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Chemistry for Sustainable Development

2013 year, number 3

1.
Outlooks and Possibilities of the Application of in situ Methods in Catalysis

V. V. KAICHEV
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
E-mail: vvk@catalysis.ru
Keywords: heterogeneous catalysis, in situ methods, self-oscillations, reaction mechanisms
Pages: 231239

Abstract >>
Methodology of in situ investigations aimed at the studies of heterogeneous catalytic reactions is presented. The advantage of this approach in comparison with ex situ studies is demonstrated with a number of examples. The outlooks and possibilities of the application of various physical methods in the in situ mode are considered.



2.
Effect of Surface Modification of γ-Al2O3 Using Oxalate Complexes of Aluminium on the Formation and Properties of Platinum Centres of Pt/Al2O3 Catalysts

R. M. MIRONENKO1, O. B. BELSKAYA1,2, O. V. MAEVSKAYA1, T. I. GULYAEVA1, M. O. KAZAKOV1, A. V. LAVRENOV1 and V. A. LIKHOLOBOV1,2
1 Institute of Hydrocarbons Processing, Siberian Branch of the Russian Academy of Sciences,
Ul. Neftezvodskya 54, Omsk 644040, Russia
ch-mrm@mail.ru
2 Omsk State Technical University,
Pr. Mira 11, Omsk 644050, Russia
Keywords: γaluminium oxide, surface modification, chloride complexes of platinum, aluminium-platinum catalysts, adsorption mechanism
Pages: 241249

Abstract >>
Modification of the oxide surface of aluminium oxide with oxalate complexes of aluminium was carried out, followed by thermal treatment for the purpose of varying the ratio between the functional groups on the surface ( groups, Lewis acid centres). It was established that the modification of γAl2O3 causes a 1.5-fold increase in the amount of adsorbed platinum (IV) complexes and the fraction of these complexes strongly bound with the surface of the support. The effect of γAl2O3 surface modification on the catalytic properties of the system Pt/Al2O3 was demosntrated. It was shown that an increase in the fraction of platinum forms strongly bound with the support causes an increase in the content of methylcyclopentane in the products of nhexane isomerization and an increase in the selectivity of the formation of propylene in propane transformations.



3.
Bifunctional Metal Complex Catalysts for the Processes of Fine Organic Synthesis

Z. P. PAI
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
E-mail: zpai@catalysis.ru
Keywords: peroxopolyoxometallates, EXAFS, Raman and IR spectroscopy, phase-transfer catalysts, fine organic synthesis
Pages: 251261

Abstract >>
Modern approaches to the development of ecologically and economically acceptable methods for obtaining a number of industrially essential products are considered. The promising character of the application of phase-transfer catalysis method for reactions proceeding in liquid two-phase systems with the use of ecologically favourable oxidizing agent hydrogen peroxide was demonstrated. Results of integrated studies of the structural characteristics of tungsten peroxopolyoxocomplexes formed in the interaction of the aqueous solutions of phosphotungstic heteropolyacid with hydrogen peroxide by means of EXAFS, Raman and IR spectroscopy are presented. The synthesized catalysts Q3{PO4[WO(O2)2]4}, where Q3 is a quaternary ammonium cation, were tested in the reactions of oxidation of organic substrates with 3035 % H2O2 solutions.



4.
Synthesis of Polynuclear Isoindolinium Salts and the Transformation of Hydroxymethylisoindolinium Derivatives

E. O. CHUKHAJIAN,K. G SHAKHATUNI and EL. O. CHUKHAJIAN
Scientific Technological Center of Organic and Pharmaceutical Chemistry,
National Academy of Sciences of the Republic of Armenia,
Pr. Azutatyan 26, Yerevan 0014 (Armenia)
E-mail: qnarsh@yandex.ru
Keywords: unsaturated ammonium salts, base-catalyzed intramolecular cyclization, recyclization, double cyclization and recyclization, condensed isoindolinium and dihydrofuran derivatives, 4-hydroxymethyl derivatives of isoindolinium, sequence of cyclization and dehydrochlorination stages
Pages: 263274

Abstract >>
The review is devoted base-catalyzed intramolecular cyclization of ammonium salts containing β,γ-unsaturated groups alongside with various enyne fragments. This process results in the formation of polynuclear isoindolinium salts and in the transformation (recyclization) of those containing the hydroxymethyl group at the position 4 in the aromatic ring.



