【作者】 赵忠奎；

【导师】 程侣柏； 李宗石； 王桂茹；

【作者基本信息】 大连理工大学 ， 应用化学， 2005， 博士

【摘要】 目前,国内油田矿场试验表面活性剂主要靠进口,价格非常昂贵;国内对驱油剂的研究也主要集中在石油磺酸盐、重烷基苯磺酸盐等混合物上,产品质量极不稳定,难以达到稳定高效驱油的要求。因此开发原料组分清楚、产品稳定的廉价高效的驱油用表面活性剂具有重要的应用价值和现实意义。 本文从分子设计的角度,以廉价的甲基萘为原料,合成系列烷基甲基萘磺酸盐表面活性剂。通过反应条件进行优化,找到了甲基萘与长链溴代烷烷基化的较佳反应条件:催化剂用量为2%,β-甲基萘与溴代烷摩尔比为3:1,溶剂环己烷与β-甲基萘摩尔比3:1,在80℃条件下,反应120-240 min。在优化反应条件下,合成了系列长链烷基甲基萘,纯度在97.6%以上。采用发烟硫酸对系列长链烷基甲基萘中间体进行磺化。采用适当浓度盐酸溶液洗涤法,直接对单、双磺酸进行分离。找到了分离不同链长的烷基甲基萘单、双磺酸所需的较佳酸浓度,有效地实现了烷基甲基萘单、双磺酸的分离。采用上述分离提纯方法,得到了系列烷基甲基萘磺酸盐表面活性剂,纯度在95.6%以上。采用HPLC、ESI/MS、IR、UV对系列产品进行表征。 研究了系列长链烷基甲基萘磺酸盐表面活性剂水溶液表面张力行为。结果表明所合成表面活性剂具有很高的降低水溶液表面张力的能力和效率。本文测定了己基、辛基、癸基、十二烷基和十四烷基甲基萘磺酸盐表面活性剂驱油体系与胜利油田和大庆四厂原油间的动态界面张力。研究了强碱、弱碱和无碱驱油体系的界面张力行为。详细考察了表面活性剂侧链长度、浓度及碱度、盐度对界面张力行为的影响。结果表明,动态界面张力在合适的条件下可以在较长时间维持超低,可以实现弱碱、甚至无碱;动态界面张力最小值在最佳条件下甚至可达10^-6mN.m^-1。烷基甲基萘磺酸盐表面活性剂、碱和无机盐之间在降低油水界面张力方面存在明显的协同和对抗效应。亲油性小的表面活性剂,协同效应占优势;亲油性大的表面活性剂,对抗效应占优势;基于这些规律,可以根据实际需要,给出所需的驱油体系。 研究了离子液体催化甲基萘与长链烯烃的烷基化,考察了反应条件对烷基化反应的影响。结果表明,在适宜的反应条件下,烯烃转化率可达90%以上。对于α-甲基萘的烷基化,反应无需有机溶剂;β-甲基萘烷基化,仅需少量溶剂（相对AlCl₃催化）,目标产物选择性约100%。基于离子液体的可调变性,合成了含有不同阴阳离子的离子液体,研究了离子液体组成和催化性能的关系。结果表明,离子液体的阴离子（包括三氯化铝摩尔分数的变化）对离子液体催化性能和物理性能影响显著;阳离子主要对离子液体的物理性能有一定影响,对催化性能影响较小。丁基吡啶氯铝酸离子液体具有较好的催化性能,经7%Cu²⁺修饰,催化活性有所改善。离子液体催化剂与反应混合物易于分离,产品后处理简单。催化剂可通过简单的倾析方法分离出来,可以循环使用。更多还原

【Abstract】 At present, the surfactants for domestic oil field lease test mainly depend on import, cost is very high. Many researches mainly focus on some mixed surfactants, petroleum sulphonates and heavy alkyl benzene sulphonates. It’s difficult to satisfy the request for stable and high efficient enhanced oil recovery, now that these products are extremely uncertain. Therefore, to explore the low price and high efficient surfactants for enhanced oil recovery, which are prepared from distinguish clearly materials, has important using value and realistic meaning.In this paper, a series of various chain-length alkyl methylnaphthalene surfonate surfactants have been synthesized on the basis of "tailoring technology". The reaction conditions for alkylation of methylnaphthalene with n-bromoalkanes are optimized, and the optimal reaction conditions are: 3:1 for methylnaphthalene to bromoalkane, and 3:1 for cyclohexane to methylnaphthalene in the presence of 2% of anhydrous aluminum chloride at 80 ℃ for 2-4 hours. The series of high purity (more than 98%, obtained by GC) of various length side-chain alkyl methylnaphthalene (AMN) intermediates have been obtained. The synthesized AMN intermediates are sulfonated by using 20% oleum as sulfonating agent. Here the appropriate concentration of hydrochloride lavation method has been adopted to separate the mono- and di- sulfonic acids directly. The optimal hydrochloride concentrations are found to separate various chain-length alkyl methylnaphthalene mono- and di- sulfonic acids, and the satisfactory separation efficiency is obtained. The separated alkyl methylnaphthalene monosulfonic acids are neutralized, eliminated salts by anhydrous ethanol and decolored by activated carbon, the series of high purity (more than 95.6%, by HPLC) of sulfonate (AMNS) surfactants are achieved, and characterized by HPLC, ESI/MS, IR and UV.The surface tensions of a series of AMNS surfactant aqueous solutions are measured with a ring method. It’s found that the synthesized surfactants possess high capacity and efficiency of lowering surface tension. The dynamic interfacial tensions (DIT) between crude oil, offered from Shengli and Daqing Oilfields, and series of AMNS surfactants, including hexyl, octyl, decyl, dodecyl, tetradecyl methylnaphthalene sulfonates, flooding systems have been measured. The flooding systems with strong alkaline, buffered alkaline and without alkaline are studied. Effects of chain-length and concentration of AMNS surfactants, alkalinity and salinity on the DIT behaviors are investigated. It’s found that, under the seemly conditions, DIT can reach and maintain ultralow at a long time, and even to reach 10-6 mN.m-1 at the optimum conditions. Results show that there exists obvious synergism and antagonism among salt, alkaline and surfactant. For the less lipophilic surfactants, the synergism is dominating, but for stronger lipophilic surfactants, antagonism is leading. The optimal surfactant concentration, alkalinity and salinity for lowering the dynamic interfacial tension to ultralow value are relative. On the basis of these results, the更多还原