The study is devoted to the conversion of tar and iron-modified lignin under the action of microwave radiation. Lignin containing 0.5 wt % Fe absorbs about 80% of the supplied microwave radiation (2.45 GHz), which leads to a rapid increase in temperature in the reaction zone with the formation of plasma. During the conversion of a lignin (0.5 wt % Fe)/tar blend a wide range of gaseous and liquid hydrocarbons was produced, therewith the amount of light hydrocarbons was 75%. The solid carbon residue containing iron(III) oxide clusters is also characterized by the ability to absorb microwave radiation; it was employed as a catalyst and as a plasma generator in the 2nd cycle of the converting only tar under the influence of microwave radiation. The structure of nanosized iron-containing components was studied by transmission electron microscopy, X-ray diffraction, and Mössbauer spectroscopy, which made it possible to describe their genesis.

Conversion of mixtures of fuel oil with iron-containing substrates (carbon adsorbent and lignin, both modified with 0.5 wt % Fe) to hydrocarbon products and hydrogen was studied. The use of microwave radiation in the presence of the above-indicated iron-containing substrates capable of its absorption with the generation of breakdown phenomena and plasma is a promising approach to rapid processing of stable organic compounds of petroleum and natural origin into hydrocarbon products used in organic synthesis and for production of fuel components.

High activity of metal complex catalytic systems comprising nitrogenous bases and copper sulfates, acetates, and basic carbonate in oxidation of hydrogen sulfide and light mercaptans with atmospheric oxygen was established. Their activities are close to that observed for the chlorine-containing analogs, while no corrosion effect is exerted. An increase in the initial concentration of H 2 S has negligible effect on its conversion rate. Mercaptans do not affect the H 2 S oxidation rate, whereas an increase in the hydrogen sulfide concentration decelerates mercaptan oxidation. This is a diffusion-controlled reaction; hence, intensification of mixing of the catalyst with the hydrocarbons affords a 30–40% increase in the demercaptanization efficiency. The efficiencies displayed in demercaptanization processes by the catalytic systems and by the conventional scavengers neutralizing light sulfur impurities were compared.

Results of the catalytic hydrogenation of lignin in a hydrogen-donor solvent medium are described. Nickel-containing systems are deposited directly on the lignin surface in an amount of 1.5–3.4 wt %. Nickel systems are deposited by two methods: from a Ni(OAc) 2 × 4Н 2 О aqueous solution and from a colloidal solution in toluene of nickel particles prepared by metal vapor synthesis (MVS). The hydrogen donor solvent is tetralin taken in a tetralin/lignin ratio of 1 : 1. Hydrogenation was carried out in a rotating autoclave at a temperature of 400°C and a pressure of 100 atm. It is shown that the preactivation of nickel-containing lignin by ultrasonication at 39 kHz for 20 min leads to an almost exhaustive conversion of the organic matter: the hydrogenation products comprise 13.1 wt % gas and 86.3 wt % liquid hydrocarbons. The liquid hydrogenation products contain aromatic hydrocarbons and nonvolatile condensed compounds with an average molecular weight of 300 Da. The effect of sonication on nickel-containing lignin and the evolution of nickel-containing components during lignin hydrodepolymerization are studied by electron microscopy and magnetic susceptibility methods.

Norbornadiene allylation by allyl formate in the presence of palladium catalytic systems has a number of features associated with different directions of β-hydride transfer in key intermediates, which can be carried out with the participation of allyl, norbornenyl, or formyl fragments. The value of the kinetic isotope effect and the nature of the limiting step in the reaction of hydroallylation of norbornadiene are determined using deuterated reagents.

The thermal behavior of hydroxylaminate uranyl complexes [UO2(NH2O)2(H2O)2] ‧ H2O, [UO2(NH2O)2], and [UO2(i-C3H7NHO)2(H2O)2] ‧ 2H2O has been studied. The complexes decompose at a low temperature (<200°C) resulting in nanoscale powders of uranium dioxide. The composition of solid decomposition products for each complex has been determined by powder X-ray diffraction. For the complex with isopropylhydroxylamine, the composition of the gaseous decomposition products has been determined. Schemes of redox reactions, which can take place during the thermal decomposition of the complexes, are proposed. It has been suggested that the redox reactions are dependent on the substituents at the nitrogen atom of the hydroxylaminate ligands.

