Catalysis and Petrochemistry最新文献

{"title":"Influence of addition of exomodified carbon nanospheres on the structuration in ethanol motor fuels","authors":"E. V. Polunkin, V. Pyliavskyi, O.O. Gaidai, S. Melnykova, O. Spaska, I. Matveeva","doi":"10.15407/kataliz2021.31.062","DOIUrl":"https://doi.org/10.15407/kataliz2021.31.062","url":null,"abstract":"The work is devoted to elucidation of a general mechanism of action of exomodified carbon nanospheres (CNOs – Brn nanoonions) on different physicochemical and chemmotological properties of ethanol motor fuels. The formation of supramolecular solvate groups in organic media is explained by the participation of different forces of intermolecular interaction, the main of which are polarization and orientation, as well as donor-acceptor forces of interaction of nanospheres with the environment. The concept of creation in an organic medium of solvation formations - domains, the size of which, determined by the method of photon correlation laser spectroscopy, varies from 21 to 1000 nm, depending on the chemical nature of the solvent - is proposed and substantiated. For ethanol, the size of such formations was ~ 400 nm, which significantly exceeds the size of individual particles of the additive. It is established that to improve the operational characteristics of ethanol fuel it is enough to introduce low concentrations (10-3 - 10-2 %, wt.) of synthesized brominated nanoparticles. It is shown that the change of the microheterogeneous structure of fuels affects the change of its physicochemical and operational characteristics: the dielectric constant and hydrophobicity of the medium decrease, the saturated vapor pressure increases, which improves the starting properties of the fuel; hydrophobization of the environment helps to reduce the corrosive properties of ethanol fuel per unit, as a result of which additional introduction of a corrosion inhibitor is not required; the bearing capacity of the fuel in the presence of brominated nanoparticles increases by 1.5 times compared to the base fuel with a corresponding decrease in damage to the metal surface of the friction pairs. It is the rearrangement of the secondary supramolecular structure of fuels in the presence of brominated carbon nanospheres that explains the multifunctionality of their influence on the physicochemical and chemmotological properties of ethanol motor fuels.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79480457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Temperature inversion of the action of multilayer fullerenoid structures in the oxidation of N-decan by molecular oxygen","authors":"I. Polunkin, V. Pilyavsky, T. Kamenieva, S. Melnykova, О.О. Gajdaj, Yu. I. Bogomolov","doi":"10.15407/kataliz2021.32.099","DOIUrl":"https://doi.org/10.15407/kataliz2021.32.099","url":null,"abstract":"It was established that at low temperatures MFS inhibit the oxidation of n-decan, and at temperatures close to the boiling point of the hydrocarbon, on the contrary, accelerate the transformation of the original alkane molecules. The composition of alkane transformation products in the high-temperature two-phase (gas-liquid) oxidation regime was analyzed by gas-liquid chromatography. It is shown that the transformation of n-decan molecules occurs according to the same schemes both in the case of oxidation without the additive of MFS, and in the presence of these compounds in a liquid. The work is devoted to the actual problem of increasing the energy efficiency of liquid motor fuels (gasoline, diesel and jet fuels) in transport power plants. One of the most acceptable ways to solve this problem at the present stage, which does not require capital expenditure, is to improve the processes of chemical transformations of fuel molecules in engines under the action of additives. The use of multilayer fullerene-like structures (MFS) as additives to motor fuels is proposed. The influence of additives modified MFS on the conversion of reagents in the processes of liquid-phase oxidation of n-decan by molecular oxygen at low (70°C) and high (150°C) temperatures has been studied. The change in the direction of the MFS action on chemical transformation of initial reagents depending on process temperature is experimentally revealed. It was established that at low temperatures MFS inhibit the oxidation of n-decan, and at temperatures close to the boiling point of hydrocarbons, on the contrary, accelerate the transformation of the original alkane molecules. The composition of alkane transformation products at high-temperature two-phase (gas-liquid) oxidation regime was analyzed by gas-liquid chromatography. It is shown that the transformation of n-decan molecules occurs according to the same schemes both in the case of oxidation without the additive of MFS, and in the presence of these compounds in a liquid.