磺基甜菜碱Gemini表面活性剂的合成与应用性能
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摘要
为了改善储层的非均质性差异,有效提高碳酸盐储层的酸化解堵效果,以长链烷基二甲基叔胺、3-氯-2-羟基丙烷磺酸钠和1,4-二溴丁烷为原料,通过两步反应合成了一系列磺基甜菜碱双子表面活性剂(2C_n-SGS,其中n为疏水链中碳原子数,n=12,14,16,18)自转向酸主剂。以2C_(16)-SGS为例,采用FTIR对中间产物(C_(16)-SGS)及2C_(16)-SGS的结构进行表征。通过表面张力法测定2C_n-SGS的表面活性,结果表明,2C_n-SGS具有良好的表面活性,随着疏水链的增长,2C_n-SGS的CMC和表面张力均减小,且胶束化能力增强。可用于黏弹性表面活性剂自转向酸酸化技术,具有良好的转向分流能力,优选配方为4%2C_(16)-SGS+20%盐酸+20%Ca~(2+),而且高黏胶束遇煤油等烃类能够自动破胶降黏,易返排对地层无伤害。
In order to change the heterogeneity difference, improve the acidizing and unplugging effect of carbonate reservoir, a series of sulfobetaine Gemini surfactants(2C_n-SGS, where n is the number of carbon atoms in the hydrophobic chain, n=12, 14, 16, 18) were synthesized by a two-step reaction using long chain alkyl dimethyl tertiary amine, 3-chloro-2-hydroxypropane sulfonic acid sodium and 1,4-dibromobutane as raw materials. Taking 2C_(16)-SGS as an example, the structures of mid product(C_(16)-SGS)and 2C_(16)-SGS were characterized by FTIR. Surface activity of 2C_n-SGS was analyzed by surface tension method. The results show that 2C_n-SGS have good surface activity, and the CMC and surface tensions of 2C_n-SGS decrease with the increase of hydrophobic chain, and the micellization ability is enhanced. It can be used in viscoelastic surfactant self-steering acidification technology, with good steering and shunting ability. The optimal formula is 4% 2C_(16)-SGS+20% hydrochloric acid + 20% Ca~(2+). The high viscosity gel of acidizing system is easy to break when mixing with hydrocarbons such as kerosene. It is easy to backflow and has no damage to the formation.
In order to change the heterogeneity difference, improve the acidizing and unplugging effect of carbonate reservoir, a series of sulfobetaine Gemini surfactants(2C_n-SGS, where n is the number of carbon atoms in the hydrophobic chain, n=12, 14, 16, 18) were synthesized by a two-step reaction using long chain alkyl dimethyl tertiary amine, 3-chloro-2-hydroxypropane sulfonic acid sodium and 1,4-dibromobutane as raw materials. Taking 2C_(16)-SGS as an example, the structures of mid product(C_(16)-SGS)and 2C_(16)-SGS were characterized by FTIR. Surface activity of 2C_n-SGS was analyzed by surface tension method. The results show that 2C_n-SGS have good surface activity, and the CMC and surface tensions of 2C_n-SGS decrease with the increase of hydrophobic chain, and the micellization ability is enhanced. It can be used in viscoelastic surfactant self-steering acidification technology, with good steering and shunting ability. The optimal formula is 4% 2C_(16)-SGS+20% hydrochloric acid + 20% Ca~(2+). The high viscosity gel of acidizing system is easy to break when mixing with hydrocarbons such as kerosene. It is easy to backflow and has no damage to the formation.
引文
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[9]高尚,符扬洋,孟祥海,等.新型砂岩自转向酸体系的研究与应用[J].钻井液与完井液, 2017, 34(2):121-125.GAO Shang, FU Yangyang, MENG Xianghai, et al. Study and application of a new self-diverting acid for use in sandstone fracturing[J]. Drilling Fluid&Completion Fluid, 2017, 34(2):121-125.
[10]刘雪峰,吴向阳,朱杰,等.黏弹性表面活性剂自转向酸增黏转向的判别标准[J].特种油气藏, 2018, 25(1):150-154.LIU Xuefeng, WU Xiangyang, ZHU Jie, et al. Viscosifying steering determination criterion of viscoelastic surfactant self-steering acid[J].Special Oil and Gas Reservoirs, 2018, 25(1):150-154.
[11] NASR-EL-DIN H A, AL-GHAMDI A W H, AL-QAHTANI A A, et al. Impact of acid additives on the rheological properties of a viscoelastic surfactant and their influence on field application[J]. SPE Journal, 2008, 13(1):35-47.
[12] ZHAO Z Y, LüG C. Visco-elastic properties of VES diverting acid for carbonate reservoirs[J]. Chinese Journal of Chemical Engineering,2010, 18(3):511-514.
[13]吴天江.一种季铵盐双子表面活性剂自转向酸的变黏特性评价[J].石油化工应用, 2011, 30(1):13-16.WU Tianjiang. Evaluation of the viscosity of a quaternary ammonium Gemini surfactant self-steering acid[J]. Petrochemical Industry Application, 2011, 30(1):13-16.
