烷基苯磺酸盐的合成与拓扑学方法的应用
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摘要
烷基苯磺酸盐类驱油剂是由结构复杂的混合物组成的表面活性剂,国内油田矿场试验的表面活性剂主要依靠进口,因此合成纯的烷基苯磺酸盐类化合物为研究烷基苯磺酸盐结构与性能间的关系及烷基苯磺酸盐类驱油剂的复配提供理论依据,以便更有效地利用其提高石油采收率。
本文以邻二甲苯为原料,经傅-克酰基化反应、格氏反应、还原反应、磺化及中和5步反应,系统合成出结构明确的6种十二烷基二甲苯基磺酸钠异构体,用FT-IR、ESI-MS、13C NMR和1H NMR鉴定了中间产品和最终产物的结构。并用拓扑学的方法预测了多烷基苯的结构与沸点的关系。
采用滴体积法测定表面活性剂水溶液25℃时的表面张力,从而确定其临界胶束浓度,研究了支链结构对其表面性质的影响。6种表面活性剂的CMC ( mmol·L-1 )和γCMC( mN·m-1 )分别为Ⅰ:0.25,30.00;Ⅱ:0.50,28.21;Ⅲ:0.79,28.10;Ⅳ:1.00,27.01;Ⅴ:2.00,26.41;Ⅵ:2.50,26.40。结果表明随着苯环向长链烷基中间移动,表面活性剂的CMC增高,γCMC减小。
采用旋转液滴界面张力仪对系列烷基苯磺酸盐与各种烷烃及大庆四厂原油间的油水界面张力进行了测试,系统地研究了6种表面活性剂的界面张力。
Surfactants of alkylbenzene sulfonates that were tested in domestic oil field for EOR are made of complicated mixtures, a majority of them depends on import, so the synthesis of pure alkylbenzene sulfonates is the academic base of the study for the relation between structure and property, the complex for surfactants of alkylbenzene sulfonates. Through these studies this kind of surfactant can be efficiently used for EOR.
Six kinds of isomers of sodium alklybenzene sulfonates were synthesized from chloride and o-xylene through five-step process, involving Friedel-Crafts reaction, Grignard reaction, reduction, sulfonation and neutralization. The structures of the intermediates and the final products were characterized by FT-IR, ESI-MS 13C NMR and 1H NMR. The relationship between boiling point of polyalkylbenzene and their molecular structure were studied
The surface tension of dilute aqueous solutions of products was measured at 25℃by Drop-volume method and then the critical micelle concentration (CMC) was determined. The values of CMC( mmol·L-1) andγCMC ( mN·m-1) were listed as follows :Ⅰ: 0.25, 30.00;Ⅱ: 0.50, 28.21;Ⅲ: 0.79, 28.10;Ⅳ: 1.00, 27.01;Ⅴ: 2.00, 26.41;Ⅳ: 2.50, 26.40. These results indicated that as the CMC increasing, theγCMC reduced with the moving of the benzene ring from the edge to the middle of the long chain alkyl.
The interfacial tension behavior of this series of alkylbenzene sulfonates was investigated in alkane/aqueous system and crude oil/aqueous system respectively. The dynamic interfacial tension behavior shows that these six kinds of surfacrants have different interfacial tension.
本文以邻二甲苯为原料,经傅-克酰基化反应、格氏反应、还原反应、磺化及中和5步反应,系统合成出结构明确的6种十二烷基二甲苯基磺酸钠异构体,用FT-IR、ESI-MS、13C NMR和1H NMR鉴定了中间产品和最终产物的结构。并用拓扑学的方法预测了多烷基苯的结构与沸点的关系。
采用滴体积法测定表面活性剂水溶液25℃时的表面张力,从而确定其临界胶束浓度,研究了支链结构对其表面性质的影响。6种表面活性剂的CMC ( mmol·L-1 )和γCMC( mN·m-1 )分别为Ⅰ:0.25,30.00;Ⅱ:0.50,28.21;Ⅲ:0.79,28.10;Ⅳ:1.00,27.01;Ⅴ:2.00,26.41;Ⅵ:2.50,26.40。结果表明随着苯环向长链烷基中间移动,表面活性剂的CMC增高,γCMC减小。
采用旋转液滴界面张力仪对系列烷基苯磺酸盐与各种烷烃及大庆四厂原油间的油水界面张力进行了测试,系统地研究了6种表面活性剂的界面张力。
Surfactants of alkylbenzene sulfonates that were tested in domestic oil field for EOR are made of complicated mixtures, a majority of them depends on import, so the synthesis of pure alkylbenzene sulfonates is the academic base of the study for the relation between structure and property, the complex for surfactants of alkylbenzene sulfonates. Through these studies this kind of surfactant can be efficiently used for EOR.
Six kinds of isomers of sodium alklybenzene sulfonates were synthesized from chloride and o-xylene through five-step process, involving Friedel-Crafts reaction, Grignard reaction, reduction, sulfonation and neutralization. The structures of the intermediates and the final products were characterized by FT-IR, ESI-MS 13C NMR and 1H NMR. The relationship between boiling point of polyalkylbenzene and their molecular structure were studied
The surface tension of dilute aqueous solutions of products was measured at 25℃by Drop-volume method and then the critical micelle concentration (CMC) was determined. The values of CMC( mmol·L-1) andγCMC ( mN·m-1) were listed as follows :Ⅰ: 0.25, 30.00;Ⅱ: 0.50, 28.21;Ⅲ: 0.79, 28.10;Ⅳ: 1.00, 27.01;Ⅴ: 2.00, 26.41;Ⅳ: 2.50, 26.40. These results indicated that as the CMC increasing, theγCMC reduced with the moving of the benzene ring from the edge to the middle of the long chain alkyl.
The interfacial tension behavior of this series of alkylbenzene sulfonates was investigated in alkane/aqueous system and crude oil/aqueous system respectively. The dynamic interfacial tension behavior shows that these six kinds of surfacrants have different interfacial tension.
引文
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