无碱表面活性剂体系特性研究
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摘要
目前,三元复合驱虽已进入工业化应用阶段,但三元复合驱所带来的采出液处理困难以及对地层造成损害等问题很大程度上限制了三元复合驱工业化推广。相比之下,二元复合驱配方中未使用碱,矿场可操作性更强,因而受到油田的欢迎。但是由于不用任何碱,原油中石油酸类活性物质不能得到充分利用,所以研发具有更高表面活性的新型表面活性剂和无碱二元复合驱配方势在必行。针对此问题本文主要对无碱驱油体系表面活性剂磺基、羧基甜菜碱界面特性进行了系统评价,并对优选出的表面活性剂进行了吸附实验、稳定性实验及驱油物理模拟实验。
研究结果表明:磺基甜菜碱表活剂SB4与SB1复配,在SP二元体系中界面张力只有0.05%,0.025%两个浓度点达到超低,其余点界面张力只有10~(-2)mN/m,SB4与11#复配的协同效应要好于SB4与SB1复配,能与大庆原油在加入聚合物的情况下形成超低界面张力(＜10~(-3)mN/m数量级);SB4与11#按1:1比例配制,0.2%浓度的样品稳定性非常好,在测试150天中界面张力数据均在(2～4.5)×10~(-3)mN/m之间;磺基羟基甜菜碱表活剂B与13#复配测大庆油田前六个厂的界面张力,均摸索出适合各个厂的复配比例,使界面张力达到了10~(-3)mN/m超低界面张力;在S、SP、ASP体系中,磺基羟基甜菜碱B的吸附量均低于羧基甜菜碱11#,羧基甜菜碱11#的吸附量均低于重烷基苯磺酸盐;综合所有均质和非均质岩心的实验结果并通过分析,我们认为采用磺基羟基甜菜碱B活性剂的无碱二元驱油体系与采用Ss的弱碱(Na_2CO_3)三元体系和采用Sy的强碱(NaOH)三元体系驱油效果基本相当。
Currently, the ASP flooding has entered the industrialization stage, but ASP flooding bringing about the difficulty in processing the produced liquid and formation damage caused to a large extent limitation to the populating ASP industrialization. By contrast, the binary compound flooding system without alkali is popular in the oil field with strong application on the spot. But as no alkali, petroleum acid active substances can not be fully utilized, so it is imperative to research and develop a new kind surfactants and non-alkali compound formula. In this paper, it mainly does the research on systematic evaluation on interfacial properties of the carboxyl betaine surfactant and sulfosalicylic and implements physical simulation experiments with the surfactant systems through the optimization of the surfactant adsorption experiments and the stability of oil displacement experiments.
The results show in the following. The binary compound systems with the surfactants compound of SB4 and SB1 can form the ultralow interfacial tension at two concentration of surfactant, 0.05%, 0.025%; others only reach 10~(-2) mN/m. While the effect of the compound of SB4 and 11# is better, which can form ultralow IFT(<10~(-3)mN/m) with crude oil in Daqing, and the concentration 0.2% has better stability, between 2×10~(-3)and 4.5×10~(-3)mN/m during 150 days' trial according to the proportion 1:1 of SB4 and 11#. We also find the best proportion of B-kind sulfosalicylic surfactant and 13# forming the ultralow IFT(10~(-3)mN/m) with oil in six oil production plant of Daqing oil field. In surfactant systems, surfactant-polymer systems and alkali-surfactant-alkali systems, the absorption of sulfosalicylic surfactant is lower than that of carboxyl betaine surfactant, which is lower than that of heavy alkyl benzene sulfonate. According to the analysis of the results of experiments on the homogeneous cores and heterogeneous cores, we consider that the non-alkali binary compound flooding system with sulfosalicylic surfactant B have the same effect of flooding as the sodium hydroxide ternary alkali flooding system and the Ss weak-alkali ternary system.
