Properties of catalytic systems based on iron oxide and inorganic matrices of oil-bearing rocks (basalt, clay, sandstone) were studied regarding the decomposition of ammonium nitrate, methane oxidation, hydrocracking of asphaltenes. The catalytic systems were iron oxide (hematite with particles of D = 11.0÷20 nm in size, preparation temperature 453–473 K) supported on the matrices through co-hydrolysis of carbamide and iron chloride under hydrothermal conditions at 433–473 K and 0.6–1.6 MPa. Iron oxide catalysts based on basalt and clay were most active to deep oxidation of methane (X_CH4 = 83 % and 72.9 % at 773 K, respectively), and Fe₂O₃ / basalt and Fe₂O₃ / sandstone systems most active to decomposition of ammonium nitrate. In hydrocracking of asphaltenes to maltene, the catalyst activity decreased in the series: Fe₂O₃ / basalt > Fe₂O₃ /clay > Fe₂O₃ / sandstone, the iron oxide supported on clay being the most selective catalysts. The obtained experimental data indicated practicability of natural materials such as oil-bearing rocks (basalt, clay, sandstone) for the development of catalytic systems to be used in situ in oil reservoirs and advanced technologies for improving the oil recovery.

A laboratory flow setup loaded with a bifunctional catalyst was used for kinetic studies of the direct synthesis of dimethyl ether (DME) from synthesis gas (21.8 vol % CO, 5.2 vol % CO₂, 5.3 vol % N₂, rest H₂) at the pressure range of 0.2–5 MPa. The bifunctional catalyst was prepared by tabletting a mixture of milled fractions of industrial components: methanol catalyst Megamax 507 and γ-alumina with a graphite additive. The data on the activation of the bifunctional catalyst agree with the TPR data of the initial Megamas 507 that indicates no influence of the catalyst preparation conditions on the copper oxide state. The oxygenate (DME and methanol) production rate increases linearly with increasing load at temperature up to 280 °C and flow rate up to 4000–10000 L/(kgcat·h) at pressure of 3 to 5 MPa. An increase in load leads to reaching the limit value that allows the estimation of the maximal oxygenate production rate of the catalyst depending on temperature and pressure. A series of experimental data on the influence of flow rate, temperature, and pressure on the composition of the converted gas and on the DME/methanol ratio are reported.

Under discussion are methodological aspects of the screening of granulated aluminochromium catalysts for dehydrogenation and methods for estimation of their operation lifetime based on the catalyst treatment in a steam-air medium. The practicability of small size reactors (with the diameter no less than four effective granule sizes) for comparing the catalyst activity at the screening stage are demonstrated with Mg- and Zr-promoted aluminochromium catalysts as an example.

Oxidation of octene-1 to heptanoic acid with hydrogen peroxide was studied in a liquid two-phase system under conditions of phase-transfer catalysis. The catalyst was tetra(oxodiperoxotungsteno)phosphate of methyltri-n-octylammonium [MeOctⁿ₃N]₃{PO₄[WO(O₂)₂]₄}. Conditions for the formation of heptanoic acid at the yield of 90 % were determined: temperature below 100 °C, atmospheric pressure, one stage and freeof organic solvents. The experimental data allow this method to be recommended for synthesis of monocarboxylic acids from α-alkenes to develop processes of green chemistry.

A gas chromatographic scheme and a method for analyzing isobutane dehydrogenation products are provided that simultaneously dosed a gas sample into three chromatographic columns, two of which are packed and one capillary. The pre-columns located in front of the packed columns remove the interfering components for the analysis of permanent gases in the gas sample. The content of hydrocarbons is determined on the capillary column. The components of the gas phase leaving the packed columns are detected by the detector with respect to the thermal conductivity and the components from the capillary column by the flame ionization detector. The composition of the sorbents in the packed columns and the porous polymer used as a stationary phase in the capillary column allows analysis of the gas sample of the dehydrogenation products of isobutane under isothermal conditions for 10 to 15 minutes.

Prospects of the conversion of refinery gas to high-octane components of motor fuel are discussed. The resource base of the Russian petrochemical complex is proposed to expand by involving light hydrocarbons – nonmarketable refinery waste products – into the production of ecologically sound high-octane components of gasoline based on tertiary butyl and isopropyl alcohols. A series of articles in the field of related research and experimental developments are announced.

The influence of conditions of hydroisomerization of benzene containing fraction of gasoline on the yield and composition of the products was studied over Pt/B₂O₃-Al₂O₃ and Pt/WO₃-Al₂O₃ catalysts. The catalysts were established to allow the complete removal of benzene from gasoline, the maximal yield of the liquid products (96.3 wt % over Pt/B₂O₃-Al₂O₃ and 95.4 wt % over Pt/WO₃-Al₂O₃) at the minimal loss in the octane number being observed at the process pressure of 2 MPa, feed flow rate 2 h–1 and 325 °C. The catalyst activity remain unchanged for 100 h.

