Thermostable oxide catalysts (Al₂O₃, ZrO₂, MgO and CaO) supported on a resistible material (carborundum) were studied in oxygen-free pyrolysis of methane. Addition of MgO, ZrO₂ and Al₂O₃ to pure carborundum resulted in a considerable increase in the methane conversion and in the selectivity to acetylene. In contrast, addition of CaO led, in general, to a decrease in the activity of the supported catalysts. The maximal selectivity to acetylene (23.6 %) was observed with the catalyst MgO/SiC at the conversion of methane equal to 68 % at 1290 °C. Studies of the sample of MgO/SiC showed that the catalyst retained its catalytic properties for methane pyrolysis (pyrolysis of 15 % of CH4 in nitrogen; methane conversion ca. 69 %, selectivity to acetylene ca. 22 %) during more than 4 hours at 1300 °C and was not destroyed due to the absence of carbon corrosion of the resistible support (carborundum) in contrast to the metal catalysts.

Literature data are reviewed in the field of catalytic reaction of the direct transformation of methane into marketable chemicals (H₂, C₂₊ hydrocarbons, methanol, formaldehyde and higher oxygenates). At present the processes based on these reactions are not implemented in industry. Catalytic systems providing achievement of the maximal parameters (in the first, the yields of target products) were identified for each of the reactions, and the proximity to their potential commercialization was determined. The processes of synthesis of C₂₊ and alkylaromatic hydrocarbons via oxidative condensation (dimerization) of methane and by the reaction of methane with C₃–C₆ alkanes, respectively, are considered most promising for the semicommercial production in the nearest future. A considerable progress in the development of new zeolite and aluminosilicate modifications makes it possible to solve the problem of the fast catalyst deactivation during olefin methylation to produce hydrocarbons of the gasoline fraction. Implementation of the process of methane pyrolysis to carbon and H₂ is mainly limited by insufficient demand for the obtained types of carbon materials and by the low strength of the available catalysts for fixed catalyst bed processes. The yields of a number of products (methanol, formaldehyde) are not as high as the ones required for the process commercialization. As to the other products (higher oxygenates), a general possibility of their synthesis is only so far demonstrated.

Results of studying an iron-nickel catalyst for steam reforming of methane, which was prepared by epitaxial deposition of the coat on the surface of spherical granules of commercial γ-Al₂O₃, are discussed. The catalyst was shown to be resistant to the presence of hydrogen sulfide in the steam gas mixture. The methane conversion was close to equilibrium at 2.0 MPa, 800 °C, H₂O : CH₄ = 2 : 1, feed flow rate 6000 h^–1, 30 ppm of H₂S. XRD, transmission electron spectroscopy (TEM) and Moessbauer spectroscopy were used to study the structure evolution and phase state of the active components of the system. The formation of paramagnetic iron oxide clusters strongly bound to the support structure and iron-nickel alloy FeNi3 particles on the catalyst surface determined the polyfunctional behavior of the catalyst, which is highly active to the steam reforming of methane and to oxidative decomposition of hydrogen sulfide to elemental sulfur.

Hydrogenation/hydrodeoxygenation of methyl-substituted carbonyl compounds to preserve the isomer structure of the product is of interest as a method for controlling the oxygen content and for improving chemical stability of motor fuel components. A single unit integrationof two catalysts – hydrogenation catalyst and dehydration catalyst – is an exciting example of the positive interinfluence of the processes occurring on the catalysts. Against the catalyst for hydrogenation of 2,4-dimethyl-3-pentanone to 2,4-dimethylpentane, the composite loading leads to a multiple increase in the hydrogenation rate and lengthening of the period of stable operation of the catalyst bed at complete hydrodeoxygenation of initial ketone. The composite loading can be used as an effective alternative to the bifunctional catalysts.