研究结果表明:磺基甜菜碱表活剂SB4与SB1复配,在SP二元体系中界面张力只有0.05%,0.025%两个浓度点达到超低,其余点界面张力只有10~(-2)mN/m,SB4与11#复配的协同效应要好于SB4与SB1复配,能与大庆原油在加入聚合物的情况下形成超低界面张力(＜10~(-3)mN/m数量级);SB4与11#按1:1比例配制,0.2%浓度的样品稳定性非常好,在测试150天中界面张力数据均在(2～4.5)×10~(-3)mN/m之间;磺基羟基甜菜碱表活剂B与13#复配测大庆油田前六个厂的界面张力,均摸索出适合各个厂的复配比例,使界面张力达到了10~(-3)mN/m超低界面张力;在S、SP、ASP体系中,磺基羟基甜菜碱B的吸附量均低于羧基甜菜碱11#,羧基甜菜碱11#的吸附量均低于重烷基苯磺酸盐;综合所有均质和非均质岩心的实验结果并通过分析,我们认为采用磺基羟基甜菜碱B活性剂的无碱二元驱油体系与采用Ss的弱碱(Na_2CO_3)三元体系和采用Sy的强碱(NaOH)三元体系驱油效果基本相当。
Currently, the ASP flooding has entered the industrialization stage, but ASP flooding bringing about the difficulty in processing the produced liquid and formation damage caused to a large extent limitation to the populating ASP industrialization. By contrast, the binary compound flooding system without alkali is popular in the oil field with strong application on the spot. But as no alkali, petroleum acid active substances can not be fully utilized, so it is imperative to research and develop a new kind surfactants and non-alkali compound formula. In this paper, it mainly does the research on systematic evaluation on interfacial properties of the carboxyl betaine surfactant and sulfosalicylic and implements physical simulation experiments with the surfactant systems through the optimization of the surfactant adsorption experiments and the stability of oil displacement experiments.
The results show in the following. The binary compound systems with the surfactants compound of SB4 and SB1 can form the ultralow interfacial tension at two concentration of surfactant, 0.05%, 0.025%; others only reach 10~(-2) mN/m. While the effect of the compound of SB4 and 11# is better, which can form ultralow IFT(<10~(-3)mN/m) with crude oil in Daqing, and the concentration 0.2% has better stability, between 2×10~(-3)and 4.5×10~(-3)mN/m during 150 days' trial according to the proportion 1:1 of SB4 and 11#. We also find the best proportion of B-kind sulfosalicylic surfactant and 13# forming the ultralow IFT(10~(-3)mN/m) with oil in six oil production plant of Daqing oil field. In surfactant systems, surfactant-polymer systems and alkali-surfactant-alkali systems, the absorption of sulfosalicylic surfactant is lower than that of carboxyl betaine surfactant, which is lower than that of heavy alkyl benzene sulfonate. According to the analysis of the results of experiments on the homogeneous cores and heterogeneous cores, we consider that the non-alkali binary compound flooding system with sulfosalicylic surfactant B have the same effect of flooding as the sodium hydroxide ternary alkali flooding system and the Ss weak-alkali ternary system.
引文
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[31]黄宏度,吴一慧,吕军等.石油梭酸盐复配体系的协同效应[J].江汉石油学院学报,1994,16(2):64-67.
[32]张路,罗澜,赵濉等.油相性质对水相中混合表面活性剂协同效应的影响[J].油田化学,2000,17(3):268-271.
[33]张路,罗澜,赵濉等.表面活性剂亲水-亲油能力对动态界面张力的影响[J].物理化学学报,2001,17(1):62-65.
[34]Pouchelon A,Meunier J,Langevin D et al.Low interfacial tensions in three-phase systems obtained with oil-water surfactant mixtures[J].Chemical Physics Letters,1980,76(2):277-281.
[35]徐桂英,竺和平,袁云龙等.石油磺酸盐/部分水解聚丙烯酰胺体系界面张力的研究[J].油田化学,1989,6(4):332-336.
[36]吴文祥,张洪亮,胡靖邦等.A-S-P三元复合体系与大庆原油间界面张力等值图[J].大庆石油学院学报,1995,19(1):115-118.
[37]吴文祥,张洪亮,侯吉瑞等.A-S-P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.
[38]Chan K S,Shah D O.The molecular mechanism for achieving ultra low interfacial tension minimum in a petroleum sulfonate/oil/brine system[J].Journal of Dispersion Science and Technology,1980,1(7):55.
[39]徐桂英,刘木辛,李干佐等.影响羧酸盐驱油体系界面张力因素的研究[J].山东大学学报(自然科学版),1996,31(1):71-75.
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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,2001,4(8):1.
[4]周润才.表面活性剂/聚合物驱油的基本原理[J].国外油气田工程,1995,3:9-11.
[5]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.
[6]刘杰.驱油用无碱表面活性剂[J].油气田地面工程,2006,25(8):63.
[7]杨普华,杨承志译.化学驱提高石油采收率[M].北京:石油工业出版社,1988.
[8]夏纪鼎,倪永全.表面活性剂和洗涤剂化学与工艺学[M].北京:北京轻工业出版社,1997.
[9]张志庆,徐桂英,王芳.十二烷基甜菜碱/十二烷基硫酸钠复配体系的表面活性[J].物理化学学报,2001,17(12):1122-1125.
