ hydrocarbons (waxes) and the probability of hydrocarbon chain growth. The effect of intradiffusion limitations is estimated at different compositions of the synthesis gas from changes in the apparent energy of activation in the temperature range of 179–225°С. In the high-temperature region, the apparent energy of activation falls from 97.1 to 67.0–82.9 kJ/mol as the H2/CO ratio rises from 1 to 5.

More

Bifunctional Cо/SiО2-Fe-ZSM-5-Al2O3 catalysts for synthesis of hydrocarbons of engine fractions

The process of obtaining motor fractions of hydrocarbons on bifunctional CO/Sio2-Fe-ZSM-5-Al2O3, catalysts obtained by mixing has been studied. The effect of the method of introduc-ing iron into a catalyst (in the form of reduced iron and its nitrate) at the molding stage is studied. The catalysts were tested in a continuous mode for 30 h at a gas volume velocity of 1000 h-1, a pressure of 2 MPa and a temperature of 240 ° C. It is shown that when iron is introduced in the form of a reduced powder, the temperature gradient in the catalyst bed decreases, and the selectivity for C5+ hydrocarbons increases by 6% in comparison with the catalyst sample without the addition of iron. It has been established that the introduction of iron into the catalyst in the form of a nitrate salt is a less effective method. It blocks the operation of polymerization and acid sites of bifunctional catalysts, contributes to a reduction in CO conversion and selectivity for C5+ hydrocarbons. It is shown that the introduction of iron significantly changes the group composition and molecular-mass distribution of the produced hydrocarbons - the shares of saturated hydrocarbons are in-creases, predominantly of a linear structure, the yield of olefins decreases. The obtained C5+ hydro-carbons mainly consist of gasoline and diesel fractions. The introduction of iron promotes an in-crease in the content of diesel fractions in synthesis products. Thus, with the introduction of iron in the form of a nitrate salt, the content of the diesel fraction increased by 1.2 times in comparison with the sample of a catalyst without iron.

More

Effect of the Composition of Synthesis Gas on a Combined Process of the Synthesis and Hydrofining of Hydrocarbons from CO and H2

The results of studying the effect of the composition of synthesis gas (CO + H2) on the combined process of hydrocarbon synthesis and hydrofining on the Co-SiO2/ZSM-5/Al2O3 composite catalyst at a pressure of 2.0 MPa and a temperature of 240°C are presented. The raw material was concentrated synthesis gas and that diluted with nitrogen with H2/CO ratios from 1 to 3 in the source gas. It was found that, as the H2/CO ratio in the processed gas was increased from 1 to 3, the degree of CO conversion increased from 28.0 to 87.0%; selectivity for C5+ hydrocarbons decreased from 74.0 to 48.0%, and the fraction of unsaturated hydrocarbons decreased by a factor of 12. The dilution of synthesis gas with nitrogen also contributed to an increase in the degree of CO conversion from 75.8 to 84.0% and a small (~3%) increase in selectivity for C5+ hydrocarbons under the condition of the same ratio H2/CO = 2 in diluted and concentrated synthesis gas. The amount of branched alkenes in a gasoline fraction increased from 14.0 to 32.5%, whereas it remained almost unchanged in a diesel fraction. The maximum catalyst productivity (108 kg m–3 h–1) was achieved with the use of synthesis gas with the ratio H2/CO = 2.

More

Thermodynamic Study of Associated Petroleum Gas Reforming to Methane

The equilibrium constants and heats of reactions of reforming of associated petroleum gas (APG) with different concentrations of methane homologues in the temperature range of 300–475°C have been calculated. It has been shown that methanation proceeds in two stages, one of which is the hydrogenolysis of methane homologues. The effect of parameters (temperature, pressure, APG composition) on the equilibrium composition of pre-reforming products, autothermality, and the formation of elemental carbon has been examined. The calculations have been carried out with allowance for nonideality of the gas components (Peng–Robinson model) in the temperature range of 350–450°C at a pressure of 0.1–2.0 MPa. It has been found that at 350–400°C and a pressure of 2.0 MPa, the autothermal reforming of methane homologues is theoretically possible at a steam : gas ratio of 1 : (1–1.25) (for APG with a methane equivalent of 1.8 to 2.6). With such parameters, the formation of elemental carbon is thermodynamically impossible. Keywords: : associated petroleum gas, pre-reforming, equilibrium constant, equilibrium composition, cocking.