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82519546","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrogenation of C`'5 olefins in vapor phase on the copper oxide catalyst","authors":"M. Sharanda, A. Mylin, O. Zinchenko, V. Brei","doi":"10.15407/kataliz2021.32.093","DOIUrl":"https://doi.org/10.15407/kataliz2021.32.093","url":null,"abstract":"Hydrogenation of unsaturated hydrocarbons is one of the important processes of the modern petrochemical industry. Quite large amount of C4-5 fractions of hydrocarbons containing paraffins and olefins are formed via pyrolysis of light petroleum products. To increase the production of ethylene and propylene, the separated C4-5 fractions are recycled for pyrolysis. Preliminary hydrogenation of olefin compounds in these fractions is necessary. Preferably, the hydrogenation is carried out in the liquid phase at temperatures of 40 – 80 °C under hydrogen pressure up to 15 bar overhigh-cost palladium-containing catalysts. The aim of this work was to elucidate the possibility of efficient hydrogenation of industrial С5 fraction containing C`5 olefins over some mixed copper-oxide catalysts. Hydrogenation of C`5 fraction of pyrolysis of light petroleum products in the vapor phase over such catalysts as CuO-ZnO-ZrO2-Al2O3 and CuO-ZnOAl2O3 in comparison with commercial Pd/Al2O3 catalyst for C4-5 olefins hydrogenation have been studied. The pyrolysis C`5 fraction containing 51 wt. % of unsaturated hydrocarbons (2-methyl-1-butene, 2-pentene, cis-2-pentene, trans-2-pentene, 2-methyl-2-butene) was used in the work. The catalytic process was carried out in a reactor with a fixed catalyst bed at 170 – 190 oC, and a pressure of 1.1 – 2.5 MPa. Analysis of obtained products was provided by gas-chromatography (Agilent 7820A) and 13C NMR (Bruker Avance 400) methods. It is shown that the hydrogenation of olefins with conversion of the C`5 fraction such high as 98 – 99 % can be carried out in the vapor phase over CuO-ZnO-Al2O3 and CuO-ZnO-Al2O3 catalysts at the temperature of 180 oC and pressure 1.2 – 1.5 MPa. The total C5 olefinsloading can reach 15 – 23 mmol/gcat/h. The residual content of unsaturated hydrocarbons is 1 %. At the pressure of 2.5 MPa, a sharp decrease in conversion is observed, as n-pentane turns into a liquid phase. Catalyst deactivation was not observed for 36 hours. Under the same conditions the drop in activity of industrial catalyst 0.35 % Pd/Al2O3 was observed after 70 minutes from the start of work.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81485617","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Activation of C–H bonds of normal alkanes in sulfuric acid solutions of Mn(III)/Mn(II)","authors":"L. Volkova, I. A. Opeida","doi":"10.15407/kataliz2021.32.075","DOIUrl":"https://doi.org/10.15407/kataliz2021.32.075","url":null,"abstract":"One of the most important directions of establishing the mechanisms of activation of C–H bonds, both in saturated and aromatic hydrocarbons in aqueous and sulfuric acid solutions of oxidants, metal complexes and radicals, is to study the kinetics of reactions and the influence of temperature, environment, nature of reagents, etc. The study of mechanisms is important for the development of technologies for processing hydrocarbons into products with high added value. In this work, to determine the nature of limiting stages and mechanisms of reactions of one group of saturated hydrocarbons, normal alkanes, we use the dependences of substrate selectivity (relative rate constants) on their characteristics: ionization potentials, energy and number of primary and secondary C–H bonds. To determine the nature of the limiting stages of reactions of normal alkanes, the correlations between the logarithms of substrate selectivity of alkanes reactions in H2SO4 solutions with one of the most active manganese(III) ions and molecule properties or C–H bond type were studied by the method of correlation analysis. Comparison of the