Petroleum Chemistry (v.54, #3)

Composition of naphthene hydrocarbons in crude oils from deposits of different ages by N. G. Voronetskaya; G. S. Pevneva; A. K. Golovko (165-170).
The composition of saturated cyclic hydrocarbons in crude oils from deposits of different ages located in various oil and gas basins has been studied. It has been found that the concentration of cyclanes in the oils decreases on passing from Paleozoic to Cenozoic deposits. For Cenozoic and Mesozoic oils, the concentration of cyclanes also decreases with the increasing occurrence depth of sediments within the same age. The group type composition of saturated cyclic hydrocarbons in oils from deposits of different ages is similar in character, where the concentration of cyclanes follows the order: monocyclanes > bicyclanes > tricyclanes > tetracyclanes > pentacyclanes.
Keywords: crude oil; petroleum hydrocarbons; composition; naphthenes; cyclanes

Dependence of the rate of formation and the P-T stability field of methane hydrate suspensions in crude oils upon oil composition by A. S. Stoporev; A. Yu. Manakov; L. K. Altunina; A. V. Bogoslovskii; L. A. Strelets; E. Ya. Aladko (171-177).
Equilibrium conditions for hydrates obtained from water emulsions in crude oils of the Yurubcheno-Tokhomskoe, Verkhnechonskoe, Gerasimovskoe, and Usinskoe fields have been studied, as well as the relative rates of hydrate formation in these systems. It has been concluded that the presence of oil does not alter the equilibrium conditions of hydrate formation. An increase in the concentration of resin-asphaltene substances and paraffins in crude oil leads to a decrease in the hydrate formation rate.
Keywords: gas hydrate; crude oil; emulsion; equilibrium hydrate formation conditionsl

Composition of products of analytical pyrolysis of resin and asphaltene fractions of Usa oil by V. R. Antipenko; A. A. Grin’ko; V. N. Melenevskii (178-186).
Resin and asphaltene fractions of crude oil from the Usa field (Timan-Pechora oil-and-gas province, Russia) obtained by fractional precipitation of asphaltenes and chromatographic separation of resins have been analyzed using Rock-Eval pyrolysis and flash pyrolysis (650°C, 20 s) with on-line chromatographic/mass spectral detection of volatile products. It has been shown that the samples under study contain organic compounds with a relatively low molecular mass in an amount of 2.3 to 15.3 wt % as either impurities or moieties bound in resin and asphaltene molecules by labile chemical bonds. The products of flash pyrolysis of the samples under study differ in the relative amount of the “unresolvable complex mixture” of unidentified compounds; the chemical group and molecular composition; and the relative amount of identified types of compounds, such as normal and isoprenoid alkanes, α-olefins, cyclohexanes, cheilanthanes and hopanes, hopenes, pregnanes and steranes, alkylbenzenes, naphthalenes, phenanthrenes and anthracenes, and benzo- and dibenzothiophenes.
Keywords: Usa oil; resins; asphaltenes; fractions; pyrolytic analysis; flash pyrolysis; volatile products; composition; comparison

Geochemical features of low-mature lacustrine oils of China by T. L. Vinogradova; S. A. Punanova (187-194).
Data on the physicochemical properties and the hydrocarbon and trace-element compositions of hydrocarbon fluids from various oil and gas basins in China have been analyzed and summarized. The distribution of a wide range of hydrocarbon biomarkers in crude oils has been correlated with the salinity of lacustrine sediments. The variety of facies that characterize the burial and transformation of the original hydrocarbon-generating organic matter is reflected in particular features of oil composition. The parameters identified are recommended for geochemical correlation of crude oils with rock organic matter and for prediction of the physicochemical properties or the hydrocarbon and trace-element compositions of oil accumulations.
Keywords: oil generation; matured oils; geochemical correlation of oils; hydrocarbon biomarkers; trace element composition of oil accumulations

Initiated conversion of ethanol to divinyl by the Lebedev reaction by V. F. Tret’yakov; R. M. Talyshinskii; A. M. Ilolov; A. L. Maksimov; S. N. Khadzhiev (195-206).
A synergistic effect has been revealed upon hydrogen peroxide initiation of the catalytic ethanol-to-divinyl conversion process, proposed by S.V. Lebedev, on the (K2O)ZnO/γ-Al2O3 catalyst. The efficiency of the initiator has been examined, depending on the form of aluminum oxide, hydrogen peroxide concentration in the system, and the linear velocity of the feed stream. The behavior of the process characteristics has been analyzed and a kinetic model of the process has been proposed on this basis, enabling the selectivity of the initiated reaction to be controlled.
Keywords: divinyl; ethanol; catalyst; kinetics; initiator; dehydrogenation; dehydration; compartmented reactor; hydrogen peroxide

