【作者】 黄毅；

【导师】 朱红；

【作者基本信息】 北京交通大学 ， 光学， 2009， 博士

【摘要】 随着经济的快速发展,我国对能源的需求量越来越大,能源的需求与产出矛盾日益突出。在新型能源还无法大规模应用、传统能源又日趋紧张的情况下,能大幅度提高原油采收率的三次采油技术已成为石油开采研究的重大课题,而表面活性剂.即驱油剂驱油是三次采油的重要研究内容之一。目前,在大量应用的三次采油驱油剂中,大部分都含有芳环,特别是有的还含有稠环结构,生物降解性差、环境毒性大,对环境不友好。同时,这些在各油田广泛应用的驱油剂都需要与碱、助表面活性剂等复配使用才能达到降低油水界面张力至超低值、提高采收率的目的。本论文的主要目的是针对现有驱油剂的缺陷,有针对性地研究环保、高效、经济的新型表面活性剂并运用在三次采油中,使其在不加碱和其它任何助剂的情况下能降低油水界面张力至超低值,达到大幅度提高原油采收率的目的。经过大量文献查阅,本论文选用一系列的不含芳香环的原料进行磺化、中和,期望得到具有较高活性的磺酸盐驱油剂。经过大量的的原料筛选和工艺优化后,本论文成功用不含芳香环结构的环烷基油和生物油做为原料,用发烟浓硫酸做为磺化试剂分别磺化两种原料,最后经氨水中和,得到了两种非芳香性磺酸盐驱油剂:环烷基石油磺酸盐和生物油磺酸盐。该制备方法工艺成熟简单,易于工业化生产。所合成的两种磺酸盐经过硅胶柱层析分离提纯后,分别做了红外和核磁共振氢谱分析,经过与两种合成原料的红外和核磁共振氢谱对比分析后,证实了两种非芳香性磺酸盐驱油剂的存在。这两种非芳香性磺酸盐驱油剂都表现出优良的界面活性。在不加碱及其它任何助剂的情况下,能降低胜利油田采油一区、采油二区及孤东、孤岛的多数采油区块的油水界面张力至10^-3mN/m以下,最低至5×10^-4mN/m,表现出较好的界面活性和一定的普适性。同时,合成的两种非芳香性磺酸盐具有较好的抗盐及抗Ca²⁺、Mg²⁺能力。其中环烷基石油磺酸盐在总矿化度为2000～50000mg/L范围内,生物油磺酸盐在盐度2000mg/L～130000mg/L范围内都具有较高的界面活性。环烷基石油磺酸盐在Ca²⁺、Mg²⁺浓度为40～450mg/L范围内,生物油磺酸盐在Ca²⁺、Mg²⁺浓度500mg/L以下时都具有较好的界面活性。本论文测试了胜利油田部分采油区块原油的等效烷烃数（EACN）和两种非芳香性磺酸盐的最低碳数值(n_min),分析了EACN与n_min之间内在的关系;同时从两种非芳香性磺酸盐的分子结构特点出发,从分子结构和界面活性关系上探讨了两种磺酸盐具有较高界面活性、较广普适性的原因,从理论上拓展了驱油剂的界面行为研究,得出了具有普遍意义的规律,为以后进一步研究新型、高效的驱油剂提供了理论上的依据和支持。更多还原

【Abstract】 With the rapid economic developing,China’s growing energy demand has become increasingly conspicuous.Now,large-scale application of new energy can’t be realized and traditional energy is becoming shortage.Under this situation,greatly enhance oil recovery technology has become a major oil research topics.Obviously,the surfactant which is used in tertiary oil recovery,become one of the important research focuses.Presently,the main surfactants used in enhanced oil recovery usually possess aromatic rings and can not be bi-degraded and be harmful to environment.The primary object of this dissertation is to design and synthesize some novel nonaromatic sulphonates which can be used in enhanced oil recovery.The novel sulphonates should be environment-friendly and biodegradable.Additionally,they have excellent ability to reduce the interfacial tension between crude oil and water.The novel sulphonates which are ester sulphonate and naphthenic petroleum sulphonate,through many experiments and reaction rout optimization,were designed and prepared in laboratory using ester or naphthenic oil reacted with fuming sulfuric acid followed by hydrolysis.The structures of two products were characterized by infrared spectra and ¹H nuclear magnetic resonancemain,at the same time,the main functional groups were approved.The results showed that the double bonds in ester were sulphonated and then converted into the corresponding saturated hydroxy ester sulphonate followed by hydrolysis when ester reacted with fuming sulfuric acid and naphthenic petroleum sulphonate was obtained through substitution reaction after naphthenic oil reacted with fuming sulfuric acid.The interfacial activities of the two products were evaluated.It revealed that the two products had excellent capacities and efficiencies to lower the tensions of oil-water interface of block 1.and block 2.in Shengli oilfield to ultra-low without alkaline and any other additives.The interfacial tension between crude oil and water could be reduced as low as 10^-3mN/m and the minimum interfacial tension was up to 5×10^-4mN/m.Furthermore,the two products possessed outstanding salt-resisting capacitis as well.The ester sulphonate could reduce interfacial tension between oil and water to 10^-3 mN/m even with the concentration of NaCl between 2000mg/L～130000 mg/L or with the concentration of Ca²⁺、Mg²⁺ below 500mg/L,and the naphthenic petroleum sulphonate could reduce interfacial tension between oil and water to 10^-3 mN/m even with the concentration of NaCl between 2000mg/L～50000mg/L or with the concentration of Ca²⁺、Mg²⁺ below 500mg/L.The two products were expected to be used in enhanced oil recovery applications.The equivalent alkane carbon number（EACN） was tested in part of Shengli Oilfield Area and the minimum number of alkane carbon(n_min) of the two surfactants were measured.The relationships between surfactant molecular structure and ability in lowering surface tension were investigated.All of this could provide theoretical fundamentals for designing new surfactant molecules in enhanced oil recovery.更多还原