Continuous mode linoleic acid hydrogenation on Pd/sibunit catalyst Catalytic hydrogenation of linoleic acid and oleic acid to stearic acid over palladium on mesoporous carbon sibunit (Pd/sibunit) catalyst was studied in a continuous trickle-bed reactor with the weight hourly space velocity 5,4 h–1 at 120 °C and 3 MPa using tall oil fatty acid (TOFA) as reactor feed. Stearic acid preparation using TOFA as a raw material is of industrial importance. Pd/sibunit catalysts with spherical particle shape of the size 1,62 mm were synthesized with the palladium loadings 0,5, 1, and 2 wt-%. The metal dispersion (%), metal particle size (nm), as well as metallic surface area (m2/g metal) of the three synthesized Pd/ Sibunit samples were measured by CO chemisorption. The Pd/C catalysts were tested in linoleic acid hydrogenation, showing promising behavior in terms of activity, selectivity and stability to be used in fixed bed applications. The product stream from the fixed bed reactor was saved and analyzed by X-ray fluorescence (XRF) and direct current plasma (DCP) spectroscopy. The catalyst activity increased with the Pd loading. The lowest metal loading of 0,5 wt-% gave the least prone to initial deactivation and thus the most stable catalyst. This catalyst can be recommended for further pilot testing.

Modified aqueous solutions of Mo–V–Р-heteropoly acids (HPA) are used as high-performance catalysts in processes of oxidation of various classes of organic compounds with dioxygen. The process of oxidation of n-butenes to methylethylketone (MEK) in the presence of aqueous (6·10-3 M Pd + 0.25 M HPA-7’) solution, where HPA-7’ is a modified HPA having overall composition Н12P3Mo18V7O85, is of considerable industrial interest. In the 1st stage, the oxidation of n-C4H8 into MEK in the presence of Pd takes place. In the 2nd stage, the catalyst is regenerated with dioxygen of air, closing the catalytic cycle. In such two-stage redox processes the HPA solutions are reversible oxidants, and their physicochemical properties are continuously varied. The modified HPA solutions are attractive because of their thermal stability and increased rate of regeneration. However, there is no information about their physicochemical and corrosive properties as yet. Doubtlessly, it hardly retards commercial development of these processes. Using the 0,5 M HPA-7’ solution as an example, we have shown how physicochemical properties of the catalyst change. It is found that pH, density (ρ), and viscosity (η) of this solution increase in the 1st stage and reach their maxima, but its redox potential (E) comes up to its minimum. In the 2-nd stage, the E value increases, but the pH, ρ, and η values decrease and reach their initial values. Thus, in the processes involving alternate reduction and oxidation of the catalyst based on the HPA solution, all alterations of its physicochemical properties are completely reversible. The data about corrosive properties of the modified HPA-7’ solution in relation to different engineering materials first are obtained in this work. It is found that resistance of different engineering materials to corrosion in the HPA-7’ solution falls in the series Ti (~ 0,009 mm·year-1) > 06KhN28MDT > 10Kh17N13M2T > 12Kh8N10T >> KhN65MV (~ 0,68 mm·year-1). The unique ability of the modified Mo-V-P HPA solution to restore entirely their properties after their regeneration with dioxygen permits to use them in many-cycled processes during a long time. It opens real prospects for development of industrial oxidation homogeneous catalytic processes using the HPA solutions.

During the primary screening, the catalysts were found, allowing to obtain a synthesis gas or hydrogen from glycerin with higher yields in a relatively mild conditions. A nickel and nickel-gold catalysts on different supports were studied in the reaction of steam reforming of glycerin. It was found that Ni catalysts on acidic supports (F–Al2O3 and B2O3– Al2O3) provide selectivity of H2 73 % and conversion of glycerin 48 % at 520 °C, thus they are suitable for hydrogen production from glycerin. 30 % Ni/Al2O3 catalyst, prepared by the original sol-gel method allows to obtain a commercial methanol at relatively low temperatures (520–570 °C) and almost complete conversion of glycerin. For 0,27 % Au–0,09 % Ni/Al2O3 catalyst the synergetic effect is bright. The conversion of glycerin reaches 67 % on this catalyst at 570 °C, the composition of the formed gas mixture is suitable for methanol production.

The process of catalytic afterburning of volatile organic compounds (VOCs) in industrial waste gases on new platinum fiberglass catalyst IC-12-S102 with a low platinum content (0,02 % wt.) is developed. This catalyst is superior to well-known in domestic and world practice of industrial catalytic afterburner. The way of glass fiber catalyst loading to a reactor in the form of vertical spiral cartridges, structured wire mesh weaving volume is described. The successful application of catalyst IC-12-S102 confirmed by its operation at «Nizhnekamskneftekhim» in the process of waste gases afterburning in industrial reactor with cleaned gases capacity up to 15 000 m3/h. During the reactor operation in harsh conditions (low oxygen content, high content of water vapor) the degree of gas cleaning was 99,5–99,9 %, and the residual VOC content in the purified gases was not more 10–15 mg/m3. For more than 15 months of the catalyst operation, the degree of gases purification was not reduced, thus overall lifetime of the catalyst IC-12-S102 may be substantially longer than the life of well-known industrial afterburning catalysts.

Mixture of the catalysts with different physical and mechanical properties (abrasion resistance, bulk density, fractional composition) is used for the unit of isobutane dehydrogenation in a fluidized bed OJSC «Nizhnekamskneftekhim» to increase the isoolefin production. There is analysis of the influence of fluidized bed height, circulation multiplicity, pressure drop in the reactor on the efficiency of unit dehydrogenation to find a causes of isobutylene yield decreasing and circulation multiplicity reducing, because it leads to by-products increasing. The main reason for reduction of the olefin yield is pressure drop increase in the reactor due to the restriction of tube free cross-section in wasteheat boilers and scrubbers lattices because of formation of solid, difficult to remove sediments, which consist of a potassium silicate, aluminum oxide, chromium oxide - component of weakest catalyst IM-2201. Rate of accumulation of the sediments is proportional to IM-2201abrasion, which increases after adding to it a high-strength impregnation catalysts. Combined exploitation of catalysts, obtained by spray-drying technology and impregnating of a supports, is not permitted for the pressure stabilization. The improving the aerodynamic characteristics is necessary, in particular, optimization of the fractional composition for self-exploitation more strength alumina-chromium catalyst impregnating type and providing the required height of fluidized bed, it have to be not less than 45 % of total height of the reactor. «Balanced» form of the catalyst, which is operated and circulated in the reactor-regenerator contour, should contain up to 30 wt.% granules smaller than 40 microns, for a required height fluidized bed without plashes, stable on the upper lattices , with less entrainment of dust granules and optimal circulation.

The characteristics of vinyl acetate (VA) synthesis from ethylene (activity, selectivity, and lifetime) are dependent on the properties of heterogeneous catalyst. Scientific basis for creation of such type industrial catalysts are stated in scientific literature insufficiently. The paper informs us about investigation of quantitative relationships of catalysts composition containing palladium, gold, potassium acetate and its activity, selectivity and lifetime, also about the selecting the optimum chemical composition of the catalyst. The mathematical functions of the catalyst activity and contenting of it components for optimal composition is proposed. The adequacy of the proposed mathematical functions is tested and verified in a pilot unit. It is shown that the 1,5 % palladium content, 0,75 % gold and 5,0 % potassium acetate, the catalyst activity is 700 g VA/(l·kat·h), and the selectivity of vinyl acetate formation on ethylene is 93–95 %.