Current state of processes for manufacturing motor fuels based on consecutive reactions of oligomerization and hydrogenation of unsaturated hydrocarbons was briefly analyzed. New catalysts based on bifunctional systems NiO/В₂O₃-Al₂O₃, PdO/В₂O₃-Al₂O₃, MoO₃/В₂O₃-Al₂O₃ for hydrooligomerization of butenes were discussed. The PdO/В₂O₃-Al₂O₃ catalyst pre-reduced in hydrogen was shown to provide the best process parameters (67 wt % yield of liquid C₅₊ products at 90 % butene conversion). A possibility in principle of acetylene hydrooligomerization over NiO/B₂O₃-Al₂O₃ was demonstrated. The presence of nickel (II) cations, which are chemically bound to the support surface, was established to be the key factor both for acetylene hydrooligomerization and for ethylene oligomerization.

The studies were aimed at the development of hydroisomerization catalysts based on nanosize molybdenum carbides. These catalysts were expected to be resistant to sulfur compounds and applicable for synthesis of low pour point diesel fuels similar in parameters to the fuel synthesized over platinum catalysts. Acidic supports were synthesized for these catalysts; the supports differ by the type of their porous structures, number and strength of Broensted acid sites; these were silicoaluminophasphate SAPO-31, zeolite ZSM-21, modified zeolite Beta, desalicided zeolite ZSM-5. Adsorption methods, TPD of ammonia, NMR, SEM techniques were used for studying physicochemical properties of the supports.

The studies were aimed at the development of hydroisomerization catalysts based on nanosize molybdenum carbides. These catalysts were expected to be resistant to sulfur compounds and applicable for synthesis of low pour point diesel fuels similar in parameters to the fuel synthesized over platinum catalysts. Part I dealt with synthesis and characterization of supports with different porous structures and acidities (Beta, ZSM-5, ZSM-12, SAPO-31). Part 2 of the work was devoted to studies of bifunctional catalysts prepared by modifying these supports with nanosize molybdenum carbides. All the samples bore identical amounts of Mo₂C (10 % expressed in terms of the equivalent amount of MoO₃). The catalysts were tested using a model reaction of isomerization of n-decane. The catalyst based on silicoaluminophosphate ATO (SAPO-31) was most active to isomerization. Larger batches of the catalysts with different Mo₂C contents (5, 7 and 10 expressed in terms of the equivalent amount of MoO₃) were prepared to optimize the composition. The catalytic properties were studied using hydroisomerization of actual diesel fractions. The optimal content of Mo₂C (7 wt %) in the bifunctional catalyst was determined.

The studies dealt with the development of an effective catalyst for deep oxidation of hydrocarbon chlorides. The solid-phase catalysts with different contents of the active component were prepared based on V₂O₅, CuCl or V₂O₅/CuCl supported alumina synthesized by various methods. The chemical (AAS-IP) and phase (XPS) compositions and textural characteristics (BET method) were determined. The catalytic activity to deep oxidation of benzene chloride (BC) was studied at 300–600 °C in air mixtures using a flow quartz reactor. The catalytic behavior of the samples were estimated based on the BC conversion, selectivity to CO₂ and the oxidation rate constant calculated by the first order equation in respect of BC. It was shown that the influence of the texture was more pronounced at 350 °C than at 400 °C except the samples with low V₂O₅ loading (1.5–2.5 wt %). The highest activity was observed with the catalysts supported on alumina synthesized by precipitation from aqueousalcoholic solution of aluminum chloride (AO3) that allowed the catalyst loading to be decreased in comparison to the catalysts supported on γ-Al₂O₃ (AO1) and amorphous alumina (AO2). The highest selectivity to CO₂ (91 %) was observed during the BC oxidation over the catalyst supported on AO2; for this reason, this catalyst seems promising to be further studied.

The experimental results on tert-butanol dehydration are discussed. The influence of the catalyst bed temperature, water content in the feed flow, and the temperature of the feed flow on the tert-butanol conversion was experimentally studied in the presence of the KU-2FPP and Purolite СТ275 catalysts. The isobutylene yield was established to depend mainly on the heat supply to the reaction zone. The countercurrent flows of the phases through the catalyst bed were shown not to allow the process to be intensified using a more active catalyst. It was experimentally demonstrated that the arrangement of downward concurrent flows in the catalyst bed led to an increase in the efficiency of tert-butanol decomposition over a more active Purolite CT275 catalyst.