双长链醇醚甜菜碱的合成及性能研究

发布时间：2018-03-15 21:33

本文选题：双长链醇醚羧基甜菜碱　切入点：合成　出处：《江南大学》2015年硕士论文　论文类型：学位论文

【摘要】：碱-表面活性剂-聚合物(ASP)三元复合驱是我国化学驱提高石油采收率的主要技术,但近年来的矿场试验表明,使用碱尤其是强碱会带来一些副作用,因此以SP二元驱取代ASP三元驱成为新的研究方向。研究发现,双十二烷基甲基羧基甜菜碱(di C12B)在无碱条件下具有优良的降低原油/水界面张力性能,但由于具有双长链烷基,其水溶性较差并且在油砂/水界面有较大的吸附损失。另一方面以椰子油醇聚氧乙烯醚(C12-14EO2OH)为原料合成的双长链醇醚甲基羧基甜菜碱,不仅保留了di C12B的优良性能,而且产品的水溶性有显著改善,在油砂/水界面的吸附损失明显减小。由于工业级醇醚中EO数具有较宽的分布,有关EO数对性能的影响尚不清晰,为此本研究试图合成具有单一EO数的双十二醇聚氧乙烯醚甲基羧基甜菜碱系列产品,以考察EO数对有关驱油性能的影响。以溴代十二烷和一缩二乙二醇(或二缩三乙二醇,三缩四乙二醇)为原料,合成了单分布的十二醇聚氧乙烯醚(C12EOnOH,n=2,3,4),再经氯代、与一甲胺缩合、最后与氯乙酸锂反应得到了目标产物双十二醇聚氧乙烯醚甲基羧基甜菜碱(di C12EOnB,n=2,3,4)。核磁、质谱、化学分析等表征证明所得产品的分子结构与目标化合物一致。对diC12EOnB(n=2,3,4)系列产品的水溶性、基本表面活性、降低正构烷烃/水和大庆原油/地层水界面张力的特性以及在石英砂/水界面的吸附损失进行了评价。结果表明,di C12EOnB(n=2,3,4)在水中的溶解度随EO数的增加而增加,25?C时di C12EO4B的溶解度达到1.5?10-4 mol/L,是di C12B的3倍。di C12EOnB(n=2,3,4)基本保持了di C12B的高表面活性。cmc在(1.15~2.0)?10-5 mol/L,?cmc为27.0~29.5 m N/m,在空气/水界面上的饱和吸附量??为(6.2~5.7)?10-10 mol/cm2。其中随着n的增大,cmc,?cmc以及分子截面积a?略有增大。di C12EOnB(n=2,3,4)单独使用时降低正构烷烃/水界面张力的性能优于di C12B,其中di C12EO2B和di C12EO4B分别能将C13~C15和C7~C9正构烷烃/水界面张力降至超低(0.01 m N/m),di C12EO3B能将C7~C16正构烷烃/水界面张力降至10-2 m N/m数量级。在降低大庆原油/地层水界面张力方面,di C12EOnB(n=2,3,4)单独使用能将大庆原油/地层水界面张力降至10-2 m N/m数量级;其中di C12EO2B亲油性仍偏大,通过与水溶性同系物C16B复配,能在较宽(1.25~7.5 mmol/L)的总浓度范围内将大庆原油/地层水界面张力降至超低;di C12EO3B亲油性略偏大,与水溶性同系物C16B复配能将大庆原油/地层水界面张力降至超低,但合适的总浓度范围缩小(5~7.5 mmol/L);而di C12EO4B亲水性略偏大,与亲油性同系物di C12B和水溶性同系物C16B三元复配,能在较宽(0.625~5.0mmol/L)的总浓度范围内将大庆原油/地层水界面张力降至超低。三种化合物中di C12EO2B为最佳。di C12EOnB(n=2,3,4)在石英砂/水界面的吸附具有饱和吸附量,饱和吸附量随n增加略有下降,其中n值最大的di C12EO4B的饱和吸附量比di C12B下降了35%。总体上EO基团的引入对降低在石英砂/水界面的吸附损失影响不够显著。
[Abstract]:Alkali surfactant polymer (ASP) three ASP flooding is the main technology to improve oil recovery of chemical flooding, but the field tests show that in recent years, especially the use of alkali and alkali will bring some side effects, so SP to two yuan three yuan to replace the ASP drive drive has become a new research direction. Found that di dodecylmethyl carboxybetaine (DI C12B) in non alkaline conditions with excellent performance to reduce the crude oil / water interfacial tension, but because of the double long Lian Wanji, due to its poor water solubility and in oil / water interface has larger adsorption loss. On the other hand with alkyl polyoxyethylene ether (C12-14EO2OH) as raw materials the synthesis of double long-chain carboxyl betaine methyl ether, not only retains the excellent performance of di C12B, and the water solubility of the product has been improved in oil / water interface adsorption loss decreases obviously. The industrial grade has a number of EO in ether Wide distribution, about the effect of EO number on the performance is not clear, the purpose of this study is to synthesize EO single number Double Twelve alcohol polyoxyethylene ether methyl carboxyl betaine series of products, in order to study the influence of EO number on the oil displacement performance. Twelve alkyl bromide with diethylene glycol and triethylene glycol (or two. Three