5.
Isolation of Sodium Chloride from the Human Exometabolite Mineralization Solutions and Vegetable Wastes as Applied to Closed Ecosystems

A. G. BELOBABA1, A. I. MASLIY1, A. A. GUSEV1, A. A. TIKHOMIROV2, YU. A. KUDENKO2 and S. V. TRIFONOV2
1 Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences,
Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: belobaba@ngs.ru
2 Institute of Biophysics, Siberian Branch of the Russian Academy of Sciences,
Akademgorodok, Build. 50, Krasnoyarsk 660036 (Russia)
Keywords: life-support systems, intersystem mass exchange, sodium chloride, fractional crystallization, evaporation, electrodialysis
Pages: 275281

Abstract >>
There were investigated two variants of NaCl isolation from the solutions of human exometabolite mineralization and plant wastes, based on the fractional crystallization of salts via evaporation and the low solubility of NaCl in concentrated HCl, respectively. It has been established that owing to preferential dissolution of the impurities in the concentrated HCl, from the mineralized solutions one could recover 99 % of NaCl contained therein, whose purity of which is not worse with respect to the standard food grade salt. The methods for proposed processing the mineralized solutions allow one to involve NaCl and H2O into the mass exchange within closed environments.



6.
Variations in the Amino Acid Composition of Human Bone Tissue

S. A. GERK1,2 and O. A. GOLOVANOVA2
1 Dostoevsky Omsk State University,
Pr. Mira 55A, Omsk 644077, Russia
gerksa_11@mail.ru
2 Omsk State Transport University,
Prospekt Mira, 35, Omsk 644046, Russia
Keywords: HPLC, bone tissue, chemical composition, coxarthrosis, cluster analysis
Pages: 283288

Abstract >>
With the use of HPLC technique, studies on the amino acid composition of human bone tissue within the age range of 3079 years were performed. Gender-features concerning the qualitative and quantitative amino acid content have been revealed. It is demonstrated that the clinical course of coxarthrosis does not lead to significant changes in amino acid composition of human bone tissue.



7.
Novel Approaches to the Utilization of LargeTonnage Industrial Wastes Such as Hydrolytic Lignin, Sulphur, Polychloroaliphatic Compounds

A. F. GOGOTOV1,2, V. K. STANKEVICH1, V. P. KISELEV3, A. A. CHAIKA2 and V. G. DRONOV2
1 Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
Ul. Favorskogo 1, Irkutsk 664033 (Russia)
E-mail: alfgoga@mail.ru
2 Irkutsk State Technical University,
Ul. Lermontova 83, Irkutsk 664074 (Russia)
3 Siberian Federal University,
Pr. Svobodny 79, Krasnoyarsk 664041 (Russia)
Keywords: lignin, organochlorine residues, sodium polysulphide, condensation products
Pages: 289294

Abstract >>
Organochlorine wastes generated in the production of epichlorohydrin, and lignin could be co-processed to obtain the sulphur-containing derivatives. For this purpose, the wastes of chloroorganic synthesis and hydrolytic lignin chlorinated under mild conditions should be entered into the reaction with sulphur in the form of sodium polysulphides. The overall process is cost-efficient due to the fact that it provides an almost complete conversion of organochlorine waste disposal, sulphur compounds as well as lignin binding. The condensation products obtained were tested as additives for modifying bitumen and demonstrated a good processability.



8.
Thermolysis Dynamics of Bituminous Sandstone from the Bayan-Erkhet Deposit (Mongolia)

N. I. KOPYLOV1, YU. D. KAMINSKY1 and A. K. GOLOVKO2
1 Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences,
Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: kolyubov@narod.ru
2 Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademicheskiy 4, Tomsk 634021 (Russia)
Keywords: bituminous sandstone, thermal analysis, thermolysis, low-melting fraction, sublimates, cinder
Pages: 295301

Abstract >>
The dynamics of thermolysis was studied for the bituminous sandstone taken from the Bayan-Erkhet deposit (Mongolia). It has been demonstrated that the thermolysis procedure could be used for the isolation of bituminous component from these raw materials to obtain valuable intermediates for coal chemistry and motor fuels.



9.
Thermal Decomposition of Coal from the Tuva Deposit

N. I. KOPYLOV and YU. D. KAMINSKIY
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy
of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: kolyubov@narod.ru
Keywords: coal, thermal analysis, mechanical activation, thermal decomposition, briquetting, condensable sublimates
Pages: 303311

Abstract >>
The results of research work are reported concerning the thermal decomposition of coal species from the Ulugh and Chadan beds of the Kaa-Khem site of the Tuva deposit as well as an effect of coal activation on the decomposition process. Potentiality is demonstrated for briquetting the coal after removing gaseous and light liquid fractions from the material.



