AbstractResults of studying the sorption-enhanced water gas shift reaction over a mechanical mixture of grains of 5 wt % Pt/Ce0.75Zr0.25O2 catalyst and 10 wt % NaNO3/MgO sorbent are presented. It is shown that pure magnesium oxide sorbs virtually no СО2 under model conditions, while its promotion with NaNO3 substantially improves the dynamic sorption capacity in the 300–350°C range of temperatures with a maximum at 320°C. The catalyst shows high activity and selectivity in the water gas shift reaction for a model mixture (CO, 11.6; H2, 61; H2O, 27.4 vol %). The concentration of CO at the outlet from the reactor is less than 1 vol % in the 220–400°C range of temperatures (the minimum is 0.3 vol % at 240°C) with СН4 at the temperatures below 320°C (0.61 vol % at this point). Using this sorbent in mixtures with a catalyst in the sorption-enhanced water gas shift reaction at 320°C substantially reduces its sorption capacity, due probably to the full conversion of NaNO3 into Na2CO3 that is not completely decomposed at the stage of regeneration. This nevertheless allows the outlet СО and СН4 concentrations to be halved, relative to values observed at this temperature in experiments with no sorbent: 6.1 × 10−4 and 8.2 × 10−2 vol % per dry gas basis at the middle of the first adsorption cycle. Prospects for using this approach in the sorption-enhanced water gas shift reaction and the need for further studies on improving the capacity and stability of the presented sorbents are described.

AbstractThe activity and selectivity of sulfidized and non- sulfidized palladium alumina supported catalysts in the hydrogenation of 1,3-pentadiene to pentenes is studied. Preliminary sulfidation of palladium catalysts substantially improves their selectivity toward olefins in a broad range of Н2 : diene ratios (from 2.5 to 10). Samples activated in Н2 at elevated temperatures display higher activity in diene hydrogenation. Palladium catalysts are more active at low temperatures of the reaction, but sulfidized Ni catalysts studied earlier are competitive with palladium ones in selectivity toward olefins and productivity, and are more selective in an excess of hydrogen. The modification of palladium with chromium, silver, or lithium improves the selectivity toward olefin.

AbstractThe processes for the production of basic monomers at Nizhnekamskneftekhim via dehydrogenation are described. The cooperative development of modern domestic catalysts with the Kazan Federal University is emphasized. The disadvantages of existing catalytic systems are considered, and the possivle ways of their elimination are presented.

AbstractThe experimence from cooperation with industrial petrachemical and oil refining enterprises in implementation of developments is systematized. The important role of cooperation and interdisciplinary studies is highlighted, and the interaction between consumers and manufacturers of catalysts is considered. The most important stages of the development and implementation of catalysts are described.

AbstractThis work is the third and final part of a series of reviews devoted to the direct synthesis of organotin compounds. This part of the series considers the conditions of and results from the reaction between metallic tin and carbofunctional organohalides. The efficiency of catalysts and the prospects for direct synthesis in the production of carbofunctional organotin compounds are analyzed.

AbstractThe data on the development and study of new catalysts for the reforming and isomerization of gasoline fractions from the Center of New Chemical Technologies BIC (Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences), including the experience in the industrial appliction of reforming catalyst PR-81, are presented. A new catalyst of increased acidity is developed for the reforming of gasoline fractions to ensure a 3–5 wt % reduction in the content of aromatic hydrocarbons in the reformate. A new sulfated zirconia catalyst supported on a porous alumina matrix is developed for the isomerization of the C5–C6 hydrocarbon fraction. An efficient catalyst based on tungstated zirconia is proposed for isomerization of the С7 hydrocarbon fraction. A flowsheet of integrated reforming and isomerization processes is proposed on the basis of the new catalysts to ensure the production of Euro-5 and Euro-6 motor gasolines alongside promising gasolines with reduced contents of aromatic hydrocarbons.

AbstractSystems for the production, storage, and accumulation of hydrogen are an important line in the development of fundamental and applied aspects of alternative energy. Liquid organic hydrogen carriers (LOHCs), polycyclic forms of the corresponding aromatic compounds, are an effective way of hydrogen storage and release with contents of up to 7.3% by mass. The authors compare LOHCs as potential substrates for hydrogen storage and release systems based on catalytic hydrogenation and dehydrogenation reactions, inclusively, with cyclohexane, methylcyclohexane, decalin, perhydroterphenyl, bicyclohexyl, perhydrodibenzyltoluene, and perhydroethylcarbazole. Some data on the activity and selectivity of Pt-containing dehydrogenation catalysts are presented for each of the perhydrogenated substrates.

