二元复合驱用表面活性剂选择及作用机理研究
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摘要
针对表面活性剂／聚合物二元体系对活性剂的要求，筛选了数十种活性刑，得到了非离子表面活性剂SNS-1和改性植物羧酸盐SNHD，并对SNS-1和SNHD体系进行了系统的研究。探讨了活性剂浓度、聚合物浓度、矿化度、温度等因素对体系界面张力的影响，两种活性剂在大庆油砂上的吸附情况以及二元体系的驱油效果。
结果表明：①SNHD具有很好界面活性，在0.05％～0.3％浓度范围内均可达到10~3mN／m数量级的超低界面张力。其二元体系只有很好的抗盐性，聚合物对其二元体系影响不大。②SNS二元体系界面张力达到10~2mN／m数量级，聚合物浓度影响SNS的平衡值，但在浓度小于1000mg／L时，影响较小。在45℃～50℃范围内，随着温度的升高，SNS体系界面张力降低。③改性植物羧酸盐SNHD吸附量随着活性剂浓度的增加出现一最大值，然后下降。④测得SNS的吸附量为1.1mg／g砂。⑤SNS二元体系使岩石润湿性亲水性增强，且表面活性剂和聚合物浓度增加，润湿程度增加。⑥在化学剂成本一致的情况下，SNS-1二元体系与二元体系提高采收率幅度与二元体系相近，在聚合物浓度为1500mg／L时，化学驱采收率略高于三元复合驱。⑦SNHD二元体系与三元体系化学剂成本相当时，化学驱采收率接近。在聚合物浓度和段塞大小相同时，二元驱采收率明显高于聚合物驱。⑧给山了二元驱油主要机理：除了表面活性剂降低界面张力提高洗油效率机理和聚合物扩大波及系数机理外，还有聚合物弹性提高洗油效率机理。
此外，探讨了二元体系动态界面张力的影响因素：碱浓度、矿化度、表面活性剂浓度、聚合物浓度。提出了聚合物浓度是影响动态界面张力的主要因素之一，认为在达到最低界面张力前，动态界面张力由扩散控制。
In this paper several dozen kinds of surfactants were screened for the polymer/surfactant (PS) system. The non-ionic surfactant SNS-1 and modified plant carbonxylate SNHD are chosen and researched in detail. The effects of surfactant concentration, polymer concentration,salinity,temperature on interfacial tension were studied. Adsorption of surfactants on the Daqing oil sand and oil displacement efficiency of two PS systems are also studied.
The results show : (1)The surfactant SNHD has a very good interfacial activity. The interfacial tension could be reduced to ultra-low (10-3 mN/m) when the concentrations are varied from 0.05% to 0.3%.The surfactant has good salt tolerance. The polymer has no effect on it. (2)The interface tension of SNS-1 system can reach 10~2mN/m. The concentration of polymer influences the time to reach the balance value. But the effect is not obvious when the concentration of polymer is smaller than 1000 mg/L. When the temperature is varied from 45@ to 50@, the interfacial tension reduces with the increasing of temperature. (3)The adsorption of carboxylate on oil sand increases to maximum and then decreases with the increasing of surfactant concentration.(4)The adsorption value of SNS-1 is 1.0 mg/g oil sand. (5)After PS flooding the rock water wettability is strengthen. The degree of wettability increases with the increasing of polymer or surfactant concentration.(6)The recovery of SNS-1 system is near to ASP system when
the cost of chemistry is equal. When the concentration of polymer is 1500 mg/L, the recovery of PS flooding is higher than ASP flooding. (7)The recovery is nearly the same when the PS and ASP systems have the same cost of chemistry (8)The mechanism of PS flooding is summarized out. Besides reducing interfacial tension to increase the displacemnt efficiency and polymer increase the sweep efficiency coefficient, the elasticity of polymer also can increase the displacement efficiency.
Furthermore, the influence factors of dynamic interface tension are discussed. They are salinity, surfactant concentration, aqueous viscosity and so one. The polymer is the main factor among them. Dynamic interfacial tension is controlled by surfactant diffusion before reaching minimum interface tension.
