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Chemistry for Sustainable Development

2014 year, number 6

1.
Effect of Anion Modification of Alumina Support on the Properties of Platinum Catalysts of Hydroisomerization of BenzeneContaining Petrol Fractions

E. D. FEDOROVA, E. A. BULUCHEVSKY, A. V. LAVRENOV, N. N. LEONTYEVA, T. I. GULYAEVA and A. V. SHILOVA
Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
Keywords: benzene, hydroisomerization, anion-modified aluminium oxide

Abstract >>
The effect of the nature of modifying agent and chemical composition on the phase state, texture characteristics and acid properties of 2O5–Al2O3, O3Al2O3, and WO3Al2O3 systems was studied. Supported platinum catalysts based on these systems were tested in hydroisomerization of a model mixture of heptane and benzene in a flow set-up at reaction temperature of 300350 °C, pressure 1.5 MPa, mass rate of raw material input 3.0 h1, molar ratio of 2/raw material equal to 5. A Pt/WO3Al2O3 sample with WO3 25.9 mass % was chosen as a promising catalyst of hydroisomerization.



2.
Single–Stage Synthesis of Propylene from Etylene on the NiORe2O7/B2O3Al2O3 Catalyst. Thermodynamic Analysis and Kinetic Model of the Process

E. A. BULUCHEVSKY, A. V. LAVRENOV and L. F. SAIFULINA
Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
Keywords: ethylene, propylene, dimerization, isomerization, metathesis

Abstract >>
It is demonstrated on the basis of thermodynamic calculations that the synthesis of propylene from ethylene with intermediate formation of n- butenes under equilibrium conditions is most probable within temperature range 450–550 °C with propylene yield up to 50 mass %. In the case of the kinetic control of ethylene dimerization into butene1, the achievement of propylene yield at a level of 60 mass % is theoretically possible at low temperatures (4060 C) and ethylene conversion degree about 80 %. For the NiORe2O7/B2O3Al2O3 catalyst, a kinetic model of the process was constructed. The model provides adequate description of process parameters within temperature range 40120 C with ethylene converison degree up to 30 % and propylene yield up to 25 mass %.



3.
Effect of the Technological Parameters of Alkylation Reactor on the Concentration of n–Propylbenzene in Product Mixture

A. A. CHUDINOVA1,2, A. E. NURMAKANOVA2, A. A. SALISHCHEVA2, E. N. IVASHKINA2 and A. A. GAVRIKOV2
1Omskiy Kauchuk JSC, Prospekt Gubkina 30, Omsk 644035 (Russia)
2National Research Tomsk Polytechnical University, Prospekt Lenina 30, Tomsk 634050 (Russia)
Keywords: alkylation, npropylbenzene, mathematical model, benzene, propylene

Abstract >>
The problem of the high concentration of n–propylbenzene as undesirable component of the product mixture formed during liquid-phase alkylation of benzene with propylene ios investigated. Monitoring of alkylation set-up (Omskiy Kauchuk JSC) was carried out; technological parameters affecting the concentration of npropylbenzene were revealed. A mathematical model of alkylation was worked out. A computer-based modeling system Alkylation involving this model was developed in Borland Delphi 7; it allows calculating the composition of product flows under variations of the most importnat technolgoical parameters of reactor operation (temperature, molar ratio of benzene to propylene, volume rate of raw material input).



4.
Structure and Properties of Nanodispersed Globular Carbon after Thermooxidative Treatment with Water Vapour

Yu. V. Surovikin, A. G. Shaitanov, V. A. Drozdov, I. V. Rezanov and I. V. Mutomtsev
Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
Keywords: nanodispersed globular carbon, thermooxidative treatment, thermal treatment, electric resistance, Raman spectroscopy, X-ray structural analysis, structure parameters

Abstract >>
The structure and properties of nanodispersed globular carbon (NDGC) after thermooxidative treatment with water vapour were studied. The properties and structural changes in non-conducting NDGC of P 145 and P 234 grades were studied in comparison with conducting grades P 267–E, Printex XE2b and Ketjen EC. A complex interconnection between electric resistance of the material and the parameters of Xray structural analysis and Raman spectroscopy was revealed.



5.
Optimization of the Technological Parameters of Thermal Treatment of Molded Carbon Sorbent

T. N. Matyushenko, O. N. Baklanova, L. G. Pyanova and V. A. Likholobov
Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
Keywords: carbon sorbent, carbonization, carbon resporation, activation, medical application materials

Abstract >>
The effect of the technological parameters of thermal treatment (carbonization, carbon restoration and activation) of molded extruded carbon on the texture and strength characteristics of final carbon sorbents for medical purposes was studied. Temperature-time parameters of carbon restoration and activation processes providing the formation of molded carbon sorbent shaped as cylinders with the external diameter of 8–10 mm, internal chanel 34 mm and the length of 4560 mm were determined; the specific surface of the sorbent is SBET = 220320 m2/g, crushing strength > 20 kgf/cm2.



6.
Application of X–Ray Photoelectron Spectroscopy and Scanning Tunneling Miscoscopy to Study Model Catalysts

A. V. Bukhtiyarov1,2, A. V. Nartova1,2,3, R. I. Kvon1, I. P. Prosvirin1,3, A. M. Sorokin1 and V. I. Bukhtiyarov1,2,3
1Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
2Research and Education Centre of Energy-Efficient Catalysis Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russia)
3Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russia)
Keywords: Xray photoelectron spectroscopy, scanning tunneling microscopy, supported metal catalysts, model systems, surface reaction intermediates

Abstract >>
Using modern methods and approaches of surface science, the model supported catalysis Au/AlOx and Ag/HOPG were studied in the reactions of NO decomposition and ethylene oxidation, respectively. It is assumed that a combination of X–ray photoelectron miscoscopy and scanning tunneling microscopy turns out to be very informative in establishing the reasons of the catalytic action of model catalysts and can be used in the studies aimed at improvement of the catalytic properties of real catalysts.