AbstractThe effect of acid activation with 0.125–0.5 M Н2SO4, HCl, and HNO3 on the physicochemical properties and catalytic performance of natural clay (the Mukhartalinskii deposit) containing 95% montmorillonite (MM) was investigated in the synthesis of solketal [(2,2-dimethyl 1,3-dioxolan-4-yl)methanol] from glycerol and acetone. The reaction rate and selectivity toward solketal are shown to depend on the type and concentration of acid. Both the yield of solketal and the reaction rate rose with increasing acid concentration, which correlates with the increase in the number of Brønsted acid sites. The efficiency of the system was found to diminish in the order MM/HCl > MM/HNO3 > MM/H2SO4 as the surface acidity decreased.

AbstractCommercial super cross-linked polystyrene (SPS) is a promising support for creating heterogeneous catalysts designed for processes of fine organic synthesis. Results from years of studying the creation of heterogeneous Pd-, Pt-, and Ru-containing catalysts based on SPS of grades MN100 and MN270. Data are presented from characterizing SPS and catalysts based on them using a complex of physical and physicochemical means of analysis. It is shown that commercial SPS can be used to synthesize catalysts in the form of spherical grains or preliminarily ground powders. Along with the nature of a metal catalyst precursor, the form of an SPS has a strong effect on the distribution of Pd, Pt, and Ru compounds and the size of metal-containing nanoparticles formed in the polymer’s medium. The catalysts in a hydrogen flow at a temperature of 300°C on the surface chemical composition of powder MN100 samples impregnated w Pd, Pt, and Ru compounds is considered for the first time.

AbstractA study is performed of the main ways of preparing aluminum oxides; the advantages of products of the thermal activation of hydrargillite (gibbsite) for preparing catalysts, supports, and sorbents; factors that influence the products of thermal activation and aluminum oxides according to the technology of thermal activation; and examples of effectively using products of the centrifugal thermal activation of hydrargillite to prepare catalysts, supports, and sorbents.

AbstractThe level of the main catalysts and industrial technologies for the conversion of natural gas into syngas further convrted into ammonia, methanol, and H2 was analyzed. The main trends in their development, aimed at reducing the energy and resources consumption, were described including process flowsheets, catalysts, and sorbents at different stages of methane reforming and CO steam reforming.

AbstractThe possibility of obtaining sorbitol from potato starch via one-pot hydrolysis-hydrogenation is demonstrated using bifunctional catalysts 0.3–3 wt % Ru/Cs3HSiW12O40 (Ru/Cs-HPA). It is found that a catalyst with 1 wt % Ru is the one most effective, since it has the optimum ratio of the concentrations of Brønsted and Lewis acid sites on the support’s surface and a large specific surface area. The kinetics of the reaction with 1% Ru/Cs-HPA is studied and the observed energy of activation of the hydrolysis-hydrogenation of starch to sorbitol is found to be 80 ± 8 kJ/mol. A kinetic model is proposed on the basis of experimental and published data. The model accurately describes the hydrolysis-hydrogenation of starch. The yield of sorbitol was 88 mol % (99 wt %) after 3 hours of the reaction using a catalyst with the optimum composition (1% Ru/Cs-HPA) at the optimum temperature (150°C).

AbstractThe problem of trapping solid particles in a production line with dehydrogenation of C4–C5 isoparaffins to iso-olefins in a fluidized catalyst bed was considered. Dust collection of fine catalyst particles for paraffin dehydrogenation units using a standard TsN-15 cyclone and a new dust collector (NDC) with arc-shaped elements was studied. The results of numerical simulation of TsN-15 and NDC were presented. Comparative studies showed NDC to be more efficient than TsN-15 for trapping fine solid particles with sizes of less than 20 μm. The pressure and flow velocity profiles for NDC were shown to change as a regular tendency, without any critical deviations. The gas flow velocity through the arc-shaped NDC elements was shown to be stable in contrast to TsN-15, which creates high flow velocities at the cyclone periphery to increase the probability of dust breakthrough into the flow.

AbstractA 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.

AbstractA review of literature on current results from work in the field of obtaining microalgae biomass and processing it into high-value products (biofuel, ethanol, butanol, hydrogen and other products) by chemical and biotechnological means is performed. The review consists of three parts: Biomass Production Methods, Biofuel Production from Microalgae, and Obtaining High-Value Products via Biotechnology. The first part considers promising strains of microalgae that produce lipids and are used to obtain biofuels that meet standards ASTM D6751 and EN 14214. Information is also given on factors affecting the accumulation and composition of lipids in microalgae (composition, illumination, temperature, and salinity of the nutrient medium). Data are presented on ways of producing microalgae biomass that include the use of flue gases and wastewater.

