西伯利亚西部天然气水合物绿色抑制剂的开发与应用

A. Voloshin, N. Nifantiev, M. Egorov, R. Alimbekov, V. Dokichev
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引用次数: 3

摘要

研究了生物可降解多糖钠(NaCMC)和羧甲基纤维素、葡聚糖和阿拉伯半乳糖乙醇铵盐对天然气水合物形成过程的影响,以期寻找新的低浓度天然气水合物形成“绿色”抑制剂。在准平衡热力学实验中研究了多糖抑制天然气水合物形成的能力。采用一种具有典型石油天然气组成成分且含有78%甲烷的碳氢化合物气体混合物作为天然气水合物形成的模型介质。结果表明,在0.005、0.0065和0.008%的浓度下,葡聚糖、NaCMC和阿拉伯半乳聚糖作为热力学抑制剂的抑制性能是甲醇的170 ~ 270倍。右旋糖酐在抑制效果、降低天然气水合物形成速率和诱导时间方面均优于NaCMC和阿拉伯半乳聚糖。由于随着多糖浓度的增加,天然气水合物的形成压降增大,天然气水合物的形成速率降低,根据作用机理,所研究的多糖可归因于热力学和动力学抑制剂。结果表明,水溶性多糖的分子量对其抑菌性能有显著影响。在研究的NaCMC样品中,分子量为250,000的多糖表现出最高的抑制活性,其抑制活性是甲醇的400倍。70万质量的NaCMC对水合物的形成没有任何影响。在乙醇铵盐中,单乙醇铵盐CMC对四氢呋喃水合物的抑制效果最好。当其浓度从0.02增加到0.1%时,晶体成核和随后生长所需的诱导时间增加了10倍。当羧甲基纤维素的单乙醇铵盐转换为二乙醇铵盐和三乙醇铵盐时,抑制效率降低。结果表明,羧甲基纤维素钠和乙醇铵盐、阿拉伯半乳聚糖和葡聚糖在其基础上有望创造出新的“绿色”高效的天然气水合物形成抑制剂。本文介绍了在西伯利亚西部油田进行的“绿色”天然气水合物形成抑制剂制备形式的实验室和现场试验结果。结果表明,在500 g/m3或更低剂量下,井环空不会形成水合物塞。
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Development and Implementation of Green Inhibitors of Gas Hydrate Formation in the Fields of Western Siberia
The effect of biodegradable polysaccharides – sodium (NaCMC) and ethanolammonium salts of carboxymethylcellulose, dextran and arabinogalactan on the process of gas hydrate formation was studied in order to search for new "green" inhibitors of low-concentration gas hydrate formation. The ability of polysaccharides to inhibit gas hydrate formation was studied in a quasi-equilibrium thermodynamic experiment. A mixture of hydrocarbon gases with a composition typical of the composition of petroleum gas and containing 78% methane was used as a gas-hydrate-forming model medium. It was found that in concentrations of 0.005, 0.0065 and 0.008%, dextran, NaCMC and arabinogalactan as thermodynamic inhibitors exceed methanol by 170-270 times in inhibitory properties. Dextran is superior to NaCMC and arabinogalactan in terms of inhibition efficiency, reduction of gas hydrate formation rate and induction time. Since with an increase in the concentration of polysaccharides, the pressure drop of gas hydrate formation increases and the rate of formation of gas hydrates decreases according to the mechanism of action, the studied polysaccharides can be attributed to both thermodynamic and kinetic inhibitors. It is established that the molecular weight of water-soluble polysaccharides has a significant effect on their inhibitory properties. A polysaccharide with a molecular weight of 250,000 demonstrated the highest inhibitory activity among the studied samples of NaCMC, which is 400 times more effective than methanol. NaCMC with a mass of 700 thousand did not have any effect on the formation of hydrates. Among the ethanolammonium salts, the monoethanolammonium salt CMC showed the greatest effectiveness in inhibiting the formation of tetrahydrofuran hydrates. An increase in its concentration from 0.02 to 0.1% leads to an increase in the induction time required for the nucleation and subsequent growth of crystals by 10 times. When switching from mono - to di - and triethanolammonium salts of carboxymethylcellulose, the inhibition efficiency decreases. It is shown that sodium and ethanolammonium salts of carboxymethylcellulose, arabinogalactan and dextran are promising for creating new "green" highly effective inhibitors of gas hydrate formation on their basis. The results of laboratory and field tests of the preparative form of the "green" gas hydrate formation inhibitor at the fields of Western Siberia are presented. It was found that at dosages of 500 g/m3 or less, there is no formation of hydrate plugs in the annulus of wells.
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