Structure groups and individual compositions of the oilstock and catcracking products from section S-200 of KT-1/1 reactor were analyzed. The data obtained were used to suppose about possible reactions of the catalytic cracking. Quantum chemical methods were applied for thermodynamic calculations of probability of the reactions under the process conditions. The formalized scheme of hydrocarbon transformations comprising the feedstock components, light and heavy gasoil was suggested using the calculation results with allowance for the reaction reversibility; it was used for developing the kinetic model of the catalytic cracking process. Kinetic parameters of the reactions were determined by solving the inverse kinetic problem using experimental data (from the industrial facilities of Gaspromneft-Omsk Refinery Co.) and laboratory analytic data. The error of the calculations based on the kinetic model is no more than 5 % that argues for the model adequacy to the real process of catalytic cracking. The developed kinetic model makes it possible to calculate variations in the concentration of the reactants, quantity and composition of the products, as well as to optimize technological modes of the process depending on the process target (an increase in the yield of gasoline of light gasoil), composition and properties of the feedstock under processing.

Main commercial catalysts developed by LLC «NIAP-KATALIZATOR» in cooperation with research institutes, industrial enterprises and universities are described. The catalysts are produced at the catalyst plant of «NIAP-KATALIZATOR» and used at more than 200 enterprises of chemical, petrochemical, metallurgical and the other industries in Russia, CIS countries and abroad. The lifetime of some catalyst is as long as 15–20 years. The developed highly effective catalysts, in particular catalysts for methanation, hydrocarbon gas conversion, desulfurization, treatment of technological and waste gases, substituted for imported catalysts at some Russian enterprises.

Pt/BEA–Al₂O₃ catalysts were prepared from two type precursors (H₂PtCl₆ and [Pt(NH₃)₄]Cl₂); the platinum content was varied between 0.02 and 0.5 wt %. The catalyst testing for hydroisomerization of a benzene-heptane mixture at 1.5 MPa and 230–330 °C demonstrated high selectivities to methylcyclopentane of the catalysts containing 0.2–0.5 wt % of platinum prepared both from acid and from ammiacate. The selectivity depended on the conversion but not on the platinum content. A higher selectivity of heptanes isomerization was observed with the catalysts prepared by supporting platinum from the H₂PtCl₆ solution. The catalysts can be used for hydroisomerization of benzene- containing gasoline fractions in order to decrease the content of aromatic hydrocarbons in commercial motor gasoline.

The influence of the composition of molybdenum modified NiCu-containing catalysts on the activity and selectivity to hydrogenation of furfural – a product of acid hydrolysis of hemicellulose biomass – was studied. The initial NiCu catalyst was prepared by the sol-gel method and stabilized with 10 wt % SiO₂ by impregnating the calcined sol-gel with ethyl silicate. Molybdenum was introduced in the form of oxide Mo(VI) on the stage of blending of oxide precursors of the metals. Selective hydrogenation of furfural was achieved using a batch reactor at 100–200 °C and 6 MPa of hydrogen. It was established that the rise of the process temperature led to an increase in the yields of 2-methylfurane and complete hydrogenation products. At low process temperatures, 2-methylfurane practically was not formed but furfuryl and tetrahydrofurfuryl alcohols were the main products. In comparison to the NiCu systems, the modified NiCuMo-SiO₂ catalysts were more active to hydrogenation of furfural and more selective to 2-methylfurane; this may be accounted for by the formation of solid NiMo(Cu) solutions and by the formation of Mo^x+ on the catalyst surface.

Hydrogen-generating solid phase compositions based on sodium boran are promising systems for storage and transportation of hydrogen to be used for low-temperature fuel cells with proton-exchange membranes. Catalysts are added to the compositions in order to generate hydrogen at ambient temperature. The studies were focused on the influence of conditions of the cobalt catalysts preparation on the rate of gasgeneration. The efficiency of hydrogen evolution depended on the nature of the cobalt salt and pH of its aqueous solution where the active component precursor was reduced under the action of the hydride; these factors determined the composition, dispersion and magnetic behavior of the cobalt systems. The maximal rate of gas generation (505 cm³/min per 1 g of the composition containing 8.4 wt % of hydrogen) was observed in the presence of the sample reduced by sodium borane in a cobalt chloride solution with pH 1.3. The results obtained can be used to develop effective and inexpensive cobalt catalysts for generation of hydrogen from solid compositions based on sodium borane.

