Interaction of «metal solutions» obtained by metal vapor condensation
(MVC) and metal oxides with different morphology was used to obtain heterogeneous compositions that allow one to activate C–H and C–C bonds in alkanes under mild conditions. Results of the physicochemical analysis suggest that the particle size of the metal catalysts is generally within the nanometer range. Catalytic properties of the prepared compositions were tested in the hydroconversion of C5–C16 n-alkanes. It was shown that these compositions can be the basis for purposeful synthesis of promising catalysts for structural transformation of n-alkaness into ecologically clean high-octane gasoline and lubricating oils.

A mathematical model was suggested for the dehydrogenation of isoamylenes to isoprene in a fixed bed reactor with industrial selfregenerating iron-potassium catalysts KDOM and ZhKD. The model takes into account the size and shape of catalyst grains, rate constants and activation energies of direct (dehydrogenation) and reverse (hydrogenation) reactions, rate constants and activation energies of cracking and self-regeneration, and accumulation of leachable and non-leachable coke. The model adequately describes physical and chemical processes occurring during dehydrogenation of isoamylenes in industrial reactors at different loadings of ironpotassium catalysts and at various regimes of reactor operation (loading of raw material, dilution of raw material with steam, temperature and pressure at the reactor inlet) and allows the optimization of technological parameters of the industrial process.

In the work the analysis of the catalytic process of methylbutenes dehydrogenation in isoprene is made. The mathematical model of the process for the adiabatic reactor with the non-moving layer of catalyst, which takes into account the change in the number of moles in the reaction gas mixture (or in the reaction volume), and the nonstationary non-isothermal reactor model for repression is developed. The computational algorithm and program for calculating the basic parameters of the process: the conversion of ethylbutenes, the isoprene yield and selectivity of its formation, are worked out. On the basis of the constructed model the technological optimization is made and the optimal values of the control parameters ( the feed rate at the reactor inlet, the temperature at the reactor inlet, the molar dilution by water vapor) are found that are allowed to obtain the desired products with a maximum yield with constraints on the minimum allowable value of the selectivity of the formation of isoprene and conversion of methylbutenes.

A synthesis of hydrocarbons from CO and H2 was carried out over a cobalt catalyst. The selectivity and productivity of the reaction were studied in dependence on temperature, pressure, space velocity, and composition of the synthesis gas. It was found that a temperature increase of 17 °C at volumetric feed rates of 60 h–1 and 100 h–1 reduces the process selectivity toward macromolecular hydrocarbons C35+ by 24 % and 69 %, respectively. The change of pressure from 0,1 to 2,0 MPa increases the selectivity, whereas a change in the gas space velocity from 60 to 300 h–1 leads to its decrease. It was shown that the production of high molecular weight hydrocarbons C35+ (ceresin) requires the use of concentrated mixtures of synthesis gas. The actual composition of resulting hydrocarbons differs from the Anderson – Schulz – Flory (ASF) distribution, which indicates that the theoretical simulation of actual distribution should use more complex dependencies. The results of this applied research are intended to design a pilot plant for production of ceresin 100.

Acid-catalyzedcondensationofsubstituted1,3-butadienewith p-uinones
and oxidation of resulting adducts was carried out as a single process in the presence of aqueous solutions of Mo-VP heteropoly acids (HPAs) of the total composition HaPzMoyVxOb. Th bifunctional catalytic properties, being both strong Brшnsted acids and quite strong reversible oxidants. Condensation of 1,4-naphthoquinone (NQ) with 1,3-butadiene in a solution of high-vanadium HPAs with total compositions H15P4Mo18V7O89 and H17P3Mo16V10O89 in the presence of water-miscible organic solvents (acetone, 1,4-dioxane) results in a formation of 9,10-anthraquinone (AQ) with a yield of about 70 % and a selectivity up to 97 % at complete conversion of NQ. The reaction between NQ and substituted 1,3-butadiene under analogous conditions produces substituted anthraquinones with the yields up to 90 % and selectivities up to 99 %. Catalysts are regenerated with oxygen in a separate step and can be used repeatedly. 

