Publishing House SB RAS:

Publishing House SB RAS:

Address of the Publishing House SB RAS:
Morskoy pr. 2, 630090 Novosibirsk, Russia



Advanced Search

Chemistry for Sustainable Development

2013 year, number 1

1.
Novel Approaches to Spectrophotometric Analyzing the Unseparated Mixtures of Organic Substances

V. I. VERSHININ
Dostoevsky Omsk State University, Pr. Mira 55A, Omsk 644077 (Russia)
E-mail: vyvershinin@yandex.ru
Keywords: analysis of organic substances, analysis of unseparated mixtures, molecular absorption spectrometry, inter-reference overlapping, non-additivity, integrated parameters
Pages: 112

Abstract >>
We discuss the tasks and methodological problems of molecular absorption spectrometry as a method for the analysis of unseparated mixtures of organic compounds (petroleum products, pharmaceuticals, and others), which method in some cases can successfully compete with chromatography. Using the chemometric algorithms, in particular the method of projection to latent structures, allows successfully solving three major problems: to eliminate the influence of inter–reference spectral overlapping, to take into account a non-additive character of absorption, to level the detection sensitivity with respect to similar analytes. A brief review of relevant studies carried out within recent years in the Omsk State University is reported.
																				  																		



2.
X–ray Absorption Spectroscopy as a Tool for Studying and Developing Novel Materials

D. I. KOCHUBEY and V. V. KANAZHEVSKIY
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
E-mail: kochubey@catalysis.ru
Keywords: EXAFS, XANES, X-ray absorption spectroscopy, platinum nanoparticles, gold nanoparticles, molybdenum sulphate, zirconium oxychloride in the sulphuric acid, cobalt valence state in compounds, ruthenium-rubidium catalysts
Pages: 1328

Abstract >>
Despite the abundance of available experimental techniques, the X-ray absorption spectroscopy often remains the only acceptable means for solving a number of problems: studying X-ray amorphous substances, determining the phase composition at a lower concentration limit for impurity samples, determining the valence state of a chemical element in the case of a low content thereof in the sample (mass percent quota). The present review reports the theory and examples of successful applying the methods of EXAFS and XANES to solve complicated problems.
																				  																		



3.
Formation of Platinum Centers in Basic Carriers of Layered Double Hydroxide Type

O. B. BELSKAYA1,2, L. N. STEPANOVA1, N. N. LEONTYEVA1, M. O. KAZAKOV1, T. I. GULYAEVA1, S. V. CHEREPANOVA3, A. V. LAVRENOV1 and V. A. LIKHOLOBOV1,2
1Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
E-mail: obelska@ihcp.oscsbras.ru
2Omsk State Technical University, Pr. Mira 11, Omsk 644050 (Russia)
3Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
E-mail: svch@catalysis.ru
Keywords: magnesium-aluminum layered hydroxides, platinum, propane dehydrogenation
Pages: 2938

Abstract >>
Results are reported on studying the interaction of Pt (IV) anionic chloride complexes with layered magnesium-aluminum hydroxides in the course of synthesizing Pt/MgAlOx catalysts. As the oxide precursors there were layered hydroxides used with different nature of interlayer anions (and ) and with Mg/Al ratio ranging within 24. The nature of an interlayer of anion is an important parameter affecting the amount of fixed platinum, the composition of surface species and the sites of location thereof in the structure of layered material. In the case of using a hydroxide carrier with the carbonate counterion the fixation of platinum occurs with the participation of the OH groups of hydroxide layers, via adsorbing the hydrolyzed forms of the complexes on the surface. The reduction thereof leads to the formation of isometric platinum particles of 24 nm in size. When attaching the platinum complexes to aluminum-magnesium hydroxide with interlayer anions , the precursor of the active component is mainly located in the interlayer space, with further forming the particles of flat morphology 50 nm long and the thickness close to the interlayer distance in the layered carrier (0.75 nm). In the case of varying the Mg/Al ratio, an increase of triply charged aluminum cation causes changing the structural characteristics and adsorption properties of aluminum-magnesium hydroxide to result in the formation of an oxide phase with a more developed surface area and higher pore volume. Increasing the positive charge density and enhancing the electrostatic interaction promote the adsorption of a greater amount of platinum (IV) anionic complexes and a stronger interaction thereof with the hydroxide layers. In the case of changing the Mg/Al ratio from 4 to 2, one can observe increasing the dispersity level of the supported platinum particles and increasing the activity of Pt/MgAlOx catalysts in the propane dehydrogenation reaction.
																				  																		



