新型无碱表面活性剂体系界面特性研究
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摘要
表面活性剂—聚合物二元复合驱(SP复合驱)由于能够发挥表面活性剂和聚合物各自的最大优点,成为复合驱的发展方向之一。在SP复合驱中,获得无碱条件下仍能与大庆原油形成10-3mN/m超低界面张力的稳定的表面活性剂是关键。
本文主要对新型芳基烷基羧酸盐表面活性剂、新型磺基甜菜碱BS11表面活性剂、新型羧基甜菜碱BS13表面活性剂的界面特性进行了研究,探讨了EDTA、同系物复配、助表面活性剂对芳基烷基羧酸盐表面活性剂体系界面特性的影响;同时探讨了表面活性剂浓度、碱浓度、温度、二价离子、矿化度等对甜菜碱表面活性剂体系界面特性的影响;考察了以BS11和BS13为表面活性剂的SP二元和ASP三元复合体系在大庆油田条件下的岩心驱油效果。
研究结果表明:苯基十八酸钾与油酸钾复配体系,苯基十八酸钾、奈基十八酸钾与油酸钾复配体系在无碱条件下与大庆原油间均能形成超低界面张力(<10-3mN/m数量级);BS11和BS13表面活性剂驱油体系在无碱和弱碱条件下与大庆原油间均能形成超低界面张力,并具有耐高温、耐盐、耐二价离子的能力,且超低界面张力活性剂浓度的范围较宽;BS11及BS13无碱二元复合驱油体系和加入少量Na3PO4作为牺牲剂的二元体系与加入强碱的三元复合驱油体系具有同样的驱油效果,且复合驱采收率均在25%以上;从均质岩心出口流出的二元体系与原油间的界面张力达到10-3mN/m数量级,即在本实验条件下整个岩心长度上工作液都能达到超低界面张力。
这一研究为各油田进行表面活性剂/聚合物二元体系驱油工业化推广提供试验及应用依据。
Surfactant-polymer binary compound flooding becomes one direction of the compound flooding systems, as it can be able to exert each biggest effect of surfactant and polymer. In this flooding system, the surfactant is the key of interfacial tension stability between this non-alkali flooding system and Daqing crude oil.
This paper is mainly about the research on the interfacial property of the new kind aryl alkyl carboxylate surfactant, the new kind sulfo-betaine surfactant (BS11), the new kind carboxyl-betaine surfactant (BS13), and it also investigates that how EDTA, homologue combination and cosurfactant influence the interfacial property of aryl alkyl carboxylate surfactant, the concentration of surfactant, the concentration of alkali, temperature, bivalence ion, salinity influence the interfacial property of betaine surfactant flooding system, and the compound flooding systems which are SP and ASP contain BS11 and BS13 have an effect on cores under the condition of Daqing.
Research indicates that benzoate-18-potassium and potassium oleic acid combination solution, benzoate-18-potassium, naphthyl-18-potassium and potassium oleic acid combination solution all can form ultra low interfacial intension (<10-3) with Daqing crude oil under the condition of non-alkali. BS11 and BS13 flooding system not only do that but also can be thermostable, salt-resisting, divalent ion-resisting, and they also have a broad concentration range of surfactant to form ultra low interfacial intension. Adding a little sodium phosphate as sacrifice agent to the BS11 and BS13 non-alkali flooding systems, they will have the same flooding effect as the ternary compound flooding adding strong alkali which the recovery ratio all can reach above 25 percentages. The exudation from cores which is the binary system fluids can form ultra low interfacial intension (<10-3) with Daqing crude oil. So it is that the working fluid can form ultra low interfacial intension with Daqing crude oil in the whole length of core under the condition of the experiment.
This research can offer the experimental and practical reference for which can industrialize the surfactant and polymer binary flooding system in each oil field.
