三采用表面活性剂和聚合物的动态界面张力研究
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摘要
在能源日趋紧张的情况下,提高原油采油率的三次采油已成为石油开采研究的重大课题。以表面活性剂和聚合物进行三次采油的方法得到人们的普遍关注。油水动态界面张力的特征是评价表面活性剂和聚合物在三次采油中性能的重要指标。因此,研究三次采油用表面活性剂和聚合物的动态界面张力具有重要的理论意义和实践意义。
本文首先对几种表面活性剂对各自区块和交叉区块的动态界面张力进行了研究,以了解不同表面活性剂对不同采油区块的动态界面张力情况。然后,通过三种石油磺酸盐对胜利油田三个采油区块油水体系的动态界面张力研究,建立了以最低界面张力、浓度窗口、时间窗口等参数来优选不同区块用表面活性剂的方法。
合成了两种阴离子型石油磺酸盐、非离子型失水山梨醇单油酸酯和季铵盐型双子表面活性剂,研究了它们对不同采油区块的动态界面张力情况。并考察了两种石油磺酸盐复配和失水山梨醇单油酸酯与Tween80复配情况下的动态界面张力。结果表明,两种石油磺酸盐复配和失水山梨醇单油酸酯与Tween80复配能够产生正的协同效应,在不同区块油水体系中油水动态界面张力达到10~(-3)mN/m的超低界面张力值。双子表面活性剂具有较好的界面活性,单独使用在浓度0.1%～0.8%范围内,油水界面张力稳定值都在10~(-3)mN/m数量级以下的超低界面张力值。
考察盐、碱、助剂、聚合物对表面活性剂的动态界面张力的影响。受到表面活性剂与聚合物的相互作用的启发,合成一种既具有表面活性又能提高波及效率的木质素磺酸盐/丙烯酸接枝共聚聚合物。考察其反应条件对其粘度的影响,确定了合成工艺参数。并考察了共聚物单独使用和与石油磺酸盐复配使用的油水动态界面张力情况。结果表明,其单独使用效果不明显;而复配使用,能够使三个采油区块的油水界面张力稳定值降低到10~(-3)mN/m。
根据失水山梨醇单油酸酯的合成和双子表面活性剂的结构与界面性能,制备改性纳米二氧化硅和有机硅-无机硅纳米复合物,并对其进行了结构和形貌的表征。发现它们是一种具有多个亲油基团和多个亲水基团的多亲多疏的新型表面活性剂。考察这种新型表面活性剂与石油磺酸盐复配时对油水动态界面张力的影响情况。结果表明,在合适复配条件下,能够有效降低油水界面张力值至10~(-3)mN/m甚至更低。并研究了其作用机理。
最后,把均匀实验设计方法应用于表面活性剂复配上,利用数理统计软件SAS建立多元回归方程,根据多元回归方程对实验进行预测与指导。结果表明,均匀实验设计在不影响优选效果的情况下,能够明显地减少实验次数,既节省时间又节约实验费用,与传统的实验方法相比具有明显的优越性。
本论文的主要创新点包括:通过动态界面张力的特征参数进行表面活性剂优选的实验方法;合成一种既具有表面活性又能提高波及效率的木质素磺酸盐/丙烯酸接枝共聚聚合物;制备一种具有多个亲油基团和多个亲水基团的多亲多疏的新型表面活性剂;在表面活性剂的复配配比确定过程中,利用均匀实验设计这一高效、简化的方法。
In the situation of energy crisis,Enhanced oil recovery has become an important research field.Methods of Enhanced oil recovery by surfactants and polymers have attracted considerable attention.Characteristics of dynamic interfacial tension are one of the important indexes of the performance of surfactants and polymers in EOR. Therefore,investigating the dynamic interfacial tension of surfactants and polymers in EOR in the interests of fundamental research or industrial applications is of great importance.
In this paper,the dynamic interfacial tensions of different surfactants were investigated in their own field or other field.In order to know the change of dynamic interfacial tensions of different surfactants in different fields.Then,based on dynamic interfacial tensions of three surfactants in three fields were investigated,screening method of surfactant in different fields was established,Parameters of this method include the minimal interfacial tensions,concentration window and time window.