The paper proposes a method for a synthesis of new catalytic systems based on titanium silicalite (TS-1) for liquid phase oxidation of phenol by hydrogen peroxide. The systems provide a production of catechol and hydroquinone (1:1) with a yield of 90–92 % and allow establishing a continuous process instead of the conventional technology with periodic discharges of powdered catalyst (titanium silicalite). The method is based on the encapsulation of TS-1 in a polymer matrix (polypropylene, polyethylene, polystyrene, or their copolymers). With TS-1/polypropylene and TS-1/polystyrene used as examples, it was shown that the nature of the polymer matrix affects the catalytic properties of the system. The catalytic properties of TS-1/polypropylene and TS-1/polystyrene were compared with the properties of a commercial catalyst available from EniChem. The use of TS-1/polypropylene was shown to increase the productivity of current technologies and to significantly reduce the energy costs.

Problems of catalytic thermal cleaning of exhaust gases with significantly changing compositions were studied by the example of gaseous wastes from electric insulator production, which contain from 1 to 15 g/m3 of toluene. Kinetic characteristics of the deep oxidation of toluene were experimentally found for both a palla dium-containing catalyst and oxide industrial catalysts. The processes in an adiabatic reactor were analyzed using mathematical modeling. The behavior of the process was studied in two regimes: under varying the flow rate of dilution air at a fixed inlet temperature and under varying the inlet temperature at a fixed dilution with air. The features of the process with one-layer and two-layer loadings of the catalyst were considered. The problems and limitations of using the Pd-containing catalyst in the first layer were discussed. Technical and technological methods of organizing catalytic processes for the abatement of wastes of varying composition

are proposed.

The partial reduction of fatty acid derivatives into corresponding fatty alcohols was studied in static and continuous flow reactors. The experiments with a static reactor showed that obtaining the maximum yield of major products requires a fatty acid as an initial substrate. The experiments in a flow reactor allowed us to determine optimal conditions for the production of alcohols and waxes: temperatures in the range 280–330 °C and pressures from 3,5 to 5,3 MPa. A theoretical scheme of the partial reduction of fatty acids was proposed. The scheme takes into account the target products (fatty alcohols) and all oxygenated side products. A mathematical model describing the scheme was suggested. Rate constants for the main steps of the conversion of oleic acid were determined. The constants may be used to evaluate the distribution of products at various contact times.

Two series of catalysts were studied: ХMo6HPC/Al2O3 and Со6(CA)-РМо12/support. Catalysts ХMo6HPC/Al2O3 were prepared from heteropoly compounds (HPC) of the Anderson structure with the heteroatom Х = Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Al. Catalysts Со6(CA)-РМо12/support (CA denotes citric acid) were prepared from 12-molybdophosphoric heteropoly acid and cobalt citrate. As a support, the following compounds were tested: Sibunit, Al2O3, carbonized alumina, and aluminas modified with zeolites ZSM-5 or BETA. The supports and catalysts were studied by low-temperature nitrogen adsorption, X-ray diffraction, temperature-programmed desorption of ammonia. Properties of catalysts in hydrodeoxygenation (HDO) of guaiacol were studied in a flow apparatus at 260 °C, 3,0 MPa, a volumetric feed rate of 80 h–1, and a ratio H2/feed = = 500 l/l. The activity of catalysts ХMo6HPC/Al2O3 was found to depend on the type of heteroatom Х: the catalysts with Х = Co, Ni were the most active, while the least active catalysts were those with Х = Cu. It was found that the activity of the catalysts in HDO decreases linearly with an increase in the acidity of the support. It was shown that the lower activity of zeolite-containing catalysts is due to their fast deactivation. The HDO of plant raw material was recommended to be performed with the catalysts supported on carbonized alumina, which showed the highest activity and resistance to deactivation.

Biocatalysts based on recombinant enzyme preparations derived from the fungus Penicillium verruculosum were comparatively tested in the hydrolysis of hardwood hemicellulose. The activity of the biocatalysts toward different types of hemicellulose and dependence of the depth of complete hydrolysis on hemicellulose grinding and drying were determined. It was shown that hemicellulose after boiling with green liquor is highly reactive in enzymatic hydrolysis with the cellulase complex and is of great interest as a substrate for scaled biotechnological processes of bioconversion of renewable raw materials.