本文主要对新型芳基烷基羧酸盐表面活性剂、新型磺基甜菜碱BS11表面活性剂、新型羧基甜菜碱BS13表面活性剂的界面特性进行了研究,探讨了EDTA、同系物复配、助表面活性剂对芳基烷基羧酸盐表面活性剂体系界面特性的影响;同时探讨了表面活性剂浓度、碱浓度、温度、二价离子、矿化度等对甜菜碱表面活性剂体系界面特性的影响;考察了以BS11和BS13为表面活性剂的SP二元和ASP三元复合体系在大庆油田条件下的岩心驱油效果。
研究结果表明:苯基十八酸钾与油酸钾复配体系,苯基十八酸钾、奈基十八酸钾与油酸钾复配体系在无碱条件下与大庆原油间均能形成超低界面张力(<10-3mN/m数量级);BS11和BS13表面活性剂驱油体系在无碱和弱碱条件下与大庆原油间均能形成超低界面张力,并具有耐高温、耐盐、耐二价离子的能力,且超低界面张力活性剂浓度的范围较宽;BS11及BS13无碱二元复合驱油体系和加入少量Na3PO4作为牺牲剂的二元体系与加入强碱的三元复合驱油体系具有同样的驱油效果,且复合驱采收率均在25%以上;从均质岩心出口流出的二元体系与原油间的界面张力达到10-3mN/m数量级,即在本实验条件下整个岩心长度上工作液都能达到超低界面张力。
这一研究为各油田进行表面活性剂/聚合物二元体系驱油工业化推广提供试验及应用依据。
Surfactant-polymer binary compound flooding becomes one direction of the compound flooding systems, as it can be able to exert each biggest effect of surfactant and polymer. In this flooding system, the surfactant is the key of interfacial tension stability between this non-alkali flooding system and Daqing crude oil.
This paper is mainly about the research on the interfacial property of the new kind aryl alkyl carboxylate surfactant, the new kind sulfo-betaine surfactant (BS11), the new kind carboxyl-betaine surfactant (BS13), and it also investigates that how EDTA, homologue combination and cosurfactant influence the interfacial property of aryl alkyl carboxylate surfactant, the concentration of surfactant, the concentration of alkali, temperature, bivalence ion, salinity influence the interfacial property of betaine surfactant flooding system, and the compound flooding systems which are SP and ASP contain BS11 and BS13 have an effect on cores under the condition of Daqing.
Research indicates that benzoate-18-potassium and potassium oleic acid combination solution, benzoate-18-potassium, naphthyl-18-potassium and potassium oleic acid combination solution all can form ultra low interfacial intension (<10-3) with Daqing crude oil under the condition of non-alkali. BS11 and BS13 flooding system not only do that but also can be thermostable, salt-resisting, divalent ion-resisting, and they also have a broad concentration range of surfactant to form ultra low interfacial intension. Adding a little sodium phosphate as sacrifice agent to the BS11 and BS13 non-alkali flooding systems, they will have the same flooding effect as the ternary compound flooding adding strong alkali which the recovery ratio all can reach above 25 percentages. The exudation from cores which is the binary system fluids can form ultra low interfacial intension (<10-3) with Daqing crude oil. So it is that the working fluid can form ultra low interfacial intension with Daqing crude oil in the whole length of core under the condition of the experiment.
This research can offer the experimental and practical reference for which can industrialize the surfactant and polymer binary flooding system in each oil field.
引文
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[2] Clark S R,Pitts M J.Design and application of an alkaline-surfac-rant-polymer recovery system to the west Kiehl Field[Z].SPE17538,1988.
[3]王德民.发展三次采油新理论新技术,确保大庆油田持续稳定发展(下)[J].大庆石油地质与开发,2001,(8):1.
[4]张景存.三次采油[M].北京:石油工业出版社,1995,55～60.
[5]吴文祥,张洪亮,侯吉瑞,等.ASP三元复合体系/大庆原油间的动态界面张力特性[J].大庆石油学院学报,1995,19(1):119～122.
[6]张国印,伍晓林,宋林,等.三次采油用烷基苯磺酸盐类表面活性剂研究[J].大庆石油地质与开发,2001,2(2):26～28.
