烷基苯磺酸盐类驱油剂精细合成与结构表征
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摘要
本文利用对二甲苯、不同碳数直链酰氯(或脂肪酸)以及卤代烷合成出6种结构相似、长链烷烃碳数为12、芳基在烷烃链不同位置的烷基苯磺酸盐类表面活性剂。通过正交试验考查了原料摩尔比、反应时间和反应温度对中间体2,5-二甲基苯基十二烷基酮收率的影响。利用红外光谱、核磁共振氢谱和碳谱对中间体酮、叔醇和烷基苯进行了结构鉴定;通过电喷雾质谱、核磁共振氢谱和碳谱对最终产物烷基芳基磺酸钠进行了结构表征。分析结果表明,所合成的中间体及最终产品的结构与所设计的分子结构相符。
通过表面张力的测定,研究了这6种产品的表面性能。结果表明,随着芳环向长烷基链中间位置移动,表面活性剂的临界胶束浓度逐渐增加,而临界胶束浓度下的表面张力则逐渐减小。本文还对表面活性剂的界面性能进行了研究,通过界面张力扫描的方法测得这6种表面活性剂的nmin值,为实际应用中的筛选与复配提供数据。此外,还研究了它们与大庆四厂脱水脱气原油间的界面张力行为。研究结果表明,各烷基芳基磺酸盐水溶液与原油间的动态界面张力随着时间的增加缓慢升高,最后趋于不变。对于平衡时的界面张力,芳环位于长烷基链中间位置的表面活性剂能使油水界面张力降低幅度最大。由此可见,烷基苯磺酸盐的支化程度越高,降低界面张力的能力越强,界面活性越好。
Using p-xylene, different acyl chloride (fatty acid) and alkylogen, six kinds of isomers (alkyl aryl sulfonates) were synthesized, with similar structure, carbons of same quantity, and the position of alkylaryl dissimilarity. By orthogonal experiments, the effect of reaction time, temperature and the ratio of raw materials on the yield of 2,5-dimethylphenyldodecyl ketone was examined. The structure of intermediates and final products were confirmed to be correct by IR, 1H NMR, 13C NMR and ESI-MS.
By measuring the surface tension, the surface properties of these six products were investigated. The results showed that as the aromatic ring shifting to the middle of the long carbonic chain, the cmc increased, andγcmc reduced gradually. The interfacial performance of the surfactant was also investigated. Through scanning interfacial tension measurement, nmin values of these six types of surfactants were given.which will offer data for screening and complex in practice. In addition, the interfacial tension behavior between surfactant and crude oil from No.4 factory of Daqing oilfield was also studied. The results showed that the dynamic interfacial tension between the surfactant and the crude oil increased slowly, and finally tended to remaining unchanged. As for the equilibrium interfacial tension, the product with aromatic ring in the middle of the long chain reduced greatly. It showed that if the degree of branching of alkylbenzene sulfonate became higher, the ability to reduce interfacial tension and the interfacial activity will be greater and better.
通过表面张力的测定,研究了这6种产品的表面性能。结果表明,随着芳环向长烷基链中间位置移动,表面活性剂的临界胶束浓度逐渐增加,而临界胶束浓度下的表面张力则逐渐减小。本文还对表面活性剂的界面性能进行了研究,通过界面张力扫描的方法测得这6种表面活性剂的nmin值,为实际应用中的筛选与复配提供数据。此外,还研究了它们与大庆四厂脱水脱气原油间的界面张力行为。研究结果表明,各烷基芳基磺酸盐水溶液与原油间的动态界面张力随着时间的增加缓慢升高,最后趋于不变。对于平衡时的界面张力,芳环位于长烷基链中间位置的表面活性剂能使油水界面张力降低幅度最大。由此可见,烷基苯磺酸盐的支化程度越高,降低界面张力的能力越强,界面活性越好。
Using p-xylene, different acyl chloride (fatty acid) and alkylogen, six kinds of isomers (alkyl aryl sulfonates) were synthesized, with similar structure, carbons of same quantity, and the position of alkylaryl dissimilarity. By orthogonal experiments, the effect of reaction time, temperature and the ratio of raw materials on the yield of 2,5-dimethylphenyldodecyl ketone was examined. The structure of intermediates and final products were confirmed to be correct by IR, 1H NMR, 13C NMR and ESI-MS.