obtained results with quantum-chemically calculated enthalpy changes of different possible variants of the course of this elementary reaction allowed to clarify the mechanism and propose tests to perform the mechanism of the slow limiting stage. It is shown that for alkanes (ethane, pentane, hexane, heptane, octane) the linear dependence with the ionization potential is most accurately performed, the least accurate is the correlation with the number of secondary C–H bonds, which indicates the electron abstraction in the slow limiting stage. For the shorter pentane – octane series, correlation dependences on both the number of secondary C–H bonds and the ionization potentials are performed with almost equal accuracy, which makes it impossible to establish the nature of the slow stage. The results of quantum-chemical calculations of hexane reactions in Mn(III)/Mn(II)–H2SO4 solutions showed that the most favorable are the electron abstraction by manganese(III) and subsequent proton transfer or homolysis of the C–H bond under the action of bisulfate radical, which is likely formed in the oxidation of sulfuric acid by manganese(III).","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81391869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of MoО2(VI), Zn(II), Cu (II) and Mg(II) complexes with N-methyldecanohydroxamic acid on the thermal oxidation stability of biodiesel","authors":"L. Koval, V. Dzyuba, V. Pekhnyo","doi":"10.15407/kataliz2021.32.054","DOIUrl":"https://doi.org/10.15407/kataliz2021.32.054","url":null,"abstract":"General climate changes and catastrophic environmental pollution cause the steadily increasing interest in the world to bio-based technical oils, including lubricants. In order that they bully comply with current environmental requirements, the additives added to them must not contain environmentally harmful components and provide the maximum thermal oxidation stability of the base oil. A significant disadvantage of zinc dialkyl dithiocarbamates and dialkyl dithiophosphates, which are widely used today as highly efficient polyfunctional additives, is that they contain ecotoxic organosulfur and organophosphorus components. In view of this, complexes of biometals with hydroxamic acids are promising. The paper presents the results of a study of the influence of MoO2L2, ZnL2, CuL2, MgL2 coordination compounds with N-methyldecanohydroxamic acid (HL) and mixtures of MoO2L2 with tert-butylcatechol and 2,6-di-tert-butyl-4-methylphenol (ionol) on the oxidation of distilled sunflower fatty acid methyl esters (one of the variants of biodiesel). Procedures for the synthesis of novel homoleptic Mg(II) and Zn(II) bis-hydroxamate complexes and their spectral characteristics are presented. The antioxidation properties of the complexes contained in the model solutions were determined by the method of oxygen absorption in a hermetically sealed system at 110 C. It has been found that the magnesium complex has no effect on the oxidation of the substrate, and that the copper complex decomposes, under experimental conditions, to metallic copper, which is an oxidation promoter. Zinc and molybdenum complexes exhibit antioxidation properties. It has been shown that ionol is an efficient co-component for MoO2L2, but no synergistic effect was detected. In view of the high tribological characteristics, the MoO2L2 complex is a promising prototype for the development of a polyfunctional eco-friendly additive to commercial biodisel-based lubricating compositions.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81555848","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lubricating materials based on waste oleo products","authors":"O. Papeikin, L. Bodachivska, I. Venger, D. Davitadze, O. Spaska","doi":"10.15407/kataliz2021.31.048","DOIUrl":"https://doi.org/10.15407/kataliz2021.31.048","url":null,"abstract":"Phosphatide concentrates and waste cooking oils - wastes that do not find qualified use and sources of environmental pollution, on the one hand, and on the other - valuable raw materials for the production of lubricating materials, additives and surfactants. The paper demonstrates the possibility of using these wastes as components in technologies for obtaining hydrated calcium greases and surfactants. By saponification of phosphatide concentrates and waste cooking oils were obtained the dispersed phases of thixotropic systems and were investigated