Tow anionic petroleum sulfonate,nonionic sorbitan monooleate and quaternary ammonium salt gemini surfactant were synthesized.The dynamic interracial tensions of them in different fields and the mixing system of sorbitan monooleate and Tween80 were investigated.Results showed that the sorbitan monooleate and Tween80 mixtures had the best synergic effect.The minimal interfacial tensions reached 10~(-3)mN/m.The interfacial activity of gemini surfactant is strong,in the range of 0.1%～0.8%,the stable value of interfacial tension can reach 10~(-3)mN/m.
Effect of salinity,sodium silicate,mixed alkaline,promoters and polymer on dynamic interfacial tension were studied.We were enlightened by interaction between surfactants and polymers,the graft copolymer of lignosulfonate and acrylic acid was synthesized,not only this graft copolymer has strong interracial activity,but also can increase sweep efficiency.The effects of the reaction conditions on the viscosity also were studied,the technology process and factors were determined.The results showed that the single use of graft copolymer had no obvious effect,but the mixing system of graft copolymer and surfactants had a coordinated effect.The stable value of interracial tension can reach 10~(-3)mN/m in three fields.
We also were enlightened by the molecular structure of sorbitol and the interracial property of gemini surfactant,the modified nanometer-silicon dioxide and the organic-inorganic nanocomposite were respectively prepared.Their structure and morphology were characterized by IR and TEM.The results showed that they were new surfactants which have a lot of hydrophilic group and lipophilic group on their surface. The dynamic interfacial tensions of them in different fields and the mixing system of these new surfactants and petroleum sulfonate were investigated.In the optimal conditions,the stable value of interfacial tension can reach 10~(-3)mN/m.The mechanism of nanometer material also was studied.
Finally,the uniform experimental design applied to the mixing system of surfactants.A multiple linear regression model was built by SAS software,through establishing multi linear regression model,experiments were predicted and guided.The results showed that the uniform experimental design can greatly reduce the number of experiments,enhance the work efficiency and save time and expenses.It has obvious advantage that uniform experimental design compares with traditional experimental method.
The main creative points in the dissertation are as followings:The screening method of surfactant in different fields was established through their characteristic parameters.The graft copolymer of lignosulfonate and acrylic acid was synthesized,not only this graft copolymer has strong interfacial activity,but also can increase sweep efficiency.The modified nanometer-silicon dioxide and the organic-inorganic nanocomposite were respectively prepared.They have a lot of hydrophilic group and lipophilic group on their surface.The uniform experimental design applied to the mixing system of surfactants.
本文首先对几种表面活性剂对各自区块和交叉区块的动态界面张力进行了研究,以了解不同表面活性剂对不同采油区块的动态界面张力情况。然后,通过三种石油磺酸盐对胜利油田三个采油区块油水体系的动态界面张力研究,建立了以最低界面张力、浓度窗口、时间窗口等参数来优选不同区块用表面活性剂的方法。
合成了两种阴离子型石油磺酸盐、非离子型失水山梨醇单油酸酯和季铵盐型双子表面活性剂,研究了它们对不同采油区块的动态界面张力情况。并考察了两种石油磺酸盐复配和失水山梨醇单油酸酯与Tween80复配情况下的动态界面张力。结果表明,两种石油磺酸盐复配和失水山梨醇单油酸酯与Tween80复配能够产生正的协同效应,在不同区块油水体系中油水动态界面张力达到10~(-3)mN/m的超低界面张力值。双子表面活性剂具有较好的界面活性,单独使用在浓度0.1%～0.8%范围内,油水界面张力稳定值都在10~(-3)mN/m数量级以下的超低界面张力值。
考察盐、碱、助剂、聚合物对表面活性剂的动态界面张力的影响。受到表面活性剂与聚合物的相互作用的启发,合成一种既具有表面活性又能提高波及效率的木质素磺酸盐/丙烯酸接枝共聚聚合物。考察其反应条件对其粘度的影响,确定了合成工艺参数。并考察了共聚物单独使用和与石油磺酸盐复配使用的油水动态界面张力情况。结果表明,其单独使用效果不明显;而复配使用,能够使三个采油区块的油水界面张力稳定值降低到10~(-3)mN/m。
根据失水山梨醇单油酸酯的合成和双子表面活性剂的结构与界面性能,制备改性纳米二氧化硅和有机硅-无机硅纳米复合物,并对其进行了结构和形貌的表征。发现它们是一种具有多个亲油基团和多个亲水基团的多亲多疏的新型表面活性剂。考察这种新型表面活性剂与石油磺酸盐复配时对油水动态界面张力的影响情况。结果表明,在合适复配条件下,能够有效降低油水界面张力值至10~(-3)mN/m甚至更低。并研究了其作用机理。
最后,把均匀实验设计方法应用于表面活性剂复配上,利用数理统计软件SAS建立多元回归方程,根据多元回归方程对实验进行预测与指导。结果表明,均匀实验设计在不影响优选效果的情况下,能够明显地减少实验次数,既节省时间又节约实验费用,与传统的实验方法相比具有明显的优越性。
本论文的主要创新点包括:通过动态界面张力的特征参数进行表面活性剂优选的实验方法;合成一种既具有表面活性又能提高波及效率的木质素磺酸盐/丙烯酸接枝共聚聚合物;制备一种具有多个亲油基团和多个亲水基团的多亲多疏的新型表面活性剂;在表面活性剂的复配配比确定过程中,利用均匀实验设计这一高效、简化的方法。
