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Texture,composition and properties of plugs formed by carbon dioxide hydrate and wax

Petroleum Exploration and Development 2021年第6期48卷 1462-1470页

作者： SKIBA Sergey SAGIDULLIN Aleksey SHAPOVALOVA Alexandra STRELETS Larisa manakov andrey Nikolaev Institute of Inorganic Chemistry SB RASAc.Lavrentiev Ave.3Novosibirsk 630090Russia Novosibirsk State University Pirogova Str.2Novosibirsk 630090Russia Institute of Petroleum Chemistry SB RAS Akademichesky ave.4Tomsk 634021Russia

Gas hydrates and wax are the major flow assurance problems for the transportation of produced hydrocarbons through ***,in most research works both these two problems are studied *** simultaneous precipitation or deposition of these compounds in pipelines can lead to different mitigation/prevention strategies,the investi-gations in which both these problems are considered simultaneously appeared only *** is no information in the literature on the texture/composition and features of decomposition process of mixed wax/hydrate *** the same time,this information could be useful to understand how to treat the problem of formation of these *** this work,three wax/gas hydrate plugs were collected at quasi-static conditions from a water-in-oil emulsion to study their texture,composition and the features of decomposition *** X-ray diffraction and IR(infrared spectroscopy)analyses showed that the plugs consisted of wax and gas *** and DSC(Differential Scanning Calorimetry)experiments showed that the main part of gas hydrate in the plugs at the ambient pressure started to decompose at about 268 *** temperature was higher than the equilibrium temperature of carbon dioxide hydrate at this pressure,indicating that the gas hydrate in the plugs could be effectively preserved at temperatures below the ice melting point(273.2 K).It was found through observation of the hydrate decomposition process in the plugs under the microscope that the gas in the samples released in small bubbles,while the hydrate particles were not visible at this magnification,indicating that the hydrate was indeed highly dispersed in the samples.A residual wax was jelly-like after decomposition of hydrate in all the *** experiments showed that the plugs residues after decomposition of the hydrates had higher yield points and viscosities than the initial waxy crude oil origi-nally used for the experiments.

关键词： carbon dioxide hydrate hydrate/wax plug plug texture hydrate decomposition

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二氧化碳水合物-石蜡段塞的结构、组分及特性

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石油勘探与开发 2021年第6期48卷 1269-1275页

作者： SKIBA Sergey SAGIDULLIN Aleksey SHAPOVALOVA Alexandra STRELETS Larisa manakov andrey 俄罗斯科学院西伯利亚分院尼克拉艾无机化学研究所新西伯利亚630090俄罗斯新西伯利亚大学新西伯利亚630090俄罗斯俄罗斯科学院西伯利亚分院石油化学研究所托木斯克634021俄罗斯

为了研究石蜡和水合物混合生成段塞的结构、组成和分解特征,在准静态条件下,从油包水乳状液中获得了3块二氧化碳水合物与石蜡形成的段塞。粉末X射线衍射和红外光谱分析表明实验室制备的段塞中含有蜡和气体水合物;热容量法和差示扫描量... 详细信息

为了研究石蜡和水合物混合生成段塞的结构、组成和分解特征,在准静态条件下,从油包水乳状液中获得了3块二氧化碳水合物与石蜡形成的段塞。粉末X射线衍射和红外光谱分析表明实验室制备的段塞中含有蜡和气体水合物;热容量法和差示扫描量热法实验表明,在环境压力下段塞中气体水合物的主要成分在268 K左右开始分解,该温度比相同压力下二氧化碳水合物的平衡温度高,说明在低于冰熔点温度(273.2 K)下,段塞中的气体水合物可以有效地自我保护;通过显微观察段塞中水合物的分解过程发现,样品中的气体以小气泡的形式析出,而水合物颗粒本身在此放大倍数下不可见,表明水合物在段塞中高度分散,段塞分解后石蜡以胶状出现;流变性测量实验发现,与含蜡原油相比,段塞分解后的残余物具有较高的动切力和黏度。

