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共聚物增黏剂在超临界CO2中的微观结构与性能
孙文超1,2,孙宝江1,汪海阁2,孙文霞3,卓鲁斌2,曾义金4,相华5
(1.中国石油大学(华东)石油工程学院,山东青岛266580;2.中国石油集团工程技术研究院有限公司,北京 102206;3.中国石化胜利石油工程公司地质录井公司,山东东营 257100;4.中国石油化工股份有限公司石油工程技术研究院, 北京100101;5.俄罗斯国立古勃金石油天然气大学,莫斯科 119991)
摘要:
以同分异构体甲基丙烯酸甲酯(MMA)、丙烯酸乙酯(EAL)分别与1H,1H,2H,2H-全氟癸基丙烯酸酯(HFDA)共聚制备5种增黏剂,实验评价其溶解性能和增黏性能,并通过分子模拟分析CO2-共聚物体系的微观结构和分子间相互作用,探讨结构和组成对共聚物性能的影响。结果表明:P(HFDA-co-EAL)可以使超临界CO2(SC-CO2)的黏度提高34~87倍,随着EAL含量的增大,其分子间缔合程度增强,增黏性能随之提高,但溶解性能随之降低;P(HFDA-co-MMA)最高仅可以使SC-CO2的黏度提高51倍,溶解性能也较差;P(HFDA-co-MMA)主链上甲基的存在,降低了其分子链柔顺性和分子间缔合程度,使其溶解性能和增黏性能变差。
关键词:  无水压裂  页岩气  超临界CO2  增黏剂  分子模拟
DOI:10.3969/j.issn.1673-5005.2019.06.008
分类号::TE 357
文献标识码:A
基金项目:教育部长江学者和创新团队发展计划滚动支持项目(IRT_14R58);中国石油天然气集团公司工程技术重大专项(2018E-2102)
Study on microstructure and activity of copolymer thickeners in supercritical CO2
SUN Wenchao1,2, SUN Baojiang1, WANG Haige2, SUN Wenxia3, ZHUO Lubin2, ZENG Yijin4, XIANG Hua5
(1.School of Petroleum Engineering in China University of Petroleum(East China), Qingdao 266580, China;2.Engineering Technology Research Institute Limited Company of China National Petroleum Corporation, Beijing 102206, China;3.Geological Logging Company, SINOPEC Shengli Petroleum Engineering Company Limited, Dongying 257100, China;4.SINOPEC Research Institute of Petroleum Engineering, Beijing 100101, China;5.Gubkin Russian State University of Oil and Gas, Moscow 119991, Russia)
Abstract:
Five kinds of thickening agents were synthesized by copolymerizing two isomers, methyl methacrylate (MMA) and ethyl acrylate(EAL),with 1H, 1H, 2H, 2H-perfluorodecyl acrylate (HFDA). The solubility and thickening capacity of the copolymers were evaluated by experiments. And the microstructure and intermolecular interaction of CO2-copolymer systems were analyzed by molecular simulation, through which the effects of structure and composition on the performances of the copolymers were discussed. The results show that P (HFDA-co-EAL)could enhance the viscosity of SC-CO2 by 34-87 times. With the enhancement of EAL content, the degree of intermolecular association increases, leading to the stronger thickening capability but the poor solubility. P (HFDA-co-MMA) could enhance the viscosity of SC-CO2 by 51 times, and the solubility is also weaker than P (HFDA-co-EAL). The presence of methyl group in the backbone of the latter reduces its molecular chain flexibility and inter molecular association degree, resulting in the poor solubility and thickening capability.
Key words:  waterless fracturing  shale gas  supercritical CO2  thickening agents  molecular simulation
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