Results from the prolonged tests of zeolite-containing cobalt catalysts for Fischer–Tropsch synthesis in reactor tubes comparable in size to those used in industrial reactors. During 3000 hours on stream catalyst activity was decreased by 13%. It is shown that the main reasons for zeolite-containing cobalt catalyst deactivation are agglomeration of cobalt clusters and carbon deposition on the catalyst surface. The authors propose one method of reducing the catalyst deactivation rate and two methods of regenerating it. It is shown that the oxidative regeneration treatment of zeolite-containing cobalt catalysts allows to recover 98% of the initial activity.

Some kinetic parameters of Fischer–Tropsch synthesis (FTS) were determined in the presence of a granular cobalt/zeolite catalyst. Usually, kinetic studies of granular catalysts are considered to be complicated by external and internal diffusion. We managed to obtain a catalyst with a special structure of the active surface, where sites active in FTS are isolated from each other due to the environment of inactive spinel CoAl₂O₄ and inter-site transport is provided by an extensive intragranular graphitic network serving simultaneously as a heat-conductive medium. As a result, FTS proceeded in the kinetic region. It was found that the reaction kinetics obey the Arrhenius law; whereas, the activation energy is different in different temperature ranges, i.e., 118.2 kJ/mol in the range of 180–210 °C, and 173.6 kJ/mol in the range of 232–243 °C. This behavior is determined by the presence of zeolite, which becomes active in the secondary transformations of FTS products at temperatures beyond 210 °C.

The deposition of nanostructured carbon particles on the surface of a catalyst (carburization) is routinely considered an inalienable and undesirable secondary process in Fischer–Tropsch synthesis. However, very little is known about the actual role of the nanocarbon particles and how they influence catalysis. This paper reports research on the influence of carbon deposition on the performance of a cobalt-based Fischer–Tropsch-synthesized catalyst in an industrial-scale fixed-bed reactor (length—6000 mm, inner diameter—16.5 mm). The comparison of the structure and catalytic performance of a pelletized cobalt catalyst with the same catalyst, which was preliminary carburized, is presented. Pellet pore structure, catalyst surface, cobalt cluster morphology and the main catalytic properties (CO conversion, C₅₊ hydrocarbon productivity and selectivity to C₅₊ hydrocarbons and CH₄ formation) were investigated. It is shown that the primary pre-carburization effect is a result of the physical blockage of the catalyst pore structure not followed by drastic changes in the cobalt cluster’s structure.

A cobalt Fischer–Tropsch synthesis catalyst supported on titania-doped silicon carbide is synthesized and comprehensively studied by a number of physicochemical means. The dynamics of the behavior and deactivation of the catalyst was studied after its stable operation for 1500 h during continuous experimental resource testing with a periodic change in the syngas flow rate and pressure and the process temperature. This catalyst has two types of active sites, on which products with different Schulz–Flory distribution parameters form. Depending on the process regime, the effective formation of soft waxes or more high-molecular-weight products is possible.

The effect of the dilution of a synthesis gas with nitrogen on the activity, selectivity and productivity of a Fischer–Tropsch reactor with a fixed bed of granular catalyst during synthesis on a pilot plant of a full cycle for the conversion of natural gas into synthetic oil is studied experimentally. Experimental data are presented that were obtained at different contents of nitrogen in the synthesis gas: up to 2, 50, and 70%. Analysis of the experimental data shows that diluting the synthesis gas contributes to an increase in the selectivity to C₅₊, and a decrease in the selectivity to methane. A drop in the reactor’s productivity observed upon the dilution of synthesis gas can be compensated for by increasing the consumption of synthesis gas. The negative effect of decrease in the pressure of FT synthesis from 2 to 1.5 and 1.0 MPa on the catalytic FT synthesis performed on a twice-diluted synthesis gas at a synthesis gas space velocity of 4000 h^–1 is demonstrated.