4.
Studying the Pt/SO42–/ZrO2 Systems Applied onto SiO2 and Al2O3in the Reaction of nHexane Isomerization

L. I. BIKMETOVA1, K. V. KAZANTSEV1, E. V. ZATOLOKINA1, V. A. DROZDOV1, A. V. SHITOVA1, E. A. PAUKSHTIS2, M. D. SMOLIKOV1and A. S. BELY1
1Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
E-mail: lbikmetova@mail.ru
2Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
Keywords: sulphated zirconia, supported catalysts, n–hexane isomerization
Pages: 3945

Abstract >>
Zirconium sulphate catalysts applied ontoSiO2 and Al2O3 were prepared and investigated. Phase composition inherent in the catalysts, acidic properties according to the adsorption of CO and textural characteristics thereof were investigated. Catalytic activity level in the isomerization reaction of n–hexane was determined. It has been demonstrated that the most active catalytic system is presented by a catalyst based on Al2O3 carrier. The yield of hexane isomers wit the use of this catalyst amounts up to 75 mass % within the temperature range of 200220 °C. It has been found that in the case of using alumina as a carrier the catalysts exhibit forming strong acid centers with the absorption bands of adsorbed CO being at 2210 and 2224 cm1.
																				  																		



5.
One-Stage Synthesis of Propylene from Ethylene UsingPd–Re2O7/B2O3Al2O3 Catalyst

E. A. BULUCHEVSKIY, M. S. MIKHAILOVA and A. V. LAVRENOV
Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
E-mail: bulu@ihcp.oscsbras.ru
Keywords: palladium sorption, ethylene, propylene, oligomerization, metathesis
Pages: 4751

Abstract >>
Equilibrium was investigated concerning the sorption of palladium from the H2PdCl4 and Pd(NH3)4Cl2 solutions onto B2O3–Al2O3 carrier. It is demonstrated that the sorption equilibrium is described by Langmuir equation. According the results of testing the Pd/B2O3Al2O3 samples in the course of oligomerization it has been found that the optimum content of palladium in the catalyst should be equal to 0.5 mass %, whereas the optimum precursor of palladium should be presented by palladium chloride complex. The catalytic properties of PdRe2O7/B2O3Al2O3 system in the one-stage propylene synthesis from ethylene were studied. It has been demonstrated that it is possible to obtain propylene with the yield equal to 7783 % with respect to the theoretically determined one.
																				  																		



6.
Synthesis, Structure and Properties of the System B2O3/Al2O3

T. R. KARPOVA, E. A. BULUCHEVSKIY, A. V. LAVRENOV, N. N. LEONTYEVA, M. V. TRENIKHIN, T. I. GULYAEVA and V. P. TALZI
Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
E-mail: ktr@ihcp.oscsbras.ru
Keywords: borate-containing aluminium oxide, phase composition, texture, coordination state of aluminium
Pages: 5360

Abstract >>
The effect of chemical composition on the formation of the crystal structure and texture characteristics of the oxide system B2O3–Al2O3 obtained through impregnation of pseudoboehmite with the solutions of ortho-boric acid was studied. It was shown that the modification with boron oxide slows down the crystallization of aluminium oxide. According to the high-resolution TEM data, borate-containing aluminium oxides are composed of amorphous and crystalline primary particles. It was established by means of 27Al MAS NMR and 11 MAS NMR that aluminium atoms in the samples occur in octahedral, tetrahedral and penta-coordination, while boron atoms occur in trigonal and tetrahedral coordinations; their relative content depends on chemical composition. The dependence of the specific surface of B2O3Al2O3 system on its composition has an extremal character; the maximum is achieved with B2O3 content 5 mass %.
																				  																		