结果表明：①SNHD具有很好界面活性，在0.05％～0.3％浓度范围内均可达到10~3mN／m数量级的超低界面张力。其二元体系只有很好的抗盐性，聚合物对其二元体系影响不大。②SNS二元体系界面张力达到10~2mN／m数量级，聚合物浓度影响SNS的平衡值，但在浓度小于1000mg／L时，影响较小。在45℃～50℃范围内，随着温度的升高，SNS体系界面张力降低。③改性植物羧酸盐SNHD吸附量随着活性剂浓度的增加出现一最大值，然后下降。④测得SNS的吸附量为1.1mg／g砂。⑤SNS二元体系使岩石润湿性亲水性增强，且表面活性剂和聚合物浓度增加，润湿程度增加。⑥在化学剂成本一致的情况下，SNS-1二元体系与二元体系提高采收率幅度与二元体系相近，在聚合物浓度为1500mg／L时，化学驱采收率略高于三元复合驱。⑦SNHD二元体系与三元体系化学剂成本相当时，化学驱采收率接近。在聚合物浓度和段塞大小相同时，二元驱采收率明显高于聚合物驱。⑧给山了二元驱油主要机理：除了表面活性剂降低界面张力提高洗油效率机理和聚合物扩大波及系数机理外，还有聚合物弹性提高洗油效率机理。
此外，探讨了二元体系动态界面张力的影响因素：碱浓度、矿化度、表面活性剂浓度、聚合物浓度。提出了聚合物浓度是影响动态界面张力的主要因素之一，认为在达到最低界面张力前，动态界面张力由扩散控制。
In this paper several dozen kinds of surfactants were screened for the polymer/surfactant (PS) system. The non-ionic surfactant SNS-1 and modified plant carbonxylate SNHD are chosen and researched in detail. The effects of surfactant concentration, polymer concentration,salinity,temperature on interfacial tension were studied. Adsorption of surfactants on the Daqing oil sand and oil displacement efficiency of two PS systems are also studied.
The results show : (1)The surfactant SNHD has a very good interfacial activity. The interfacial tension could be reduced to ultra-low (10-3 mN/m) when the concentrations are varied from 0.05% to 0.3%.The surfactant has good salt tolerance. The polymer has no effect on it. (2)The interface tension of SNS-1 system can reach 10~2mN/m. The concentration of polymer influences the time to reach the balance value. But the effect is not obvious when the concentration of polymer is smaller than 1000 mg/L. When the temperature is varied from 45@ to 50@, the interfacial tension reduces with the increasing of temperature. (3)The adsorption of carboxylate on oil sand increases to maximum and then decreases with the increasing of surfactant concentration.(4)The adsorption value of SNS-1 is 1.0 mg/g oil sand. (5)After PS flooding the rock water wettability is strengthen. The degree of wettability increases with the increasing of polymer or surfactant concentration.(6)The recovery of SNS-1 system is near to ASP system when
the cost of chemistry is equal. When the concentration of polymer is 1500 mg/L, the recovery of PS flooding is higher than ASP flooding. (7)The recovery is nearly the same when the PS and ASP systems have the same cost of chemistry (8)The mechanism of PS flooding is summarized out. Besides reducing interfacial tension to increase the displacemnt efficiency and polymer increase the sweep efficiency coefficient, the elasticity of polymer also can increase the displacement efficiency.
Furthermore, the influence factors of dynamic interface tension are discussed. They are salinity, surfactant concentration, aqueous viscosity and so one. The polymer is the main factor among them. Dynamic interfacial tension is controlled by surfactant diffusion before reaching minimum interface tension.
引文
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[2] Song ,W. et al. Alkaline/surfactant/polymer combination flooding for improving recovery of the oil with Hihj Acid Value. Paper SPE 29905 presented at the 1995 International Meeting on Petroleum Engineering, Beijing ,PR China Novl 14-17.
[3] Wang,D. et al. Analkaline/surfactant/polymer field test in a reservoir with a long-term 100％ water cut. Paper SPE 49018 presented at the 1998 SPE Annual Technical Conference and Ex2 hibition ,New Orleans ,LA ,Sept127-30.