More

Production of Motor Fuel Hydrocarbon Fractions from Pine Wood (Short Communication)

The possibility of producing motor fuel hydrocarbon fractions from pine sawdust with the use of a Co–SiO2/HZSM-5/Al2O3 hybrid catalyst at the stage of the Fischer–Tropsch synthesis was demonstrated. It was determined that 163.6 kg of liquid hydrocarbons consisting of 87.6% gasoline (with an octane number of 92) and diesel (with a cetane number of 51) fractions can be obtained from 1000 kg of dry sawdust.

More

Effect of the Type of the Cobalt-Containing Component of a Composite Catalyst on the One-Stage Synthesis of Liquid Hydrocarbons from СО and Н2

The effect of the type of the cobalt-containing component (Со-Al2O3/SiO2, Co-Re/Al2O3, and Co-Re/TiO2) of a composite catalyst on the combined synthesis and hydroconversion of hydrocarbons by the Fischer–Tropsch process are investigated. The catalytic properties of catalyst samples are studied in a flow reactor with a fixed catalyst layer at 2 MPa and GHSV of 1000 h–1 within a the temperature range of 240–280°С for 40–90 h of continuous operation. The highest values of output and selectivity to C5+ hydrocarbons are obtained for composite catalyst Со-Al2O3/SiO2(35%)/ZSM-5(30%)/Al2O3(30%) at a temperature of 240°C and are 106 kg/(mcat3 h) and 67.1%, respectively. It is shown that using Co-Re/Al2O3 instead of Со-Al2O3/SiO2 catalyst produces comparable values of catalytic activity, but considerably fewer unsaturated hydrocarbons are found in the products of synthesis. Using Co-Re/TiO2 catalyst and raising the temperature (to 280°С) shifts the molecular weight distribution of the products of synthesis toward the formation of a gasoline fraction. It is found that the rate of catalyst deactivation grows in the order Со-Al2O3/SiO2 > Co-Re/Al2O3 > Co-Re/TiO2.

More

Deactivation of Co-Al2O3/SiO2 Fischer—Trospch Synthesis Catalyst in Industrially Relevant Conditions

The deactivation rate of Co-Al2O3/SiO2 Fischer–Tropsch synthesis catalyst have been experimentally assessed at industrially relevant conditions (T 198–237 °C, P = 60 bar, H2/CO = 1.85, GHSV 2000–7000 h–1). The fresh and spent catalyst was characterized by XRD, XPS, BET, TEM, and SEM–EDX techniques. Decreasing active surface area due to cobalt oxidation by product water and sintering of cobalt crystallites were found to be minor factors for the deactivation. The principal reason of activity loss seems is diffusion limitations arising due to catalyst pores plugging by product wax. The linear dependence between gas flow rate and estimated catalyst lifetime was revealed. High GHSV of fresh synthesis gas and/or high circulation ratio of product gas should be employed to prevent rapid loss of catalyst activity.

More

Deactivation of a Commercial Co—Al2O3/SiO2 Catalyst in Fischer—Tropsch Synthesis under High-Pressure and Gas Recycling Conditions

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.

More

Effect of Re and Al2O3 Promotion on the Working Stability of Cobalt Catalysts for the Fischer—Tropsch Synthesis

The results of the working stability studies of cobalt catalysts based on SiO2 and Al2O3 promoted with Re and Al2O3 in the synthesis of hydrocarbons from CO and H2 in continuous tests for 200–300 h are presented. The prepared catalysts were characterized by transmission electron spectroscopy, temperature-programmed reduction with hydrogen, temperature-programmed desorption of CO, and X-ray fluorescence spectroscopy and tested at a temperature 200°C, a pressure of 0.1 MPa, and a GHSV of 100 h–1. It was determined that a cobalt–silica catalyst promoted with Al2O3 had the highest activity. It was established that the addition of Al2O3 to a cobalt–silica catalyst increased the conversion of CO and selectivity for C5+ hydrocarbons and inhibited the agglomeration of Co particles under the action of a reaction atmosphere in the Fischer–Tropsch synthesis. It was found that the initial conversion of CO increased by a factor of 2 upon the introduction of 0.1 wt % rhenium into the Co/γ-Al2O3 catalyst; however, the rate of its deactivation increased in this case due to an almost twofold increase in the size of cobalt particles in the course of synthesis after operation for 300 h.