Activated carbon materials (CM) were prepared from rice husk carbonized in a fluidized bed reactor. Low temperature nitrogen adsorption at 77 K was used for characterizing the EM texture. Variations in the preparation conditions (carbonization followed by activation) allowed the materials to be synthesized with the BET surface area from 440 to 2290 m²/g. Application of potassium or sodium carbonates as activating agents led to the formation of CM with the BET surface area up to 1200 m²/g. CM with a larger surface area – up to 2290 m²/g – were obtained upon activation with sodium hydroxides. Electrochemical properties and capacitive characteristics were studied using voltammetry and chronopotentiometry in the galvanostatic mode in aqueous 1M H₂SO₄ electrolyte and ionic liquid BMIMBF₄. At low charging/discharging rates (0.2 A/g), a linear dependence of bulk capacity on the specific surface area of CM but not on the electrolyte nature was shown. At high charging/discharging rates (2 A/g), negligible or considerable decrease in the specific capacity was observed in 1M H₂SO₄ and in the ionic liquid, respectively. These observations were accounted for by the influence of the porous structure.

The traditional processes of catalytic acid hydrolysis of wood are low effective due to the low quality of the formed glucose solutions contaminated with admixtures that inhibit fermentation of glucose to ethanol. This is a particularly acute problem in hydrolysis of birchwood containing hemicelluloses in large proportions. In the present paper, quality glucose solutions are suggested to produce via sulfuric acid hydrolysis (80 % H₂SO₄, 25 °C) of cellulose products formed during catalytic peroxide delignification of birchwood. The composition of the cellulose products are established to affect considerably the content of glucose, xylose and admixtures (furfural, 5-hydroxymethylfurfural, levulinic acid) in glucose, which inhibit enzymatic synthesis of bioethanol. High yields of glucose (80.4–83.5 wt %) are achieved with cellulose products prepared by integrated processes of sulfuric acid hydrolysis of birchwood hemicelluloses and peroxide delignification of pre-hydrolyzed wood in the presence of catalysts 2 % H₂SO₄ and 1 % TiO₂. Concentrations of inhibitors of enzymatic processes are lower of the admissible levels in these hydrolyzates. The hydrolyzates with the maximal glucose content (86.4–88.5 wt %) and minimal concentration of inhibiting impurities are prepared by acid hydrolysis of cellulose products treated with 18 % NaOH. The hydrolyzate composition was studied using gas chromatography, HELC, chromatomass spectroscopy. IRS, XPS and chemical techniques were used for characterization of cellulose products.

Polysaccharide monooxygenases (PMO) was discovered several years ago in the composition of cellulase complexes to improve their saccharification capacity considerably. Methods of genetic engineering were used for creation of a chimeric PMO Thielavia terrestris based on enzyme with a cellulose-binding module (CBM) from cellobiohydrolase I Penicillium verruculosum attached through a peptide linker to the C-end. The chimeric PMO was more active (by 24 %) to amorphous cellulose and wider substrate specific than the initial PMO. With the attachedCBM, the chimeric PMO became capable of cleaving not only cellulose and β-glucane, but also xylane and CMC, while its activity to xyloglucane increased by an order of magnitude. In hydrolysis of MCC and aspen sawdust, when the chimeric PMO was substituted for 10 % of the highly active cellulase preparation hBGL2 produced by P. verruculosum at the retained total enzyme dosage with respect to the protein concentration, the yield of sugars increased by 24 and 47 %, respectively, the maximal sugar yield being reached in 24 hours of the reaction against 48 hours in the presence of the PMO-free preparation.

Liquid phase hydrogenation of biomass derived (–)-carvone into industrially valuable dihydrocarvone was studied over monometallic Au catalysts supported on alumina, titania and zirconia, as well as on mesoporous carbon support Sibunit in methanol as a solvent (100 °C, hydrogen pressure 9 bar). It was shown that among the three types of functional groups present in carvone, which can be hydrogenated, namely C=O, conjugated and isolated C=C groups, hydrogenation of the latter was predominant. The catalytic activity was found to depend on the catalyst support type. Under comparative reaction conditions conversion of carvone increased in the following sequence: Au/C << Au/ZrO₂ < Au/Al₂O₃ << Au/TiO₂. Higher activity of Au catalysts over metal oxides compared to Au/C can be caused by the presence of acid sites as well as oxygen vacancies in their structure allowing strong adsorption of carvone through its carbonyl moiety. All catalysts supported on oxides showed similar selectivity to trans- and cis-dihydrocarvone with the ratio between isomers (trans- : cis-isomer) being about 1.8, while this value for Au/C is close to 3.9, which can be related to much low carvone conversion in the latter case.