[14]陈馥,罗娇,吴柯颖.自转向酸稠化剂两性双子表面活性剂的合成及酸岩反应动力学研究[J].应用化工, 2015(5):799-803.CHEN Yu, LUO Jiao, WU Keying. Synthesis of amphoteric Gemini surfactant from self-turning acid thickener and kinetics of acid rock reaction[J]. Applied Chemical Industry, 2015(5):799-803.
[15]王军,陈玉菲,李妮妮,等.糖基双子阳离子表面活性剂的表面活性[J].日用化学工业, 2015(10):541-545.WANG Jun, CHEN Yufei, LI Nini, et al. Surface activity of glycosyl Gemini cationic surfactants[J]. China Surfactant Detergent&Cosemetics, 2015(10):541-545.
[16] LI Pengfei, CHEN Qihu, ZHAO Jiale, et al. Synthesis and properties of x-type alkyl sulfonate Gemini surfactants derived from cyanuric chloride[J]. Journal of Surfactants&Detergents, 2012, 15(4):449-456.
[17]周龙.羧酸盐型双子表面活性剂的设计、合成及性能研究[D].大连:辽宁师范大学, 2012.ZHOU Long. Design, synthesis and properties of carboxylate gemini surfactants[D]. Dalian:Liaoning Normal University, 2012.
[18]王瑞娟,李刚森,闫海涛,等.磺酸盐型双子表面活性剂的合成及性能[J].精细化工, 2017, 34(2):166-171.WANG Ruijuan, LI Gangsen, YAN Haitao, et al. Synthesis and properties of sulfonate Gemini surfactants[J]. Fine Chemicals, 2017, 34(2):166-171.
[19]曲占庆,曲冠政,齐宁,等.黏弹性表面活性剂自转向酸液体系研究进展[J].油气地质与采收率, 2011, 18(5):89-92.QU Zhanqing, QU Guanzheng, QI Ning, et al. Research progress of viscoelastic surfactant self-turning acid system[J]. Petroleum Geology and Recovery Efficiency, 2011, 18(5):89-92.
[20]乐宏,刘飞,薛衡,等.四川盆地下寒武统龙王庙组气藏转向酸酸化模拟及其应用[J].天然气工业, 2017, 37(10):46-53.YUE Hong, LIU Fei, XUE Heng, et al. Numerical simulation and field application of diverting acid acidizing in the Lower Cambrian Longwangmiao Fm gas reservoirs in the Sichuan Basin[J]. Natural Gas Industry, 2017, 37(10):46-53.
[21] BERNHARD L, CHRIS F, MARK B, et al. Diversion and cleanup studies of viscoelastic surfactant-based self-diverting acid[J]. SPE Production&Operations, 2007, 22(1):121-127.
[22]曲占庆,曲冠政,齐宁,等.甜菜碱类自转向酸酸化技术室内实验研究[J].特种油气藏, 2012, 19(5):120-123.QU Zhanqing, QU Guanzheng, QI Ning, et al. Laboratory experimental study of betaine self-turning acidification technology[J]. Specialty Oil&Gas Reservoirs, 2012, 19(5):120-123.
[2]刘平礼,李凤,兰夕堂,等.海上砂岩储层新型自转向酸液体系研究[J].钻采工艺, 2017, 40(3):90-93.LIU Pingli, LI Feng, LAN Xitang, et al. Development of new selfdiverting acid for sandstone reservoirs offshore[J]. Drilling&Production Technology, 2017, 40(3):90-93.
[3]王宗圣,冯浦涌,崔波,等.甜菜碱活性剂用作碳酸盐岩酸液转向剂研究[J].科学技术与工程, 2015, 15(15):147-153.WANG Zongsheng, FENG Puyong, CUI Bo, et al. Study on betaine active agent used as carbonate acid turning agent[J]. Science Technology and Engineering, 2015, 15(15):147-153.
[4]李亚林,敬显武,鲁红升.碳酸盐岩气藏清洁转向酸的研究[J].精细石油化工进展, 2015, 16(4):9-11.LI Yalin, JING Xianwu, LU Hongsheng. The study of clear diverting acid for tight carbonate reservoir[J]. Advances in Fine Petrochemicals,2015, 16(4):9-11.
[5]仲岩磊.黏弹性表面活性自转向酸及应用技术研究[D].青岛:中国石油大学(华东), 2014.ZHONG Yanlei. Research on viscoelastic surface active self-steering acid and application technology[D]. Qingdao:China University of Petroleum(East China), 2014.
[6]陈亚楠.凝灰岩储层耐高温转向酸液体系的研究[D].西安:西安石油大学, 2018.CHEN Yanan. Research and evaluation of heat resistant self-diverting acid applicable to tuff reservoir[D]. Xi’an:Xi’an Shiyou University,2018.
[7]李永寿.酸基黏弹性液体体系研究及应用[D].成都:成都理工大学, 2011.LI Yongshou. Research and application of acid-based viscoelastic liquid system[D]. Chengdu:Chengdu University of Technology, 2011.
