L. K. ALTUNINA, L. A. STASYEVA, V. A. KUVSHINOV, V. V. KOZLOV, I. V. KUVSHINOV
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia
Keywords: thermotropic inorganic and polymer gels, rock reinforcement, waterproofing, plugging, steam breakthroughs, mines, oil mines
Pages: 157-164
The article presents the results of laboratory studies and pilot tests of compositions developed to eliminate steam and water breakthroughs from the rock mass into oil mine workings, and to fill voids in the rock mass in places where steam breakthroughs occur. The effect of individual components is investigated, which allows combining them to achieve the required properties of the composition. Laboratory studies have shown a high efficiency of compositions with two gelling components (polymer and inorganic) with the addition of a dispersed filler - basalt fibre. The compositions functions well within a wide temperature range (20-200 °C), are non-toxic and fireproof. Pilot tests of the developed composition for blocking steam breakthroughs into the mine were carried out in early 2024 at an experimental site of the Yaregskoye oil mine, using standard equipment available at the mine. The tests have shown applicability of the composition under oil mine conditions. The results of control observations show that the composition successfully plugs cracks and pores in the rock and in the concrete jacket, blocks steam breakthroughs, and retains its properties for a long time. It is planned to develop this area of experimental work, including refining the technology of injecting the composition to fill large voids, to determine the required composition volume, injection rate and location of injection points. In the future, it planned to test these compositions for surface steam injection wells.
L. M. VELICHKINA, YA. E. BARBASHIN
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia
Keywords: zeolite, pentasil, alkaline treatment, nickel nanopowder, gasoline, coke, regeneration
Pages: 165-172
A catalyst for the process of upgrading the straight-run gasoline fraction of oil was developed on the basis of pentasil zeolite by means of postsynthetic alkaline treatment, followed by the introduction of nanosized nickel powder. Three reaction-regeneration cycles were carried out, textural, acidic and catalytic properties of the initial and regenerated samples were studied, the amount of carbon compaction products and temperature range of their removal were determined. It is shown by IR spectroscopy that triplicate regeneration of carbonised zeolite catalysts does not change their crystal structure. It is shown by low-temperature nitrogen adsorption that multiple regenerations of the catalyst lead to an insignificant decrease in total specific surface area and total specific pore volume, with an increase in the specific surface area of mesopores. The temperature-programmed desorption of ammonia has been used to determine that the strength and concentration of acid sites in the regenerated samples decreased significantly, compared to the initial zeolite, only after the third regeneration. The activity of initial zeolite catalyst and its regenerated forms has been studied in processing the straight-run gasoline fraction of oil by the flow method in a reactor with a fixed catalyst bed, without using hydrogen-containing gas, at atmospheric pressure. It has been shown that after each reaction-regeneration cycle, the catalytic activity decreases slightly, but at the same time, the octane numbers of the resulting gasolines remain fairly high, and the yield of the catalysates increases. Using differential thermal analysis, it was determined that the number of regenerations has almost no effect on the amount of carbon compaction products on zeolite catalysts, as well as on the temperatures of decomposition peaks and termination of coke removal, but slightly reduces the temperature at which carbon deposits begin to burn out.
L. N. VOSMERIKOVA, A. A. VOSMERIKOV, YA. E. BARBASHIN, A. V. VOSMERIKOV
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia
Keywords: ethane, propane, n-butane, olefinic hydrocarbons, activity, selectivity, acidity
Pages: 173-179
Results of studies on the conversion of gaseous hydrocarbon feedstock with different compositions into olefin hydrocarbons over zeolite-containing catalysts are presented. The results of catalyst testing indicate that zeolites modified with phosphorus and manganese exhibit high activity in the conversion of lower C2-C4 alkanes into olefin hydrocarbons. It has been determined that the P-containing zeolite catalyst has the highest dehydrogenating activity, and the Mn-containing zeolite catalyst is characterized by a higher overall activity. It is shown that significant conversion of the feedstock is observed within the temperature range of 600-650 °С, depending on the hydrocarbon chain length of the initial alkane molecule. For the P-containing zeolite catalyst, almost linear dependence of the yield of olefin hydrocarbons on the conversion of the initial С2-С4-hydrocarbons is observed. At the same time, for the Mn-containing zeolite, the dependence of the yield of olefin hydrocarbons on conversion is determined by the type of initial hydrocarbon feedstock. The acid and textural characteristics of the original zeolite and its modified samples were studied by temperature-programmed desorption of ammonia and low-temperature adsorption of nitrogen, and their distinctive features affecting the properties of the catalysts in the conversion of C2-C4 alkanes into olefin hydrocarbons were established.