7.
Studies on the Structure of Mg–Al and NiAl Oxide Carriers Obtained from Layered Double Hydroxides for HydrocarbonProcessing Catalysts

N. N. LEONTYEVA1, S. V. CHEREPANOVA2, O. B. BELSKAYA1, V. A. DROZDOV1 and V. P. TALZI1
1Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
E-mail: n_n_leonteva@list.ru
2Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
Keywords: boratecontaining aluminium oxide, phase composition, texture, coordination state of aluminium
Pages: 6169

Abstract >>
TThe structure of oxides obtained by the calcination of layered Mg–Al and NiAl (Mg/Al = Ni/Al = 2 : 1) double hydroxides with the structure of hydrotalcite. It is demonstrated that the formation mechanisms for the oxides are different: the MgAl oxide retains the original cation ratio, whereas the structure of the oxide formed represents a kind of layered defective spinel. Calcining the NiAl hydroxide results in the fact that the majority of Al3+ ions reaches the surface of the oxide particles, thereby forming aluminum hydroxide with retaining the nickel oxide phase in the course of hydration. It is established that, depending on the number of aluminum atoms in the bulk of the particles there are different structures of oxides formed, those determine the oxide ability either of restoring the layered oxide structure in the case of MgAl hydrotalcite, or saving the structure NiAl oxide in the course of hydration.
																				  																		



8.
Studying the Aluminum–Palladium Catalysts for Selective Acetylene Hydrogenation into Ethylene Prepared by Surface SelfPropagating Thermal Synthesis

O. O. MIRONENKO1, N. B. SHITOVA1, N. S. SMIRNOVA1, D. I. KOCHUBEY2, L. S. KIBIS2, R. V. GULYAEV2, A. I. BORONIN2 and P. G. TSYRUL'NIKOV1
1Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
E-mail: olesyashsh@rambler.ru
2Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
Keywords: self-propagating surface thermal synthesis, liquid-phase hydrogenation of acetylene, EXAFS, XPES, Pd/Al2O3
Pages: 7181

Abstract >>
Studies concerning supported aluminum-palladium catalysts obtained via surface self-propagating thermal synthesis (SSTS) for the selective liquid-phase hydrogenation of acetylene into ethylene in the presence of CO were performed. According to the results of catalytic testing, in the case of running the reaction at 60 °C the SSTS catalysts are inferior to the samples prepared in a conventional manner. At a temperature of 90 C, the catalyst prepared via SSTS with using citric acid as a fuel additive is almost similar to the sample prepared via traditional method, in the catalytic properties thereof. According to the results obtained by EXAFS and XPS, the original SSTS catalysts contain palladium in oxidized and reduced forms, whose ratio depends on the nature and content of the fuel additive. It has been found that palladium oxide in SSTS catalysts can be quickly reduced under the reaction conditions to produce zero-valent Pd, which is indicated by the results of studying the SSTS catalysts before and after the reaction by means of EXAFS.
																				  																		



9.
Effect of Reaction Conditions on the Formation of the Products of Oxidative Pyrolysis of Methane on the Resistive Fechral Catalyst

S. S. SIGAEVA, A. A. SLEPTYREV, V. L. TEMEREV and P. G. TSYRUL'NIKOV
Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
E-mail: s_in_cube@mail.ru
Keywords: catalytic pyrolysis, methane, Fechral, resistive catalysts
Pages: 8390

Abstract >>
The effect of reaction conditions (methane concentration, flow rate, catalyst position, gas dynamic mode) on methane pyrolysis within temperature range 700–1200 °C on preliminarily annealed Fechral wire heated with electric current, at a ratio 4/2 = 15 : 1 was investigated. It was shown that independently of conditions the process runs in two temperature regions differing in the selectivity of the formation of major products 2hydrocarbons. Reaction conditions have a substantial effect on methane conversion and selectivity with respect to reaction products. The maximal selectivity with respect to 2 products can be achieved with the transversal coil position to the gas flow and with the use of flow-circulation set-up instead of flow one. An increase in methane concentration in the initial mixture has ambiguous effect on the selectivity with respect to 2 hydrocarbons within different temperature ranges: for temperature not hgiher than 1000 C, this causes an increase in selectivity with respect to ethylene and acetylene, while at 1000 and above this causes a decrease in selectivity with respect to these components.
																				  																		