More

Effect of Gas Circulation on the Synthesis of C35+ Long-Chain Hydrocarbons from CO and H2 at a High Pressure

The effect of gas recirculation on the preparation of C35+ long-chain hydrocarbons on a supported Co-Al2O3/SiO2 catalyst at 6.0 MPa, 225°C, and the gas hourly space velocity of 1000 h–1 is studied. It is shown that the circulation regime allows the catalyst bed to be isothermal and improves the selectivity and productivity of C35+ hydrocarbons. It is found that the rate of catalyst deactivation slows by a factor of eight when the circulation ratio is raised from 2.2 to 6, while the amount of unsaturated hydrocarbons in the products of synthesis doubles.

More

Conversion of Liquefied Hydrocarbon Gases on Industrial Nickel Catalysts

The two-stage conversion of industrial liquefied hydrocarbon gases (LHGs) on NIAP-07-01 (NKM-1) and NIAP-03-01 catalysts is studied to obtain hydrogen-containing gases. The experiments are performed in flow reactors with fixed catalyst layers at a pressure of 0.1 MPa under the conditions of pre-reforming: temperature, 350–450°С; GHSV = 1000–3000 h−1; steam : gas ratio, (4 : 1)–(8 : 1). For steam–air reforming: temperature, 700°С; GHSV = 2000 h–1; air : gas ratio, 1.2 : 1. The concentrations of converted gas components under these conditions correspond to equilibrium values calculated using the Peng–Robinson model. The conversion of methane homologs is almost 100% during the pre-reforming stage, while the concentrations of methane and hydrogen are 32–54 and 24–47%, respectively. The main condition for the pre-reforming of hydrocarbon gases with a high methane equivalent is a Н2О : С ratio greater than 2 to avoid the formation of elemental carbon (carbonization). The yield of hydrogen-containing gas during two-stage reforming is 15.6 m3, obtained from 1 m3 of initial LHGs with a hydrogen content of 41.81%, and the total amount of CO and H2 is more than 52%.

More

Development of a Highly Productive Supported Bifunctional Catalyst Based on Zeolite ZSM-5 for the Production of Fuel Grade Hydrocarbon Fractions from CO and H2

The highly productive supported bifunctional catalyst based on cobalt, zeolite ZSM-5, and a binding agent (boehmite) is developed for the production of gasoline and diesel hydrocarbon fractions. Influence of the concentration of the ZSM-5 zeolite in the range of 0–70 wt % and cobalt (6.4–18.0 wt %) on activity and selectivity for individual groups of hydrocarbons in the synthesis of hydrocarbons from CO and H2 is studied. The catalysts are characterized by X-ray powder diffraction, the Brunauer–Emmett–Teller method, and hydrogen temperature-programmed reduction and tested in the synthesis of hydrocarbons from CO and H2 in the continuous mode at a pressure of 2.0 MPa, a gas space velocity of 1000 h−1, and a temperature of 240°C. It is found that the time of reduction of the supported catalyst should be at least 10 h. In the case of an increase in the fraction of the zeolite in the catalyst, iso-alkanes are predominantly synthesized; to a lesser extent, branched alkenes. On the contrary, in the case of a decrease in the concentration of cobalt, the branched alkene selectivity grows and iso-alkane selectivity drops. The optimum concentrations of the zeolite and cobalt for the highly productive supported bifunctional catalyst are within 60–70 and 6–12 wt %, respectively.

More

Preliminary evaluation of a commercially viable Co-based hybrid catalyst system in Fischer-Tropsch synthesis combined with hydroprocessing

Syngas conversion via the Fischer-Tropsch synthesis (FTS) protocol provides a promising alternative to flaring or re-injection of associated petroleum gas to monetize it. The most attractive method for this is direct conversion of syngas into transportation fuels over hybrid catalyst systems comprising both a catalyst for FTS and a zeolite component that catalyzes hydroprocessing (HP) of primary hydrocarbons. Here we describe a hybrid catalyst system in which a pre-formed silica-supported cobalt catalyst for FTS and a ZSM-5 zeolite component as an HP catalyst reside within a single extruded particle, in nanoscale vicinity to each other, while the sizes of the extrudates are suitable for their commercial application. The prepared hybrid catalysts were tested for their performance in a bench-scale fixed bed reactor operating at T = 240-250 °C, P = 1.0-2.0 MPa, GHSV = 1000 h-1 and H2/CO = 1-3 and showed higher activities in both FTS and HP as compared with some recently reported catalysts. The prepared catalysts were characterized by temperature-programmed desorption of hydrogen (H2-TPD) and ammonia (NH3-TPD), X-ray diffraction (XRD) using synchrotron radiation, high-resolution transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). As has been shown by TEM, the procedure applied to prepare the hybrid catalyst system does not change the size distribution of cobalt nanoparticles in the resulting hybrid catalyst as compared with the parent FTS catalyst.