N. N. GERASIMOVA, R. S. MIN, T. A. SAGACHENKO
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia
Keywords: asphaltenes, thermolysis, chemical degradation, structures
Pages: 180-189
The composition of fragments linked by sulphide bridges in the molecules of resin-asphaltene substances isolated from the liquid products of thermal destruction of asphaltene components of heavy high-sulphur oils from the Usinskoye and Ashalchinskoye fields in supercritical n-hexane is investigated using a complex of physicochemical methods (selective chemical degradation, IR spectroscopy, gas chromatography - mass spectrometry). The set of compounds identified in the products of C-S bond cleavage in the molecules of secondary asphaltenes and resins is largely identical to that identified in the products formed in the chemical destruction of the molecules of initial asphaltene components. They are represented by normal and branched alkanes, n-alkylcyclopentanes, n-alkylcyclohexanes, steranes, hopanes, phenylalkanes differing from each other in the position of phenyl ring in the carbon chain, diphenyls, naphthalenes, phenanthrenes, dibenzothiophenes, n-alcanoic acids, ethyl and isopropyl esters of n-alkanoic acids, and pentacyclic compounds of the oleanene series. A distinctive feature of secondary asphaltene molecules is the presence of n-alk-1-enes with an even number of carbon atoms and monocyclic aromatic hydrocarbons linked through sulphide bridges in their structure. The similarity of the set of compounds linked through sulphide bridges in the structure of initial asphaltenes and the products of their thermal decomposition under supercritical conditions is established, which suggests that the secondary asphaltenes and the resulting resins are fragments of the molecules of initial samples. These molecular fragments are linked in their structure through the least thermally stable functional groups - ether, disulphide and sulphide. The revealed differences in the pattern of molecular mass distribution for similar sulphur-bound compounds in the structure of secondary asphaltenes and resins allow us to assume that the resulting resinous components are located at the periphery of the asphaltene macromolecules of heavy high-sulphur oils.
N. S. KOBOTAEVA1, O. S. ANDRIENKO2 1Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia 2V.E. Zuev Institute of Atmospheric Optics, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia
Keywords: oxidation of sulphur-containing compounds of oil, catalysts, composite materials, transition metals
Pages: 190-195
Composite metal-carbon material based on technical carbon and metals (NiCo) was created, its physicochemical and catalytic properties in the oxidative desulphurisation of oil were studied. It has been established that the process of oil desulphurisation can be carried out under sufficiently mild conditions: temperature 60 °C, process time 90 min, catalyst content 1-1.3 wt%, the molar ratio of sulphur feedstock/oxidizer = 1 : 4. A more effective extraction system for extracting oxidised sulphur compounds from oil is a mixture of dimethylformamide (DMF) and water at the volume ratio of 9 : 1. In this case, it is possible to achieve a high degree of sulphur removal from oil - more than 70 %.
E. YU. KOVALENKO1, T. V. CHESHKOVA1, K. A. CHEREDNICHENKO2, T. A. SAGACHENKO1, R. S. MIN1 1Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia 2Gubkin Russian State University of Oil and Gas (National Research University), Moscow, Russia
Keywords: heavy oils, asphaltenes, morphology, structural-group characteristics, chemical destruction
Pages: 196-209
The structural organisation and chemical composition of asphaltenes of heavy oils from the sediments of the Paleozoic complex of the Volga-Ural and Timan-Pechora oil and gas provinces are studied using a mix of physicochemical research methods (electron microscopy, proton magnetic resonance spectroscopy, X-ray diffraction, chemical destruction, and combined gas chromatography-mass spectrometry). It is shown that the asphaltenes of oils from the Permian-Carboniferous and Devonian sediments, unlike the asphaltenes of Permian oil with their smooth surface, are characterised by a loose and porous surface, and smaller sizes of nanoaggregates forming a disordered tangled structure caused by the presence of a branched alkyl chain configuration, which hinders aromatic sheets stacking. The crystallites of asphaltene nanoaggregates of heavy oils are characterised by similar thickness, average diameter, and number of aromatic layers in their cluster core, as well as the distance between the aromatic layers and saturated fragments. It has also been determined that the mean molecule of asphaltenes of the Permian oil is larger in size due to the high content of aromatic and naphthenic cycles in the naphthenoaromatic system. A structural feature of the asphaltene components of Devonian oils is a more branched alkyl chain configuration. The structure of the asphaltenes of heavy oils includes fragments linked through sulphide, ether, methylene and polymethylene bridges. Among them, acyclic, mono- and polycyclic naphthenic and aromatic hydrocarbons, as well as sulphur- and oxygen-containing compounds have been identified. The same representatives of sulphur-bound and ether-bound saturated and aromatic hydrocarbons in the structure of asphaltene molecules of heavy oils are similar in composition, but differ from each other in molecular mass distribution. The results of the investigation expand our understanding of the structure of asphaltenes of heavy oils, which may be used to model their structure for developing new controlled methods for processing hydrocarbon raw materials.