AbstractThe fine crystal structure of hematite samples used for preparing potassium promoted iron oxide catalysts of dehydrogenation is studied via X-ray diffraction and scanning electron microscopy. α-Fe2O3 samples are synthesized under non-equilibrium conditions from several precursors in different regimes of thermolysis. The most important characteristic of hematite that causes the activity and selectivity of a hematite-based catalyst is its fine crystal structure (FCS). The fine crystal structure of hematite predetermines the phase composition of the catalyst. The fine crystal structure of hematite forms during its synthesis and is determined by the nature of the precursor, the temperature of synthesis, the temperature gradient, and the rate of the removal of gaseous thermolysis products. The highest activity is displayed by the catalyst prepared on the basis of hematite with mosaic blocks 70–90 nm in size and a minimum SF concentration caused by half and quaternary dislocations. Such hematite was synthesized via the thermolysis of iron sulfate at 950 K under fluidized bed and low temperature gradient conditions. Hematite from iron carbonate is not recommended for use in synthesizing a catalyst due to the high concentration of low-temperature SFs, which result in the formation of catalytically low-active potassium β-polyferrite.

AbstractThe ways for the production of zeolite powders, which are currently manufactuired on an industrial scale, and their conversion into grained zeolite-containing adsorbents and catalysts are studied. Some data on the Russian manufacturers of these materials are presented. A brief overview on the utilization of these materials in adsorption drying, the purification and separation of gaseous and liquid media, and the catalytic processing of hydrocarbons in Russia and worldwide is given.

AbstractThe effect of the tungsten oxide content (10–35 wt %) in Pt/WO3-ZrO2 catalysts on hydroisomerization of a heptane–benzene mixture (80 : 20, wt %) has been studied. The catalysts with 15–25 wt % WO3 are characterized by the highest fraction of the tetragonal phase of zirconia (t-ZrO2, 87–96%), which makes it possible to achieve the highest yield of the sum of heptane isomers, including high-octane di- and trimethyl-substituted isomers (DTMS; 69.4–76.7 and 24.5–27.9 wt %, respectively). In the presence of these catalysts, the yield of methylcyclopentane is 52.1–61.3 wt % at 72.6–90.9% selectivity of isomerization of cyclohexane to methylcyclopentane.

AbstractThe in situ formation of a catalytic heterohomogeneous system containing Al–M alloy (M is Ni, Co, Cu) and Al(M)/Cl complex in a benzene–ethylene medium at a temperature of 80°C and a pressure of 0.2–0.3 MPa is studied. The characteristic patterns of interaction between Al–M alloys activated with a liquid metal Ga–In eutectic and a chlorinating agent (CCl4) with the formation of catalytically active metal–aluminum chloride Al(M)/Cl complexes are established. Results from spectrokinetic measurements show the order of the reactivity of activated alloys with respect to excess CCl4 is Al–Cu ≈ Al–Ni > Al > Al–Co. The highest catalytic activity is displayed by nickel–aluminum chloride complexes whose selectivity toward ethylbenzene is 48%. Data from IR and UV-VIS spectroscopy show that the structure and composition of metal chloride complexes formed in situ in the aromatic reaction medium is determined by a combination of coupled ionic pairs \([{\text{AlC}}{{{\text{l}}}_{4}}]_{{{\text{tetr}}}}^{ - }{\text{/[NiC}}{{{\text{l}}}_{{\text{6}}}}]_{{{\text{oct}}}}^{{4-}}\) and \(\left[ {{\text{AlC}}{{{\text{l}}}_{{\text{4}}}}} \right]_{{{\text{tetr}}}}^{ - }/\left[ {{\text{CuC}}{{{\text{l}}}_{{\text{2}}}}} \right]_{{{\text{lin}}}}^{ - }\), which are stabilized by (C6H5)3C+ carbocation.

AbstractThe review presents an analysis of the current state in the field of partial oxidation of alcohols to carbonyl compounds on Ag catalysts, including the partial oxidation of methanol to formaldehyde, oxidation of ethylene glycol to glyoxal, and oxidation of ethanol to acetaldehyde. For methanol oxidation, conditions for BASF and ICI processes were considered, and the whole chain of transformations from natural gas to formaldehyde was evaluated from the viewpoint of exergy. Recent publications on the kinetics of partial oxidations of alcohols on silver were analyzed, including those that considered the use of a ring-shaped reactor to suppress the homogeneous decomposition stages of formaldehyde, the development of a new approach to process modeling taking into account different degrees of catalyst reactivity, and the creation of a simulator for calculating methanol oxidation based on a neural network using a genetic algorithm. The main stages of process development of partial oxidation of ethylene glycol to glyoxal on Ag catalysts are briefly described. Recent experimental and theoretical studies on the mechanisms of formation of oxygen-containing active sites on the silver surface and their participation in the conversion of alcohols into carbonyl compounds, as well as new Ag-containing catalytic composites, are presented.