[4] Wang,D. et al. Summary of ASP pilots inmaqing Oil Field. Paper SPE 57288 presented at the 1999 SPE Asia Pacific Improved Oil Recovery Conference, Kuala Lumpur, Malaysia, Oct. 25-28.
[5] French ,T.R. et al. Design and operation of the sho-vel-tum alkali-surfactant-polymer project, Hart's Pet. Eng. International, (Dec. 1998) 35.
[6] 程杰成，廖广志，杨振宁等．大庆油田三元复合驱矿场试验综述．大庆石油地质与开发，2001，20(2)：45～49．
[7] 张景存．三次采油[M]．北京：石油工业出版社，1995．
[8] 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．
[9] 张国印，伍晓林等．三次采油用烷基苯磺酸盐类表面活性剂研究，大庆石油地质与开发，2001，2(2)，26-28．
[10] 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(5)：1-5．
[11] 黄宏度．驱油用石油羧酸盐的研制[J]．油田化学，1991，8(3)：235-239．
[12] Hongdu Huang, Youzhen Yang, et al. Preparation of Petroleum Carboxylate for Tertiary Oil Recovery, Proceedings of Fouth Asian Chemical Congress, Beijing, 1991, P.158.
[13] 康万利，吴文祥，宋文玲，张祥云，胡靖邦．石油竣酸盐及其复配体系／大庆原油间的界面张力．大庆石油学院学报，1997，19(1)：123-127．
[14] Li Ganzuo, Lin Yuan, Xu Guiying. Enhanced oil recovery usingnatural sodium carboxylate surfactant systems for the typical midcontinent crude oil. in : Proceedings of 34th IUPAC Congress. Beijing ,993:867.
[15] 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(5)：26-30．
[16] 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．
[17] 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．生物学杂志，2000(6)：25-27．
[18] Y.P. Zhu, A. Masuyama. Preparation and properties of double-or triple-chain surfactants wit two sulfonate groups derived from N-acylidiethanolamines[J]. J. Am. Oil Chem. Soc. 1991(68):539-543.
[19] 王景良．三元复合驱用石油磺酸盐表面活性剂研究进展．国外油田工程．2000(12)：1-5．
[20] SISLEY J P. Encyclopedia of Surface-active Agent[J]. Chemical publ, 1(3):167.
[21] 赵国玺．表面活性剂物理化学[M]．北京大学出版社，1991，459．
[22] P.D. Berger, C. H. Lee. Ultra-low concentration for sandstone and limestone floods. SPE 75186, 2002.
[23] 黄宏度，杨又震等．驱油剂石油羧酸盐的研制[J]．油田化学，1991，8(3)：235-239．
[24] 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．
[25] 伍晓林，张国印，刘庆梅．石油羧酸盐的研制及其在三次采油中的应用．油气地质与采收率2001，8(1)：62-63．
[26] 李干佐，沈强等．新型驱油用表面活性剂天然羧酸盐[J]．油田化学，1999，16(1)：57-59．
[27] 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]．大庆石油学院院报，1999，23(1)：32．
[28] 王业飞，李继勇，赵福麟．高矿化度条件下应用的表面活性剂驱油体系．油气地质与采收率，2001，8(1)，67-69．
[29] Hodyson P K G, et al. Alkyl ethoxy-ethane, Two techniques for improving syntetic conversions [J]. JAOCS, 1990,67(11):730-732.
[30] Kalfoglou George. Surfactants fluid suitable for use in waterflood oil recovery method [P]. US:4373711,1982.
[31] 赵福麟．羧甲基型的非离子-阴离子表面活性剂与石油磺酸盐的混合[J]．石油大学学报，1996，20(4)：52-55．
[32] 韩冬，沈平平．表面活性剂驱油原理及应用．北京：石油业出版社，2001．
[33] Kalpakci, Bayram, Jeans, et al. Surfactant Combinations and Enhanced Oil Recovery Method Employing Same [P] US4811788, 1989-03-14.
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