10.
Studying the Catalytic Activity of Naturally Occurring Zeolites in the Gas-Phase Nitration Reaction of Aromatic Compounds

A. P. KOSKIN1, K. S. GOLOKHVAST2, I. G. DANILOVA1, A. A. VEDYAGIN1,3 and I. V. MISHAKOV1,3
1 Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
E-mail: koskin@catalysis.ru
2 Far East Federal University,
Ul. Sukhanova 8, Vladivostok 690950 (Russia)
3 3Novosibirsk State Technical University,
Ul. K. Marksa 20, Novosibirsk 630092 (Russia)
Keywords: naturally occurring zeolites, acidic properties, gas-phase nitration of benzene, toluene, nitrobenzene, nitrotoluene
Pages: 313321

Abstract >>
An alternative gas phase nitration process was investigated wherein the reaction between an aromatic substrate (benzene/toluene) and a nitrating agent (either a 68 mass % HNO3 aqueous solution, or a mixture of nitrous gases) occurs on a fixed-bed solid acidic catalyst. There have been studied physicochemical properties (elemental composition, pH, crystallinity) and catalytic properties inherent in the samples of naturally occurring zeolites taken from the deposits of Siberia and the Far East. An effect of zeolite preliminary treatment (calcination and acid extraction method) exerted on the activity thereof was investigated. It has been demonstrated that the highest activity is exhibited by a sample with the highest concentration of Bronsted acid sites (99 mol/g according to NH3 adsorption), taken from the Kulikovo deposit (the Amur Region). The productivity of the sample amounted to 161 mg/(gcat h).



11.
Chemical Trace of Emissions from Aluminum Production (Soil Ecology Aspect)

E. V. NAPRASNIKOVA
Sochava Institute of Geography, Siberian Branch of the Russian Academy of Sciences,
Ul. Ulanbatorskaya 1, Irkutsk 664033 (Russia)
E-mail: napev@irigs.irk.ru
Keywords: soil cover, aerotechnogenic emissions, microorganisms, biochemical activity
Pages: 323328

Abstract >>
Studies were performed concerning the features of soil ecological, microbiological and biochemical properties under influenced by the emissions of aluminum plants in Siberia. It has been found that the anthropogenically transformed soils of sub-taiga influenced by water-soluble fluoride species (1020 MPC) cause the greatest inhibition of actinomycetes and chemoorganotrophic asporogenous bacteria. The steppe chernozem under the influence of fluorine (14 MPC) demonstrates a decrease in the level of biochemical activity.



12.
Sorptive Extraction of Tungsten from the Solution of Sodium Tungstate

S. N. CHEGRINTSEV,A. N. DYACHENKO andR. I. KRAIDENKO
National Research Tomsk Polytechnical University,
Pr. Lenina 30, Tomsk 634050 (Russia)
E-mail: chesen@tpu.ru
Keywords: tungsten, sorption, desorption, anionite, AV-17-8, Ambersep 920U, autoclave leaching
Pages: 329332

Abstract >>
Integrated studies of ion exchange extraction of tungsten was carried out in application to the carbonate solutions of autoclave leaching of raw material with low tungsten content. Anionite and desorbent for tungsten extraction were chosen. The integrated technology of processing tungsten-containing raw material was proposed, resulting in obtaining metal tungsten, with the possibility of regeneration of the treating reagent sodium carbonate.



13.
Oxygen- and Nitrogen-Containing Structural Fragments of Resin and Asphaltene Macromolecules Inherent in Heavy Oil from the Usinsk Oilfield

T. V. CHESHKOVA, E. YU. KOVALENKO and T. A SAGACHENKO
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademicheskiy 4, Tomsk 634021 (Russia)
E-mail: azot@ipc.tsc.ru
Keywords: resins, asphaltenes, nitrogen bases, esters and ethers, composition
Pages: 333340

Abstract >>
The composition and structural features of the resin-asphaltene macromolecular fragments inherent in the substances from the Usinsk oilfield were investigated. It has been demonstrated that they contain ether and/or ester groups. Nitrogenous bases in the form of supramolecular structures are present only in the structure of the resinous components.



14.
Changes in the Chemical Composition of the Major Components of Peat under Cavitation Action

A. S. ZMANOVSKAYA and D. V. DUDKIN
Yugra State University,
Ul. Chekhova 16, Tyumen Region, Khanty-Mansiysk 628011 (Russia)
E-mail: a_tolstyak@ugrasu.ru
Keywords: peat, humic acids, humification
Pages: 341345

Abstract >>
Changes of the quantitative and qualitative characteristics of peat components (bitumen, lignin, cellulose, humic acids) under cavitation action of aqueous alkaline media are considered. It was demonstrated that the cavitation treatment of peat in alkaline solutions involves the structural rearrangement, changes of separate fragments of macromolecules. As a result, additional amount of humic acids is formed. To obtain humic acids, it is preferable to use the aqueous solution of ammonia as the base. In water-ammonia medium, nitrogen fixation occurs with the participation of all the components of humatecarbohydrate complex.