By measuring the surface tension, the surface properties of these six products were investigated. The results showed that as the aromatic ring shifting to the middle of the long carbonic chain, the cmc increased, andγcmc reduced gradually. The interfacial performance of the surfactant was also investigated. Through scanning interfacial tension measurement, nmin values of these six types of surfactants were given.which will offer data for screening and complex in practice. In addition, the interfacial tension behavior between surfactant and crude oil from No.4 factory of Daqing oilfield was also studied. The results showed that the dynamic interfacial tension between the surfactant and the crude oil increased slowly, and finally tended to remaining unchanged. As for the equilibrium interfacial tension, the product with aromatic ring in the middle of the long chain reduced greatly. It showed that if the degree of branching of alkylbenzene sulfonate became higher, the ability to reduce interfacial tension and the interfacial activity will be greater and better.
引文
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[13] 焦艳华,徐志刚,乔卫红,等.改性木质素磺酸盐表面活性剂合成及性能研究[J].大连理工大学学报,2004,44(1):44-47.
[14] 张统明,徐广宇,周宇鹏,等.改性碱木质素表面活性剂在三次采油中的应用研究[J].油气井测试,2004,13(1):12-15.
[15] 韩冬,沈平平.表面活性剂驱油原理及应用[M].北京:石油工业出版社,2001.26-54.
[16] 刘继德,牛亚斌.油田化学品[M].北京:中国物质出版社,2001.39-78.
[17] 陈茂齐,吕祖芳,赵国安,等.十二烷基苯磺酸钠及石油磺酸钠的 GC/MS 分析[J].油田化学,1987,4(3):214-219.
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[19] 俞稼镛,宋万超,李之平.化学复合驱基础及进展[M].北京:中国石化出版社,2002.18-43.
[20] 林玉.三次采油技术获重大突破[J].中国石油石化,2005,(4):32.
[21] 张越,张高勇,王佩维,等.重烷基苯磺酸盐的界面性质和驱油机理[J] 物理化学学报,2005,21(2):161-165.
[22] 崔正刚,邹文华,孙雪芳,等.重烷基苯磺酸盐/碱/原油体系的界面张力[J].油田化学,1999,16(2):153-157.
[23] 崔正刚,邹文华,张天林,等.重烷基苯磺酸盐的合成及其在三次采油中的应用[J].华东理工大学学报(自然科学版),1999,25(4):339-346
[24] 邹文华,刘世霞,张天林,等.用普通 SO3 膜式磺化器磺化重烷基苯[J].无锡轻工大学学报,2000,19(6):604-609.
[25] 郭东红,张雅琴,崔晓东,等.三次采油用重烷基苯磺酸盐表面活性剂不同组分的协同效应[J].应用化学,2003,20(1),86-88.
[26] 张树彪.三次采油用表面活性剂的合成及其界面张力性能的研究[D].辽宁:大连理工大学,2000.
[27] Kassem T M,Marei A A,Shalaby A M.Surface active agents from alkylnaphthalenes,Part II:New surfactants from Egyptian petroleum paraffins[J].Tenside Detergents,1984,21(1):20-23.
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[29] Gutierrez M C, Gago N,Crespi M,etal.The use of H.P.L.C.in the determination of aromatic sulphonates[J].Tenside Surf Det,1993,30(1):15-17.
[30] 赵忠奎,李宗石,付新梅,等.长链烷基甲基萘单磺酸盐和双磺酸盐分离研究[J].大连理工大学学报,2005,45(4):501-504.
[31] 赵忠奎,乔卫红,袁冰,等.长链烷基甲基萘的合成[J].南京理工大学学报,2004,28(3):311-315.
[32] Sanz C A.Alcohol-free chemical flooding:from surfactant screening to coreflood design[J].SPE 28956-MS,1995.
[33] Berger P D,Lee C H.Ultra-low concentration surfactants for sandstone and limestone flood[J].SPE 75186-MS,2002
[34] 彭朴.采油用表面活性剂[M].北京:化学工业出版社,2003.43-46.
[35] 刘璞.用于强化采油的表面活性剂的一些进展[J].油田化学,1985,2(1):1-8.
[36] 马涛,王俊涛,缪庆林.耐盐型表面活性剂在油田中的应用[J].日用化学品科学,2006,29(12):25-27.
[37] 康万利,董喜贵.表面活性剂在油田中的应用[J].北京:化学工业出版社,2005.4-5.
[38] 朱莉,王利平.红外光谱法测定石油磺酸盐含量[J]无锡轻工大学学报,1997,16(2):76.
[39] 赵斌元,胡克螯,范永忠,等.木质素磺酸及其衍生物红外光谱研究[J].分析化学,2000,28(6):716-719.
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