7.
Influence of TiO2 on the Efficiency of Low–Temperature Generation of H2 from SolidPhase Compositions Based on NH3BH3

N. L. Kayl, O. V. Komova, O. V. Netskina, G. V. Odegova, A. M. Ozerova and V. I. Simagina
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
Keywords: amminborane, titanium dioxide, thermolysis, hydrothermolysis, water adsorption

Abstract >>
Low-temperautre hydrogen generation from solid-phase compositions based on amminborane (NH3BH3) and TiO2 under external heating to 80 °C depending on the physicochemical properties of titanium dioxide, its content in the composition and the amount of adsorbed water was studied. It was established that the maximal yield and rate of hydrogen formation are achieved for the system prepared on the basis of fine titanium dioxide witht eh participation of adsorbed water. It is assumed that an increase in the efficiency of hydrogen obtaining from the composition in comparison with initial hydride is due to a conjugation of the exothermal process of amminborane hydrolysis with its dehydrogenation (thermolysis).



8.
Adsorption Properties of Single Gold Nanoparticles

A. A. Kirsankin, M. V. Grishin, N. N. Kolchenko and B. R. Shub
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ul. Kosygina 4, Moscow 119991 (Russia)
Keywords: adsorption, nanoparticles, gold, surface, cluster, SHM

Abstract >>
Adsorption properties of gold nanoparticles deposited on pyrolytic graphite were studied. It was established that water molecules are formed as a result of serial adsorption of hydrogen and oxygen on the surface of nanoparticles. The energies of bonding between chemisorbed hydrogen and gold were determined.



9.
Deactivation of Zeolite–Containing Catalysts of Nonoxidative Conversion of Methane

V. V. Kozlov1, L. L. Korobitsyna1, A. V. Vosmerikov1 and V. I. Zaikovsky2
1Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 4, Tomsk 634021 (Russia)
2Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
Keywords: zeolite of ZSM5 type, nanosized metal powders, methane, converison, dehydroaromatization, coke

Abstract >>
Deactivation of tungsten-containing zeolite at different stages of nonoxidative conversion of methane into aromaic hydrocabrons was studied. The factors causing a decrease in the activity of the catalyst were revealed. The distribution and state of the active components in the catalytic system were studied. The nature of carbon deposits formed during the reaction on the catalyst under investigation was studied, and the amount of the deoposits was determined.



10.
Investigation of the Catalytic Activity of High–Silica Zeolite Catalysts in the Joint Conversion of Butane and Hexane

N. V. Ostanina1, D. V. Golinky1, A. S. Belyi1,2, V. V. Pashkov1, I. E. Udras1, A. V. Vosmerikov3 and T. I. Gulyaeva1
1Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
2Omsk State Technical University, Pr. Mira 11, Omsk 644050 (Russia)
3Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 4, Tomsk 634021 (Russia)
Keywords: zeolite, aromatic hydrocarbons, conversion, selectivity, butane, hexane, joint transformation

Abstract >>
Acid properties and catalytic activity of high-silica zeolites of ZSM–5 type modified with platinum and gallium were studied in the process of joint conversion of butane and hexane. It was demonstrated that the introduction of modifying metals (Ga, Pt) at the stage of hydrothermal synthesis changes the acid and catalytic properties of initial zeolite. The highest efficiency in the process of aromatization of alkanes under study is exhibited by GaZSM5. With all samples (͖ZSM5, GaZSM5, PtZSM5), the effect of the joint transformation of butane and hexane was not discovered.



11.
Development of Modified Carbon Sorbents for Medical Purposes

L. G. Pyanova1,2, O. N. Baklanova1, V. A. Drozdov1, V. A. Likholobov1,2, A. V. Sedanova1 and M. S. Drozdetskaya1
1Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
2Omsk State Technical University, Pr. Mira 11, Omsk 644050 (Russia)
Keywords: carbon sorbent, modification, polyvinylpyrrolidone, hydroxyacetic acid, physicochemical properties, application materials, antibacterial activity, antimycotic properties

Abstract >>
Results of the studies dealing with the development of application carbon sorbents for medical purposes are presented. The directions of the synthesis of carbon application materials are outlined, the methods of carbon surface modification are described. Physicochemical and medical–biological studied of the resulting sorbents were carried out.



12.
Bifunctional Catalysts of Halogen–Free Carbonylation of Diemthyl Ether into Methylacetate

G. G. Volkova and E. A. Paukshtis
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
Keywords: carbonylation, dimethyl ether, methylacetate, acid cesium salt, heteropolyacid

Abstract >>
Acid centres of bifunctional catalysts Rh/SO4/ZrO2, Rh/WOx/ZrO2 and Rh/CsH3–W12O40 were studied by means of IR spectroscopy of adsorbed pyridine. The effect of type, concentration and strength of acid centres on the activity and selectivity of catalysts in halogen-free carbonylation of dimethyl ether was established. It was demonstrated that the most efficient catalysts are those with the high concentration of strong Brøensted acid centres Rh/CsH3W12O40 (1.5 ≤ x ≤ 2).