their rheological properties. Derivatives of phosphoric acid in the composition of greases form a stronger structural framework, which is characterized by increased melting point and tribological properties capable of operating in high-load friction points. Surfactants were obtained by amidation of phosphatide concentrates and waste cooking oils. Synthesized alkanolamides combine with almost all mineral and synthetic oils and based on them developed compositions of lubricating materials. Tests of these compositions shown that synthesized surfactants from waste prove as effective multifunctional additives. Due to the chelating groups -OH, -NH2, -CONH, -COOH, -PO(OH)2, hydrophobic chelate complexes are formed, which not only impart systems homogeneity, but also provide improved protective, antioxidant and tribochemical properties of oils and lubricating compositions. Bench tests of resistance to oxidation of lubricating compositions with amidated phosphatide concentrates conducted at a temperature of 150 ºC confirmed their inhibitory effect, which allows to recommend them for use in high-temperature greases.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84757617","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Vapour-phase conversion of methyl lactate into lactide over TiO2/SiO2 catalyst at the lowered pressure","authors":"А.М. Vаrvarin, S. Levytska, А.М. Mylin, V. Brei","doi":"10.15407/kataliz2020.30.038","DOIUrl":"https://doi.org/10.15407/kataliz2020.30.038","url":null,"abstract":"Now polylactide (PLA) widely use as biodestructive packing material. Usually monomeric lactide produce from lactic acid. Also, methyl (ethyl) lactate could be used for lactide obtaining via its vapour-phase condensation on TiO2/SiO2 catalyst at 2600C in N2 carrier-gas flow. However, at that it is necessary to heat carrier-gas to the reaction temperature. In this communication the results on methyl lactate vapour condensation into lactide with the lowered pressure of 100-150 mbar, without carrier-gas, are presented. Supported TiO2/SiO2 catalyst with 5 wt.% titania content has been prepared by impregnation of silica with Ti(OC4H9)4. After calcination at 5000C prepared catalyst has amorphous mesoporous structure with 335 m2/g surface area and 0.83 сm3/g pore volume. The catalytic experiments were performed in such way. Liquid methyl lactate was dosed into the evaporator (2500C) and further in the flowing reactor (2600C) under pressure of 100 mbar that produced by vacuum pump. Load on a catalyst was varied from 25 to 55 mmol ML/(gcath). Cooled product was analyzed on Agilent 7820A chromatograph and NMR Bruker Avance-400 spectrometer. It was shown that TiO2/SiO2 catalyst provide 74% selectivity towards lactide at 50-53% methyl lactate conversion with lactide productivity of 7.8 mmol L/(gcath) at 2600C/100 mbar. The catalyst stable work is more 80 h. Main impurities are methyl lactoillactate, 1-methoxyethanol and 1,1-dimethoxyethane.","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2020-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77038518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of the dioxygen complex of oil cobalt (II) porphyrin complex and study of its oxygenating properties","authors":"M. M. Aghaguseynova, Azerbaijan State Oil, G. I. Amanullayeva, Z. E. Bayramova","doi":"10.15407/kataliz2019.28.069","DOIUrl":"https://doi.org/10.15407/kataliz2019.28.069","url":null,"abstract":"","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88247843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Growth of monocrystals of double polyphosphate NaMn (PO3)3 and its structure","authors":"R. Lavrik, V. Trachevsky, V. Diamant","doi":"10.15407/kataliz2019.28.061","DOIUrl":"https://doi.org/10.15407/kataliz2019.28.061","url":null,"abstract":"","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85716074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The influence of a polymer waste pyrolysis product on rheological properties of high viscosity oil","authors":"O. Konoval, A. S. Makarov, T. M. Dymytryuk","doi":"10.15407/kataliz2019.28.050","DOIUrl":"https://doi.org/10.15407/kataliz2019.28.050","url":null,"abstract":"","PeriodicalId":9649,"journal":{"name":"Catalysis and Petrochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2019-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82923655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}