[7]罗跃国.内油田应用表面活性剂的现状与展望[J].精细石油化工,1992,34(5):1～5.
[8]黄宏度.驱油用石油羧酸盐的研制[J].油田化学,1991,8(3):235～239.
[9] Hongdu Huang,Youzhen Yang,et al.Preparation of Petroleum Carboxylate for TertiaryOil Recovery[R].Proceedings of Fouth Asian Chemical Congres,Beijin,1991,158.
[10]康万利,吴文祥,宋文玲,等.石油羧酸盐及其复配体系/大庆原油间的界面张力[J].大庆石油学院学报,1997,19(1):123～127.
[11] Li Ganzuo,Lin Yuan,Xu Guiying.Enhanced oil recovery using natural sodiumcarboxylate surfactant systems for the typical midcontinent crude oil[R].In Proceedings of34th IUPAC Congress.Beijing,1993,867.
[12]李干佐,徐桂英,毛宏志,等.开发天然羧酸盐在油田中的应用[J].日用化学工业,1998,23(5):26～30.
[13]李干佐,林元,徐桂英,等.天然混合羧酸(盐)复合驱油体系的研究[J].日用化学工业,1994,11(1):61～65.
[14]伍晓林,陈坚,伦世仪.生物表面活性剂在提高原油采收率方面的应用[J].生物学杂志,2000(6):25～27.
[15]新疆石油管理局.三元复合驱注入、采出及集输处理工艺技术研究[J].“八五”国家重点科技攻关专题成果报告.1996.2～6.
[16]崔正刚,张天林,邹文华.重烷基苯磺酸盐的合成及其在提高石油采收率中的应用研究[J].表面活性剂/洗涤剂技术与经济进展,2002,25(2):95.
[17]朱友益,沈平平.三次采油复合驱用表面活性剂合成、性能及应用〔M].北京:石油工业出版社,2002:19～68.
[18]谭中良,韩冬,杨普华.孪连表面活性剂的性质和三次采油中应用前景[J].油田化学,2003,20(2):187～191.
[19] ShawJE,StaPPPR.Synthesis of carbonxylate used in EOR[J].J.Colloid Interfaee Sei..1995,107(l):120～131.
[20]李干佐,沈强,郑立强.新型驱油用表面活性剂天然混合羧酸盐[J].油田化学,1999,19(l):57～60.
[21]王业飞,赵福麟.醚羧酸盐及其与石油磺酸盐和碱的复配研究[J].油田化学,1998,18(4):340～343.
[22]朱友益,沈平平.三次采油复合驱用表面活性剂合成、性能及应用[M〕.北京:石油工业出版社,2002:183～207.
[23]乔卫红,张树彪,王绍辉,等.三次采油用表面活性剂的研究[J].精细化工,1999,16(增刊):71～77.
[24]郝爱军.重烷基苯磺酸盐的合成及其在三次采油中的应用研究[J].无锡:无锡轻工业学院,1997,12(5):21～26.
[25]黄宏度.从烷烃汽相氧化产物直接制备(不磺化)驱油用活性剂[J].油田化学.1987, 4(3):191～196.
[26] Berger Paul D,Berger Christie H,Hsu Iris K.Anionic surfactants based on alkene sulfonicaeid [P].US 6043391,2000—3—28.
[27]杨金华,曹亚,李惠林.高分子表面活性剂与原油形成超低界面张力的研究[J].精细化工,1999,2(3):20～26.
[28]单希林,康万利,孙洪彦,等.烷醇酰胺型表面活性剂的合成及在EOR中的应用[J].大庆石油学院学报,1999,23(1):32.
[29]唐军等,驱油型石油环烷酸二乙醇酰胺的合成[J].精细化工,2004,21(增刊):47～52.
[30] P.D.Berger,C.H.Lee.Ultra-low concentration for sandstone and limestone floods[J].SPE 7518,2002.475～478.
[31] RosenM.J.Gemini:a new generation of surfacetants[J].Chemtech,1993,23(3):30～33.
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