Alternative methods for production of alicyclic epoxides by N. V. Vereshchagina; T. N. Antonova; I. G. Abramov; G. Yu. Kopushkina (207-212).
The salient and peculiar features of the oxidation of dicyclopentene and unsaturated alicyclic hydrocarbons with a medium-sized carbon ring into the corresponding epoxides have been studied. Organic hydroperoxides, aqueous hydrogen peroxide, and peracids have been used as oxidizing agents. The reactivity of the substrates in each of the oxidation processes under consideration has been estimated, and conditions providing a high epoxide yield have been chosen. The advantages and disadvantages of each process taking into account the problems of isolation of the desired product are considered. The results obtained allow the peracid method to be recommended for the synthesis of dicyclopentene epoxide as an effective and convenient for practical implementation.
Keywords: dicyclopentadiene; dicyclopentene; epoxides; unsaturated hydrocarbons; alicyclic hydrocarbons; hydroperoxides; peracids; hydrogen peroxide

Salient features of deactivation of an iron oxide catalyst for dehydrogenation of methylbutenes to isoprene in industrial adiabatic reactors by E. Kh. Karimov; L. Z. Kas’yanova; E. M. Movsumzade; R. R. Daminev; O. Kh. Karimov (213-217).
The problems of deactivation of iron oxide catalysts in the process of industrial dehydrogenation of methylbutenes to isoprene have been considered. The dependence of deactivation of the catalyst fixed bed on the time on-stream of different sections of the catalyst along the reactor height has been examined. The cause of poor performance of a part of the catalyst bed has been revealed and substantiated. Based of the results of the study, the authors propose an approach to predicting the catalyst performance during a long time on-stream.
Keywords: dehydrogenation of olefins; catalyst deactivation; methylbutenes; isoprene; iron oxide

Immobilization by covalent bonding of copper complexes with amino alcohols, amino acids, hydroxyalkylpyridine, and quaternary ammonium ionic liquids on the surface of mineral supports makes it possible to prepare heterogeneous catalysts for oxidation of mercaptans. An advantage of these catalysts is the combination of high performance with stability.
Keywords: catalysts; mercaptans; immobilized metal complexes; oxidation

The influence of admixtures of chemically different polar organic solvents on the yield of distillates in atmospheric and vacuum distillation of crude oil has been studied. A comparative assessment of the compositions of asphaltenes isolated from vacuum residues has been made with the use of IR spectroscopy. The distillate recovery efficiency has been found to increase to the greatest extent in the presence of N-methylpyrrolidone as an additive during atmospheric distillation and ɛ-caprolactam in the case of vacuum distillation. However, the admixture of ɛ-caprolactam to crude oil does not provide an increase in aromaticity of vacuum-residue asphaltenes.
Keywords: crude oil; activating additive; organic matter; distillation; distillate fractions; yield; properties

Arylsulfonyl-N-2-carbamoylguanidines in synthesis of hetarylsulfonamides and characterization of the compounds obtained by S. A. Mamedov; S. I. Mamedova; N. P. Ladokhina; I. Sh. Guseinov; F. A. Fatalizade; Sh. K. Kyazimzade (229-233).
It has been found that despite the presence of three active amino moieties of carbamoylguanidine, it adds to sulfonyl chloride by the amino group, not the carbamoyl groups, to give monosulfonamides. Being 1,3-dipolar compounds, the arylsulfonylcarbamoylguanidines obtained readily add to polarophiles, such as chloroacetonitrile and benzoin, to form imidazolylsulfonamides or make pyrimidinylsulfonamides by reacting with arylidene malonodinitrile. A study of the reactivity of sulfonyl-2-carbamoylguanidine in the N-alkylation reaction has revealed that the reaction proceeds exceptionally via the replacement of the hydrogen atom at the sulfonamide nitrogen. Examination of some sulfonyl-N-carbamoylguanidine derivatives has shown their high rust-preventing and tribological properties in lubricating oils and greases, as well as antimicrobic activity.
Keywords: arylsulfonylcarbamoylguanidines; N-alkylation reaction; tribological properties; antimicrobial activity; antirust properties

Integrated assessment of anthropogenic contamination of oil-producing territories in Western Siberia by L. K. Altunina; L. I. Svarovskaya; M. N. Alekseeva; I. G. Yashchenko (234-238).
Hard-to-reach, vast wetlands areas of Western Siberia oil-producing companies allow neither timely assessing the scale of pollution nor planning remediation measures. We have developed a technique of mapping and evaluating anthropogenic transformation of vegetation cover in oil-polluted areas on the basis of satellite images. To assess environmental oil pollution and revegetation dynamics, the normalized difference vegetation index (NDVI) calculated on the basis of satellite images has been used. The index values obtained have been confirmed by the results of instrumental and microbiological analyses of samples collected in the contaminated area. Using topographic maps and Landsat satellite images for inaccessible wetland areas of oil producing companies in Western Siberia, a network of pipelines that pose special risk to environmental resources has been highlighted.
Keywords: contamination of oil-producing areas; anthropogenic transformation of vegetation; environmental risk; normalized difference vegetation index; GIS technology

NaY/Beta was firstly modified using two ion-exchanged and two calcinations method to prepare CeY/Beta and CaY/Beta composite molecular sieve, which were characterized by means of XRD and ICP-MS. Static adsorption experiments were carried out to study the adsorption of organic thiophene and quinoline. The desulphurization and denitrogenation adsorption effect of the modified molecular sieve was enhanced greatly, and CeY/Beta molecular sieve exhibited better performance in the desulphurization rate and denitrogenation rate.
Keywords: Y/Beta composite molecularsieve; zeolite; modifiability; adsorption; desulfurization; denitrogenation