R. N. MUSTAFIN, L. K. ALTUNINA, V. V. KOZLOV, M. R. SHOLIDODOV, A. R. SAIDENTSAL
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia
Keywords: acid treatment, acid composition, rocks, methods of enhancing oil recovery, dissolving ability
Pages: 210-213
Results of the study of a multifunctional acid composition GBС-F based on surfactants, polyol, an adduct of inorganic acid and carbonic acid diamide are presented. The dissolving ability of the acid composition in concentrated and diluted forms in relation to terrigenous and carbonate rocks, quartz and pyrite was studied. The use of the GBС-F composition was determined to cause different dissolving effects on the rocks of different types. It is shown that concentrated or diluted GBC-F affects the rocks to different extents: quartz and pyrite dissolved better in the diluted solution of the acid composition, while the use of concentrated GBC-F (the liquid commercial form) had the maximum effect when dissolving carbonate rock. In the study of terrigenous reservoir, rock solubility in the concentrate of GBC-F during the first hours was better than in the diluted solution, but after soaking for 24 h the values became equal.
A. N. OCHERED’KO, A. V. LESHCHIK, A. YU. RYABOV, S. V. KUDRYASHOV
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia
Keywords: plasma chemistry, dielectric barrier discharge, aromatics, benzene, cumene, oxidation
Pages: 214-218
The oxidation of cumene and its mixture with benzene by oxygen in the low-temperature barrier discharge plasma has been studied under the efficient removal of reaction products from the reactor, which makes it possible to avoid the deep oxidation of initial reagents and the formation of polymer deposits on reactor walls. Experiments were carried out in a setup with a plasmachemical reactor, under barrier discharge in the flow mode. The major products of cumene oxidation, namely acetophenone and dimethylphenylcarbinol, are formed with a total selectivity of up to 78 wt%. Cumene oxidation is not accompanied by the formation of phenol and its derivatives. Cumene conversion does not exceed 1.2 wt%. Oxidation of a mixture of cumene and benzene leads to the formation of cumene oxidation products (acetophenone and dimethylphenylcarbinol) along with the products of phenol oxidation (phenol and diphenols). It is shown that both aromatic hydrocarbons are oxidised independently in their mixture. Based on the research results and literature data, a probable mechanism of cumene oxidation in a barrier discharge is discussed and an attempt is made to simulate the process of its oxidation. The possibility to govern the oxidation of aromatic hydrocarbons in the low-temperature barrier discharge plasma by reactor temperature control is demonstrated.
T. O. PEREMITINA, I. G. YASHCHENKO
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia
Keywords: satellite data, vegetation index, geoinformation systems, vegetation cover
Pages: 219-223
The dynamics of the state of vegetation cover has been analysed in the hydrocarbon deposits of the Tomsk region, specifically Luginetskoye, Katylginskoye, Olenye, Lomovoye. The territory of the Oglatsky Nature Reserve was chosen as the background area. Based on satellite data from Terra/MODIS (Moderate Resolution Imaging Spectroradiometer), the average values of the NDVI vegetation index (Normalized Difference Vegetation Index) were calculated from June, 26 to July, 11 for the years 2012 to 2022. It has been found that the same trend in NDVI values is observed for the vegetation in the studied oilfields Luginetskoye, Katylginskoye, and Olenye: the maximum NDVI values were recorded in 2016, while the minimum values occurred in 2012. For the territory of the Lomovoye oilfield, the highest NDVI value was established in 2022, with the lowest in 2012. Overall, a positive trend in NDVI values was noted across all studied areas, with an average increase by 9.7 % from 2012 to 2022, indicating a stable (not suppressed) state of the vegetation cover of these territories.
YU. V. SAVINYKH, T. O. PEREMITINA, S. P. ZADOROZHNYKH
Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia
Keywords: diesel fuel, petroleum, plants, pigments, satellite data, vegetation indices
Pages: 224-229
The dependence of vegetation indices NDVI (Normalized Difference Vegetation Index) and EVI (Enhanced Vegetation Index) on the content of pigments in plants was studied at three sites with environmental disturbance: at the territory of diesel fuel spill, in the region of natural oil occurrence, and at a post-fire site. The studies have shown that the stability of plant species against pollution with petroleum products increases in the sequence: sedge < cereals < field horsetail < willow < moss. Determination of interrelation between remotely measured optical characteristics of the vegetation cover and the concentrations of pigments revealed a direct dependence of NDVI and EVI values on the concentrations of pigments in field horsetail and cereals, and inverse dependence for willow, moss, and sedge. In the region of natural oil occurrence under the conditions of pollution with oil, a substantial decrease in total chlorophyll content is observed for wild strawberry, artemisia, and thyme in comparison with the reference conditions. A decreased content of chlorophylls and carotenoids was detected at the post-fire site in padus, and an increased pigment content in dwarf elder, which provides evidence of the higher stability of dwarf elder to the action of high temperatures. The vegetation indices at the post-fire site are substantially lower than at the background (intact) site.