[10]张志庆,徐桂英,肖莉等.十二烷基甜菜碱/十二烷基硫酸钠复配体系与原油间的界面张力[[J].山东大学学报(理学版),2002,37(2):153-156.
[11]Danov K.D.,Kralchevska S.D.,Kralchevsky P.A.,et al.Mixed Solutions of Anionic and Zwitterionic Surfactant(Betaine):Surface-Tension Isotherms Adsorption,and Relaxation Kinetics[J].Langmuir,2004,20(13):5445-5453.
[12]丁慧君,田彬,赵国玺.正负离子表面活性剂与两性表面活性剂的相互作用[J].物理化学学报,1991,7(4):414.
[13]Li F.,Li G.Z.,Chen J.B.Synergism in mixed zwitterionic-anionic surfactant solutions and the aggregation numbers of the mixed micelles[J].Colloids and Surfaces A,1998,145-167.
[14]朱怀江.碱-聚合物中部分水解聚丙烯酰胺溶液性质热稳定性研究[J].油田化学,1987,4(4):284-292.
[15]王克亮.改善聚合物驱油技术研究[M].北京:石油工业出版社,1997,1-3.
[16]徐燕莉.表面活性剂的功能[M].北京:化学工业出版社,2000.
[17]张景存.三次采油[M].北京:石油工业出版社,1995,55-60.
[18]Mungan N.Role of wettability and interfacial tension in water flooding[Z].SPE705,1963.
[19]Wagner O R.Leach R O.Effect of interfacial tension on displacement efficiency[Z]. SPE1564,1966.
[20]Taber J J.Dynamic and static forces required to remove a discontinuous oil phase from porous media containing both oil and water[Z].SPE2098,1968.
[21]Foster W R.A low-tension waterflooding process[Z].SPE3803,1973.
[22]Taylor K C,Hawkins B F,Islam M R.Dynamic interfacial tension in surfactant enhanced alkaline flooding[J].The Journal of Canadian Petroleum Technology,1990,29(1):50-55.
[23]Chiwetelu C I,Hornof V,Neale G H.A dynamic model for the interaction of caustic reagents with acidic oils[J].AIChE Journal,1990,36(2):233-241.
[24]Borwankar R P,Wasan D T.Dynamic interfacial tensions in acidic crude oil/caustic systems Part Ⅰ:A chemical diffusion-kinetic model[J].AIChE Journal,1986,32(3):455-466.
[25]Borwankar R P,Wasan D T.Dynamic interfacial tensions in acidic crude oil/caustic systems Part Ⅱ:Role of dynamic effects in alkaline flooding for enhanced oil recovery[J].AIChE Journal,1986,32(3):467-476.
[26]赵宇.系列烷基苯磺酸盐纯化合物的合成及界面性能的研究(D).大连:大连理工大学,2006.
[27]Wilson P M D,Brandner C F.Aqueous surfactant solutions which exhibit ultra-low tensions at the oil-water interface[J].Journal of Colloid and Interface Science,1977,60(3):473-479.
[28]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.
[29]绳德强,杨普华,刘彦丽.碱/聚合物相互作用与碱十聚合物/原油界面张力研究[J].油田化学,1993,10(1):46-50.
[30]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.
[31]黄宏度,吴一慧,吕军等.石油梭酸盐复配体系的协同效应[J].江汉石油学院学报,1994,16(2):64-67.
[32]张路,罗澜,赵濉等.油相性质对水相中混合表面活性剂协同效应的影响[J].油田化学,2000,17(3):268-271.
[33]张路,罗澜,赵濉等.表面活性剂亲水-亲油能力对动态界面张力的影响[J].物理化学学报,2001,17(1):62-65.
[34]Pouchelon A,Meunier J,Langevin D et al.Low interfacial tensions in three-phase systems obtained with oil-water surfactant mixtures[J].Chemical Physics Letters,1980,76(2):277-281.
[35]徐桂英,竺和平,袁云龙等.石油磺酸盐/部分水解聚丙烯酰胺体系界面张力的研究[J].油田化学,1989,6(4):332-336.
[36]吴文祥,张洪亮,胡靖邦等.A-S-P三元复合体系与大庆原油间界面张力等值图[J].大庆石油学院学报,1995,19(1):115-118.
[37]吴文祥,张洪亮,侯吉瑞等.A-S-P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.
[38]Chan K S,Shah D O.The molecular mechanism for achieving ultra low interfacial tension minimum in a petroleum sulfonate/oil/brine system[J].Journal of Dispersion Science and Technology,1980,1(7):55.
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