More

Production of Motor-Fuel Hydrocarbon Fractions from Sunflower Husk Biomass

The production of synthetic hydrocarbons from sunflower husk biomass including the stages of gasification and the Fischer–Tropsch (FT) synthesis of hydrocarbons was studied. It was found that H2/CO = 2 was an optimal ratio for the production of motor-fuel hydrocarbon fractions, and steam–oxygen gasification provided a minimum concentration of ballast components in the synthesis gas. The synthesized hydrocarbons mainly consisted of gasoline and diesel fractions and contained to ~60% isomeric structures.

More

Hybrid Catalyst for the Selective Synthesis of Fuel Range Hydrocarbons by the Fischer—Tropsch Method

The results of the development of a hybrid catalyst for the one-pot synthesis of liquid hydrocarbons by the Fischer–Tropsch method are presented. The catalyst was synthesized by the mechanical mixing and molding of Co–Al2O3/SiO2, zeolite HZSM-5, and boehmite powders. The zeolite was promoted with palladium by ion exchange (1.0 wt %). The catalysts were characterized by X-ray diffraction analysis, BET, scanning and transmission electron spectroscopy, and temperature-programmed desorption of ammonia and hydrogen and tested at a temperature of 240°C, a pressure of 2.0 MPa, and a GHSV of 1000 h–1. The preparation method proposed makes it possible to obtain a hybrid catalyst with a stable structure and an average cobalt particle size of 8 nm; this catalyst exhibited high productivity and selectivity for the formation of liquid hydrocarbons from CO and H2.

More

Effect of the Means Used to Synthesize Bifunctional Fischer—Tropsch Catalysts on the Composition and Properties of Synthetic Fuels

The effect of the means used to synthesize bifunctional cobalt catalysts with HZSM-5 zeolite and a boehmite binder on the catalytic performance of Fischer–Tropsch (FT) synthesis is studied. The synthesized catalysts are characterized via BET, XRD, EDA, SEM, TEM, H2 TPD, and NH3 TPD. They are tested in hydrocarbon synthesis at a pressure of 2.0 MPa, a temperature of 240°C, and a gas hourly space velocity of 1000 h−1. It is shown that the hydrocarbon and fractional composition of the FT synthesis products can be controlled, depending on the means of catalyst synthesis. A promising composite catalyst system for the single-stage synthesis of a low–pour-point diesel fuel has been proposed.

More

Bifunctional Cobalt-Containing Catalytic Systems Based on SAPO-11 Molecular Sieves in Fischer—Tropsch Synthesis of Fuels

The study investigated, for the first time with respect to Fischer–Tropschsynthesis of fuels, cobalt-containing catalytic systems based on SAPO-11molecular sieves with differing secondary porous structure characteristics.Various methods, such as XRD, low-temperature nitrogen adsorption/desorption,SEM, TEM, H2-TPD, and NH3-TPD,were used to characterize the prepared catalysts, which were subsequentlyexamined in hydrocarbon synthesis at 2.0 MPa, 240°C, and gas WHSV = 1000h–1. The study demonstrated good prospects formicro/mesoporous-structured SAPO-11 as an acid catalyst component for fuelproduction.

More

Combined Synthesis and Hydroprocessing of Hydrocarbons over Co/SiO2 + ZSM-5 + Al2O3 Catalysts Promoted by Nickel

The study investigates the effects of nickel introduction methods on theproperties of a hybrid cobalt catalyst in a combination of Fischer–Tropschsynthesis and the hydroprocessing of the synthesized products. At 240°C, 2 MPa,and syngas WHSV 1000 h–1, the catalytic performanceswere compared, the products were analyzed for the hydrocarbon and fractionalcompositions, and the characteristics of the synthesized fuels were determined.Among the catalysts differing in nickel introduction method, the sample with anickel-containing zeolite component prepared by ion exchange was found to havethe highest hydrogenation activity, while the sample with a metal componentgenerated by joint cobalt/nickel introduction [Co/SiO2 +Ni(i)/HZSM-5 + Al2O3] exhibitedthe highest isomerization activity.