The conversion of ethanol and fusel oils to a С3–С12 alkane–aromatic fraction with high activity and selectivity in the presence of the Pd–Zn/TsVM pilot catalyst has been demonstrated. It has been shown that the ethanol conversion to alkanes and aromatic hydrocarbons in the presence of this catalyst proceeds by various routes to give ethylene and diethyl ether as intermediate products providing a 90–95% yield on the converted ethanol carbon basis for the target С3–С12 fraction containing up to 40% of branched alkanes.

MALDI-TOF was used to study molybdenum dioxide (MoO 2 ) containing a nanosized fraction. The composition of cationic clusters of nonstoichiometric lower molybdenum oxides in the gas phase was determined, and the thermodynamic stabilities and configurations of isomers were calculated for selected symmetric molecular structures and for cations MoSO 8 + and Mo 5 O 9 + . Molecular orbital analysis was performed for two trigonal-bipyramidal clusters Mo 5 O 8 and Mo 5 O 9 . Changes in molybdenum–molybdenum interatomic distances in going from MoO 8 + and Mo 5 O 9 + cations to neutral clusters are discussed.

A method for the production of a С 3 –С 11 alkane–aromatic hydrocarbon (HC) fraction by the coconversion of a mixture of alcohols simulating biomass fermentation products and vegetable oil without using molecular hydrogen has been developed. A characteristic feature of this method is the occurrence of coupled alcohol aromatization reactions evolving hydrogen consumed for the hydrogenation of unsaturated HC moieties formed from fatty acid triglycerides in the presence of a pilot sample of the Pd–Zn/TsVM/Al 2 O 3 catalyst. It has been found that the optimum amount of vegetable oil in the feed mixture is 25–50 vol %; this amount provides the target fraction yield of up to 95% on a fed carbon basis.

Allylation of norbornadiene with allyl formate in the presence of the palladium catalytic systems is characterized by several peculiarities associated with the new reaction route: hydroallylation (reductive allylation) occurs along with the traditional allylation (oxidative allylation). Both processes are considered from the single point of view, and the mechanism assuming different routes of the hydride transfer in the key intermediates was proposed. It was proved by using deuterated reactants that the hydride transfer can involve the allyl, norbornenyl, or formyl moieties. In all cases, the hydrogen atom bound to the carbon atom in the β-position relative to palladium is eliminated in this step.

Molybdenum dioxide (Mo-2) synthesized through thermal decomposition of the [MoO2(i-C3H7NHO)(2)] complex and containing a nanosized fraction has been studied by MALDI-TOF. The composition of clusters of lower nonstoichiometric molybdenum oxide cations in the gas phase has been determined, and theoretical calculations of the thermodynamic stability and structure of the isomers of the most symmetric structures have been performed. Molecular orbitals of the cationic and neutral clusters Mo5O8 and Mo5O9 have been examined, and the aromaticity of the Mo-Mo bonds in metallacycles has been demonstrated.

Методом MALDI-TOF исследовали диоксид молибдена (MoO), полученный путём термического разложения комплекса [MoO(i-CHNHO)] и содержащий наноразмерную фракцию. Установлен состав кластеров катионов низших нестехиометрических оксидов Мо в газовой фазе и проведены теоретические расчёты термодинамической стабильности и строения изомеров некоторых наиболее симметричных структур. Проведён анализ молекулярных орбиталей катионных и нейтральных кластеров MoO и MoO и показана ароматичность связей Mo-Mo в металлоциклах.

Development of alternative approaches to fuel components and basic organic synthesis precursors producing based on biomass treatment products is important objective for ecology and chemistry. In this work, a number of original Pt–Sn containing catalysts were used for the mixture of fatty acids conversion. The peculiarities of used catalysts are usage of heterometallic precursors that possesses metal–metal bonds. Such kind of catalysts precursors allow obtaining more active and selective catalysts then ones based on a mixture of monometallic Pt and Sn precursors. Structural peculiarities of catalysts were characterized with TEM&EDS and XAS technique. Relations between Pt clusters structure and its catalytic properties were determined.