[8]李侠清,张弛,张贵才,等.黏弹性表面活性剂在油田中的应用[J].日用化学工业, 2014, 44(9):521-524, 538.LI Xiaqing, ZHANG Chi, ZHANG Guicai, et al. Application of viscoelastic surfactants in oilfields[J]. China Surfactant Detergent&Cosemetics, 2014, 44(9):521-524, 538.
[9]高尚,符扬洋,孟祥海,等.新型砂岩自转向酸体系的研究与应用[J].钻井液与完井液, 2017, 34(2):121-125.GAO Shang, FU Yangyang, MENG Xianghai, et al. Study and application of a new self-diverting acid for use in sandstone fracturing[J]. Drilling Fluid&Completion Fluid, 2017, 34(2):121-125.
[10]刘雪峰,吴向阳,朱杰,等.黏弹性表面活性剂自转向酸增黏转向的判别标准[J].特种油气藏, 2018, 25(1):150-154.LIU Xuefeng, WU Xiangyang, ZHU Jie, et al. Viscosifying steering determination criterion of viscoelastic surfactant self-steering acid[J].Special Oil and Gas Reservoirs, 2018, 25(1):150-154.
[11] NASR-EL-DIN H A, AL-GHAMDI A W H, AL-QAHTANI A A, et al. Impact of acid additives on the rheological properties of a viscoelastic surfactant and their influence on field application[J]. SPE Journal, 2008, 13(1):35-47.
[12] ZHAO Z Y, LüG C. Visco-elastic properties of VES diverting acid for carbonate reservoirs[J]. Chinese Journal of Chemical Engineering,2010, 18(3):511-514.
[13]吴天江.一种季铵盐双子表面活性剂自转向酸的变黏特性评价[J].石油化工应用, 2011, 30(1):13-16.WU Tianjiang. Evaluation of the viscosity of a quaternary ammonium Gemini surfactant self-steering acid[J]. Petrochemical Industry Application, 2011, 30(1):13-16.
[14]陈馥,罗娇,吴柯颖.自转向酸稠化剂两性双子表面活性剂的合成及酸岩反应动力学研究[J].应用化工, 2015(5):799-803.CHEN Yu, LUO Jiao, WU Keying. Synthesis of amphoteric Gemini surfactant from self-turning acid thickener and kinetics of acid rock reaction[J]. Applied Chemical Industry, 2015(5):799-803.
[15]王军,陈玉菲,李妮妮,等.糖基双子阳离子表面活性剂的表面活性[J].日用化学工业, 2015(10):541-545.WANG Jun, CHEN Yufei, LI Nini, et al. Surface activity of glycosyl Gemini cationic surfactants[J]. China Surfactant Detergent&Cosemetics, 2015(10):541-545.
[16] LI Pengfei, CHEN Qihu, ZHAO Jiale, et al. Synthesis and properties of x-type alkyl sulfonate Gemini surfactants derived from cyanuric chloride[J]. Journal of Surfactants&Detergents, 2012, 15(4):449-456.
[17]周龙.羧酸盐型双子表面活性剂的设计、合成及性能研究[D].大连:辽宁师范大学, 2012.ZHOU Long. Design, synthesis and properties of carboxylate gemini surfactants[D]. Dalian:Liaoning Normal University, 2012.
[18]王瑞娟,李刚森,闫海涛,等.磺酸盐型双子表面活性剂的合成及性能[J].精细化工, 2017, 34(2):166-171.WANG Ruijuan, LI Gangsen, YAN Haitao, et al. Synthesis and properties of sulfonate Gemini surfactants[J]. Fine Chemicals, 2017, 34(2):166-171.
[19]曲占庆,曲冠政,齐宁,等.黏弹性表面活性剂自转向酸液体系研究进展[J].油气地质与采收率, 2011, 18(5):89-92.QU Zhanqing, QU Guanzheng, QI Ning, et al. Research progress of viscoelastic surfactant self-turning acid system[J]. Petroleum Geology and Recovery Efficiency, 2011, 18(5):89-92.
[20]乐宏,刘飞,薛衡,等.四川盆地下寒武统龙王庙组气藏转向酸酸化模拟及其应用[J].天然气工业, 2017, 37(10):46-53.YUE Hong, LIU Fei, XUE Heng, et al. Numerical simulation and field application of diverting acid acidizing in the Lower Cambrian Longwangmiao Fm gas reservoirs in the Sichuan Basin[J]. Natural Gas Industry, 2017, 37(10):46-53.
[21] BERNHARD L, CHRIS F, MARK B, et al. Diversion and cleanup studies of viscoelastic surfactant-based self-diverting acid[J]. SPE Production&Operations, 2007, 22(1):121-127.
[22]曲占庆,曲冠政,齐宁,等.甜菜碱类自转向酸酸化技术室内实验研究[J].特种油气藏, 2012, 19(5):120-123.QU Zhanqing, QU Guanzheng, QI Ning, et al. Laboratory experimental study of betaine self-turning acidification technology[J]. Specialty Oil&Gas Reservoirs, 2012, 19(5):120-123.
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