More

Bifunctional Cobalt Catalyst for the Synthesis of Waxy Diesel Fuel by the Fischer—Tropsch Method: From Development to Commercialization

The effect of the quality of Russian commercial zeolites HZSM-5 of various grades on the properties of a bifunctional cobalt catalyst in the form of a composite mixture used in the Fischer–Tropsch synthesis was studied. The activities and selectivities of the catalyst samples were compared. The fractional and hydrocarbon composition of the synthesis products was investigated. The viscosity and temperature characteristics of the diesel fraction of fuel were determined. A promising sample of zeolite HZSM-5 was chosen for practical implementation of the catalytic technology.

More

Influence of operating conditions on the main characteristics of a cobalt Fischer-Tropsch catalyst

Three stages of extraction of the contents of the porous space of cobalt catalysts, continuously operating for different periods of time (Time on stream (TOS) is from 40 to 800 h) in a Fischer-Tropsch fixed bed reactor, were performed to identify carbon-containing compounds using chromatographic analysis. At each stage of extraction, the surface of the samples under study was investigated by SEM and BET methods. It was determined that during operation, as a result of accumulation of linear alkanes in the pores of the catalyst with an average number of carbon atoms from 20 to 25 and a decrease in the specific surface area, the reaction rate reduces by 25-30 %. With the help of oxidative treatment, it was found that elemental carbon is contained in the porous space of the spent catalysts.

More

Prospects for Technologies in the Production of Synthetic Base Stocks for Engine Oils (A Review)

The paper presents a review of modern industrial and competitive experimental approaches to gas-to-liquid (GTL) and polyalphaolefin (PAO) oil technologies for the production of synthetic base oils. The key aspects of the synthesis of environmentally friendly isoparaffin and PAO base oils are discussed: the feedstocks, process designs, and catalysts. Based on an analysis of relevant scientific and engineering advances reported to date, the current trends of synthetic base oil technologies are shown, including the creation of novel high-performance homogeneous and heterogeneous catalysts, as well as the prospects for the Fischer-Tropsch process and the GTL technology in general for the production of isoparaffin oils (including those with improved low-temperature properties) and of synthetic PAO oil components.

More

Reasons for the Rapid Deactivation of a Cobalt Catalyst in the High-Efficiency Fischer—Tropsch Synthesis of C19+ Hydrocarbons

The results of a study on the deactivation of an industrial Co–Al2O3/SiO2 catalyst under the conditions of highly productive Fischer–Tropsch synthesis of long-chained hydrocarbons at high pressure (6 MPa) are presented. It was found that an increase in the synthesis temperature led to a decrease in the rate of catalyst deactivation. The effect of the thermal agglomeration of cobalt particles and the carbonization of catalyst surface on the activity of the catalyst under the test conditions was insignificant. A correlation between the rate of catalyst deactivation and the selectivity for С19+ hydrocarbons was found; this correlation indicated the blocking of chain growth centers by synthesized waxes as the main reason for the rapid loss of catalyst activity.

More

Effects of SiO2/Al2O3 Ratio in ZSM-5 Zeolite on the Activity and Selectivity of a Bifunctional Cobalt Catalyst for Synthesis of Low-Pour-Point Diesel Fuels from CO and H2

This study investigates the production of diesel fuels by integrated Fischer–Tropsch synthesis over a bifunctional cobalt catalyst consisting of a cobalt component (Co–Al2O3/SiO2) and a zeolite-containing component (ZSM-5). The catalytic properties were tested in a continuous-flow reactor with a stationary catalyst bed at 240–250 °C, 2 MPa, and gas WHSV 1000 h–1. The effects of the SiO2/Al2O3 ratio in a HZSM-5 zeolite on the catalytic performance, catalyst deactivation rate, and hydrocarbon and fractional compositions of the synthetic product were identified. The low-temperature properties of the synthesized diesel fuel satisfy the current requirements for winter fuels.

More

Relation between Morphology and Porous Structure of SAPO-11 Molecular Sieves and Chemical and Phase Composition of Silicoaluminophosphate Gels

The formation of silicoaluminophosphate gels using boehmite, Al isopropoxide, and di-npropylamine as a template of silicoaluminophosphate gels as well as their subsequent crystallization into SAPO-11 molecular sieves was studied in detail using X-ray fluorescence spectroscopy (XRF), powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption–desorption methods. The effect of the chemical and phase composition of silicoaluminophosphate gels on the physicochemical properties of SAPO-11 molecular sieves was shown. The secondary structural units that the AEL lattice is composed of were found to be formed at the initial stage of preparation involving aluminum isopropoxide. Several approaches to control their morphology and secondary porous structure are also proposed.

More