shrink four ethylene glycol) as raw materials, twelve alcohol polyoxyethylene ether single distribution were synthesized (C12EOnOH, n=2,3,4), and then by chlorination, condensation and methylamine, finally reacted with chloroacetic acid lithium to obtain target products Double Twelve methyl alcohol polyoxyethylene ether (DI C12EOnB, n=2,3,4 carboxybetaine). NMR, mass spectrometry, chemical analysis indicates that the molecular structure of the target compound and the product of diC12EOnB (n=2,3,4) series of products of the basic water solubility, surface activity, lower n-alkanes / water and Daqing crude oil / water interfacial tension characteristics and Quartz sand / water interface adsorption loss were evaluated. The results showed that di C12EOnB (n=2,3,4) in water solubility increases with the increase in the number of EO increased 25? C solubility of di C12EO4B reached 1.5? 10-4 mol/L, di C12B.Di C12EOnB (n=2,3,4) 3 times remained the high surface activity of.Cmc di C12B (1.15~2.0) in 10-5? Mol/L, CMC? 27.0~29.5 m N/m, the saturated adsorption capacity of the air / water interface (6.2~5.7) for??? 10-10 mol/cm2. with the increase of N, CMC, CMC and a molecular cross-sectional area of?? (n= 2,3,4 C12EOnB.Di increased slightly when used alone) reduce the n-alkane / water interfacial tension is better than di C12B, di C12EO2B and di C12EO4B respectively, which can be C13~C15 and C7~C9 alkanes / water interfacial tension to ultra low (0.01 M N/m), di C12EO3B C7~C16 can be normal alkane / water interfacial tension to 10-2 m N/ m magnitude. In lower Daqing crude oil / formation Water interfacial tension, di C12EOnB (n=2,3,4) can be used alone in Daqing crude oil / water interfacial tension to 10-2 m N/ m magnitude; Di C12EO2B lipophilic is still relatively large, and the water soluble homologue C16B was in wide (1.25~7.5 mmol/L) Daqing crude oil / water interfacial tension to super low total concentration range; Di C12EO3B lipophilic slightly, and the water soluble compound can be C16B homologues of Daqing crude oil / water interfacial tension to low, but the total suitable concentration range reduced (5~7.5 mmol/L); while di C12EO4B is slightly larger and hydrophilic, lipophilic homologues Di and water C12B soluble homologue C16B three compound, in a wide (0.625~5.0mmol/L) Daqing crude oil / water interfacial tension to ultra low concentration range. The total three compounds in di C12EO2B is the best.Di C12EOnB (n=2,3,4) has full adsorption on quartz sand / water interface And the amount of adsorption and saturated adsorption decreased slightly with the increase of n. The saturated adsorption capacity of di C12EO4B with maximum n value decreased by 35%. compared with that of di C12B. In general, the introduction of EO group had little effect on reducing the adsorption loss at quartz sand / water interface.

【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TE357.46

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