关键词：二氧化碳水合物水合物-石蜡段塞段塞结构水合物分解

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Growth rate of CO_(2) hydrate film on water-oil and water-gaseous CO_(2) interface

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Chinese Journal of Chemical Engineering 2023年第4期56卷 266-272页

作者： Tatyana P.Adamova Sergey S.Skiba andrey Yu.manakov Sergey Y.Misyura Kutateladze Institute of Thermophysics SB RAS Lavrentiev Ave.1Novosibirsk 630090Russian Federation

It is known that injection of carbon dioxide into the petroleum reservoir(CO_(2) flooding) is one of the effective methods for enhanced oil recovery. CO_(2) flooding may be complicated by formation of CO_(2) hydrate plugs. It makes topical investigation of CO_(2) hydrate formation in the system gaseous CO_(2)-oil-water. In this work, the growth rates of carbon dioxide hydrate films at the water-oil as well as the water-gas interface are studied in the pressure range of 2.30-3.04 MPa and at temperatures between -5.4 and 5.0℃. It is found that the growth rate for the water-oil interface is 3.5 times lower than that for the water-gas interface with carbon dioxide. It is hypothesised that the observed decrease in the growth rate is related to the mechanical resistance of the oil components adsorbed on the interface to the growth of the hydrate film. The growth rate of the film has been shown to depend on the experimental procedure,most likely due to the different initial concentrations of carbon dioxide in the aqueous solutions.

关键词： Gas hydrate Oil Carbon dioxide Growth rate Hydrate film

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Dissociation behavior of “dry water” C_3H_8 hydrate below ice point:Effect of phase state of unreacted residual water on a mechanism of gas hydrates dissociation

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Journal of Energy Chemistry 2015年第3期24卷 309-314页

作者： andrey O Drachuk Vladimir P Melnikov Nadezhda S Molokitina Anatoliy N Nesterov Lev S Podenko Aleksey M Reshetnikov andrey Yu manakov Institute of Earth Cryosphere SB RAS625026Malygin str.86TyumenRussian Federation Tyumen State Oil and Gas University 625000Volodarsky str.38TyumenRussian Federation Nikolaev Institute of Inorganic Chemistry SB RAS630090Lavrentiev av.3NovosibirskRussian Federation

The results on a dissociation behavior of propane hydrates prepared from ＂dry water＂ and contained unreacted residual water in the form of ice inclusions or supercooled liquid water（water solution of gas） were presented for temperatures below 273 *** temperature ramping or pressure release method was used for the dissociation of propane hydrate *** was found that the mechanism of gas hydrate dissociation at temperatures below 273 K depended on the phase state of unreacted water in the hydrate *** hydrates dissociated into ice and gas if the ice inclusions were in the hydrate *** samples of propane hydrates with inclusions of unreacted supercooled water only（without ice inclusions） dissociated into supercooled water and gas below the pressure of the supercooled water-hydrate-gas metastable equilibrium.

关键词： gas hydrates dry water supercooled liquid water ice hydrate dissociation

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Decomposition of carbon dioxide hydrate in the samples of natural coal with different degrees of metamorphism

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Chinese Journal of Chemical Engineering 2020年第2期28卷 492-501页

作者： Vyacheslav G. Smirnov Valeriy V. Dyrdin andrey Yu. manakov Zinfer R. Ismagilov Kuzbass State Technical University Vesennaya str.28Kemerovo 650000Russian Federation Nikolaev Institute of Inorganic Chemistry SB RAS Ac.Lavrentiev ave.3Novosibirsk 630090Russian Federation Novosibirsk State University Pirogov Str.2Novosibirsk 630090Russian Federation Institute of Coal Chemistry and Material Science SB RAS Sovetsky ave.18Kemerovo 650000Russian Federation