10.
Investigation of the State of Active Component in Pd/Ga2O3 and Pd/In2O3 Catalysts of Liquid-Phase Hydrogenation of Acetylene into Etylene

N. S. SMIRNOVA1, D. A. SHLYAPIN1, O. V. PROTASOVA1, M. V. TRENIKHIN1, T. I. GULYAEVA1, E. YU. GERASIMOV2, L. S. KIBIS2, N. B. SHITOVA1, D. I. KOCHUBEY2 and P. G. TSYRUL'NIKOV1
1Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
E-mail: everinflame@gmail.com
2Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
Keywords: liquid-phase hydrogenation of acetylene, EXAFS, XPES, TCD, chemisorption of CO, Pd/Ga2O3, Pd/In2O3
Pages: 91100

Abstract >>
Catalysts of liquid-phase hydrogenation of acetylene deposited on the oxides of aluminium, gallium, and indium were studied. According to the results of catalytic tests and examination using the physical methods, decoration of the active component by partially reduced support is observed in Pd/Ga2O3 and Pd/In2O3 catalysts. An increase in the atomic catalytic activity for the samples deposited on gallium and indium oxides can be connected with the change of the electron density of the active component or with the formation of bimetallic phases.
																				  																		



11.
Structural Transformations of Technical Carbon under the Action of Nanosecond Laser Radiation

M. V. TRENIKHIN1, O. V. PROTASOVA1, G. M. SEROPYAN2 and V. A. DROZDOV1,3
1Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences, Ul. Neftezvodskya 54, Omsk 644040 (Russia)
E-mail: tremv@ihcp.ru
2Dostoevsky Omsk State University, Pr. Mira 55A, Build. 1. Omsk 644077 (Russia)
3Omsk Scientific Centre, Siberian Branch of the Russian Academy of Sciences, Pr. K. Marksa, 15, Omsk 644024 (Russia)
Keywords: technical carbon globules, extension and curvature of graphene layers, transmission electron microscopy, laser irradiation
Pages: 101106

Abstract >>
The structural features and morphology of the particles (globules) of technical carbon (TC) samples, both initial and those treated with pulsed laser radiation, were studied by means of high-resolution transmission electron microscopy. Measurements were carried out; the average distances between graphene layers (<i>d</i><sub>002</sub>), length and curvature of graphene layers in TC globules were calculated. Results of the investigation of structural transformations in TC samples irradiated with nanosecond laser pulses are presented. Changes of the average diameter of globules in TC samples determine the essential difference in the morphology of irradiated nanoparticles and in the lattice parameter <i>d</i><sub>002</sub>.
																				  																		



12.
Optimization of the Composition of Pt/B2O3–Al2O3 Catalyst for Hydroisomerization of BenzeneContaining Fractions

E. D. FEDOROVA, M. O. KAZAKOV, A. V. LAVRENOV, K. S. BUYALSKAYA, 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)
E-mail: jane@ihcp.ru
Keywords: boratecontaining aluminium oxide, hydroisomerization, decrease in benzene content
Pages: 107113

Abstract >>
The possibility to use available and easily synthesized borate-containing aluminium oxide as an acidic support for the catalyst of hydroisomerization of benzene-containing gasoline fractions was demonstrated for the first time. The phase composition, texture characteristics and acid properties of B2O3–Al2O3 systems with boron oxide content 0.939.0 mass %, obtained by mixing pseudo-boehmite with solid orthoboric acid followed by annealing at a temperature of 600 °C were studied. For hydroisomerization of the model mixture of n-heptane with benzene it was shown that the most efficient sample is Pt/B2O3Al2O3 with the support containing 27.5 mass % of boron oxide. This catalyst provides almost complete benzene hydrogenation and the maximal yield of methylcyclopentane (12.1 mass %) and isoheptanes (43.5 mass %) at a temperature of 350 C. Higher selectivity of isomerization reactions in this case is connected with the smaller amount of strong acid centres on the catalyst surface.