In the situation of energy crisis,Enhanced oil recovery has become an important research field.Methods of Enhanced oil recovery by surfactants and polymers have attracted considerable attention.Characteristics of dynamic interfacial tension are one of the important indexes of the performance of surfactants and polymers in EOR. Therefore,investigating the dynamic interfacial tension of surfactants and polymers in EOR in the interests of fundamental research or industrial applications is of great importance.
In this paper,the dynamic interfacial tensions of different surfactants were investigated in their own field or other field.In order to know the change of dynamic interfacial tensions of different surfactants in different fields.Then,based on dynamic interfacial tensions of three surfactants in three fields were investigated,screening method of surfactant in different fields was established,Parameters of this method include the minimal interfacial tensions,concentration window and time window.
Tow anionic petroleum sulfonate,nonionic sorbitan monooleate and quaternary ammonium salt gemini surfactant were synthesized.The dynamic interracial tensions of them in different fields and the mixing system of sorbitan monooleate and Tween80 were investigated.Results showed that the sorbitan monooleate and Tween80 mixtures had the best synergic effect.The minimal interfacial tensions reached 10~(-3)mN/m.The interfacial activity of gemini surfactant is strong,in the range of 0.1%～0.8%,the stable value of interfacial tension can reach 10~(-3)mN/m.
Effect of salinity,sodium silicate,mixed alkaline,promoters and polymer on dynamic interfacial tension were studied.We were enlightened by interaction between surfactants and polymers,the graft copolymer of lignosulfonate and acrylic acid was synthesized,not only this graft copolymer has strong interracial activity,but also can increase sweep efficiency.The effects of the reaction conditions on the viscosity also were studied,the technology process and factors were determined.The results showed that the single use of graft copolymer had no obvious effect,but the mixing system of graft copolymer and surfactants had a coordinated effect.The stable value of interracial tension can reach 10~(-3)mN/m in three fields.
We also were enlightened by the molecular structure of sorbitol and the interracial property of gemini surfactant,the modified nanometer-silicon dioxide and the organic-inorganic nanocomposite were respectively prepared.Their structure and morphology were characterized by IR and TEM.The results showed that they were new surfactants which have a lot of hydrophilic group and lipophilic group on their surface. The dynamic interfacial tensions of them in different fields and the mixing system of these new surfactants and petroleum sulfonate were investigated.In the optimal conditions,the stable value of interfacial tension can reach 10~(-3)mN/m.The mechanism of nanometer material also was studied.
Finally,the uniform experimental design applied to the mixing system of surfactants.A multiple linear regression model was built by SAS software,through establishing multi linear regression model,experiments were predicted and guided.The results showed that the uniform experimental design can greatly reduce the number of experiments,enhance the work efficiency and save time and expenses.It has obvious advantage that uniform experimental design compares with traditional experimental method.
The main creative points in the dissertation are as followings:The screening method of surfactant in different fields was established through their characteristic parameters.The graft copolymer of lignosulfonate and acrylic acid was synthesized,not only this graft copolymer has strong interfacial activity,but also can increase sweep efficiency.The modified nanometer-silicon dioxide and the organic-inorganic nanocomposite were respectively prepared.They have a lot of hydrophilic group and lipophilic group on their surface.The uniform experimental design applied to the mixing system of surfactants.
引文
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