Methane and carbon dioxide hydrates are one of the possible forms in which these gases exist in natural coal(for more detailed discussion see Refs [1,2]). In this work, the decomposition of carbon dioxide hydrate in five samples of natural coal differing from each other in metamorphism degree was investigated experimentally. Carbon dioxide hydrate dispersed in coals was synthesized from water adsorbed in these coals. During a linear temperature rise in an autoclave with the coal + hydrate sample the hydrate decomposition manifests itself as a step of increase in gas pressure, accompanied by a decrease/stabilization of the temperature of coal sample. The dependencies of the amount of hydrate formed on initial coal humidity and on gas pressure during hydrate formation were studied. It was demonstrated that each coal sample is characterized by its own humidity threshold below which hydrate formation in natural coal is impossible. With an increase in gas pressure, the amount of water transformed into hydrate increases. For the studied coal samples, the decomposition of carbon dioxide hydrates proceeds within a definite temperature and pressure range, and this range is close to the curve of phase equilibrium for bulk hydrate.

关键词： Gas hydrate Carbon dioxide Coal Coal rank Phase transformation Coal bed gas

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Synergistic effect of combination of surfactant and oxide powder on enhancement of gas hydrates nucleation

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Journal of Energy Chemistry 2017年第4期26卷 808-814页

作者： Anatoliy N.Nesterov Aleksey M.Reshetnikov andrey Yu.manakov Tatyana P.Adamova Institute of Earth’s Cryosphere SB RAS Malygina str.86Tyumen 625026Russian Federation Tyumen State University Volodarskogo Str.6Tyumen 625003Russian Federation Tyumen Industrial University Volodarskogo Str.38Tyumen 625000Russian Federation Nikolaev Institute of Inorganic Chemistry SB RAS Lavrentieva ave.3Novosibirsk 630090Russian Federation Novosibirsk State University Pirogova Str.2Novosibirsk 630090Russian Federation

In the present work we studied the induction periods of hydrate formation of natural gas in pure water, aqueous solutions of surfactants, and in the presence of surfactant together with aluminum oxide nanopowder, the activity of which as hydrate formation inducer was studied previously. Sodium dodecyl sulfate（SDS） or neonol AF-9-12 were used as the surfactants. It was demonstrated that the addition of either surfactants or aluminum oxide powder under our experimental conditions causes a decrease in the induction period of hydrate formation from;05 min for pure water to 30–35 min for water with additives. In the case of the simultaneous presence of surfactants and aluminum oxide powder in the system, induction period decreased to;0 min. So, the synergistic effect of the combination of surfactant and oxide powder on gas hydrate nucleation was demonstrated. Possible reasons of this effect have been discussed.

关键词： Gas hydrate Hydrate formation Nucleation Induction period Surfactant Nanopowder

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Nucleation of methane hydrate and ice in emulsions of water in crude oils and decane under non-isothermal conditions

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Chinese Journal of Chemical Engineering 2019年第3期27卷 668-676页

作者： andrey S. Stoporev Lidiya I. Svarovskaya Larisa A. Strelets Lubov’ K. Altunina Galina V. Villevald Tamara D. Karpova Tatyana V. Rodionova andrey Yu. manakov Nikolaev Institute of Inorganic Chemistry SB RAS Novosibirsk State University Institute of Petroleum Chemistry

Achievable supercooling for the formation of methane hydrate from water emulsions was studied in seven different crude oils and in decane. The experiments were performed under constant rate cooling from + 20 to-15 °C and a pressure of methane of 12 MPa. It was demonstrated that the shapes and positions of the resulting survival curves depend on the density, viscosity and dispersive power of oil samples used in the experiments, as well as on the degree of oil oxidation. In addition, results of the experiments on ice freezing under the same emulsions are presented. The results obtained in the work allowed us to discuss the possibility and features of primary and secondary nucleation of the hydrate and ice in the systems under consideration.

关键词： Methane hydrate Crude oil Oil dispersive system Nucleation

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