【作者】 彭秀花；

【导师】 钟传蓉；

【作者基本信息】 成都理工大学 ， 应用化学， 2011， 硕士

【摘要】 本文主要研究一种接枝缔合型丙烯酰胺共聚物(PAAV)与五种不同分子结构的表面活性剂间的相互作用机理,五种典型表面活性剂分别为十二烷基硫酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、十六烷基三甲基溴化铵(CTAB)、烷基酚聚氧乙烯(10)醚(OP-10)以及十二烷基二甲基胺乙内酯(BS-12)。研究了温度、盐浓度、剪切速率以及共聚物浓度对溶液表观粘度和对复合盐水溶液表、界面张力的影响,结果表明,聚合物PAAV由于很强的分子间缔合作用,具有较好的增粘性能、抗盐性能、耐温性能以及两亲性能。研究了纯水和盐水中五种表面活性剂浓度分别对聚合物溶液增粘性能的影响规律。并得到各表面活性剂与接枝缔合共聚物复配的最佳浓度。研究并得到了聚表二元体系在纯水中的流变规律,以及pH值对复合溶液表观粘度的影响规律。研究了表面活性剂浓度对聚合物盐水溶液表面张力和界面张力的影响规律,揭示出接枝缔合共聚物与各表面活性剂的相互作用机理。在宽的NaCl浓度范围内,PAAV显示了较好的增粘能力和两次盐增稠效应。在5000 mg/L NaCl盐水溶液中,0.20 g/dL PAAV溶液粘度为693.9 mPa·s;当NaCl浓度为30000 mg/L和90000 mg/L时,溶液粘度分别为265.9 mPa·s和193 mPa·s。在20～80℃范围内,0.20 g/dL PAAV由于强的分子间缔合作用,在5000 mg/L NaCl溶液中显示了良好的耐温性能和两次热增稠行为,且在25℃时溶液中粘度最高,为889.8 mPa·s;高于45℃后,溶液粘度随温度升高缓慢下降,即使在80℃时共聚物盐水中的溶液粘度仍然高达510.9 mPa·s。0.2 g/dL PAAV在纯水和盐水溶液中,聚合物表观粘度随着SDS、SDBS、CTAB浓度的增加都是先急剧增大再减小,然后趋于平衡。在纯水溶液中,溶液表观粘度极值分别为3443 mPa·s、3521 mPa·s和2879 mPa·s,此时最佳增粘浓度为分别为2 mmol/L、0.8 mmol/L和0.5 mmol/L;在5000 mg/L NaCl盐水溶液中,溶液的粘度极值分别为869.3 mPa·s、905.1 mPa·s和1107.8 mPa·s,此时最佳增粘浓度为分别为1 mmol/L、0.3 mmol/L和0.3 mmol/L。随着BS-12浓度的增加,聚合物表观粘度先增大后趋于平衡。当BS-12浓度为1 mmol/L时,0.2 g/dL PAAV纯水溶液表观粘度为1036 mPa·s,盐水溶液表观粘度下降为753.5 mPa·s。随着OP-10浓度的增加,聚合物溶液表观粘度先急剧降低,然后趋于一稳定值。当OP-10浓度为1 mmol/L时,0.2 g/dL PAAV纯水溶液表观粘度为84 mPa·s;在盐水溶液中,相同OP-10浓度时,溶液表观粘度为12 mPa·s。结果表明,OP-10增粘能力最弱。淡水中SDBS对复合溶液的增粘能力更强,但盐水中CTAB更强。从pH对复合溶液表观粘度的影响规律看出:对于SDS或SDBS参与的复合溶液,在纯水溶液中,加入盐酸时,随着pH值的降低,溶液粘度下降;当加入碱时,pH值在7～9时,粘度下降。在盐水溶液中,当加入盐酸时,随着pH值的降低,溶液粘度先增加再减小;当加入碱时,pH值在7～9时,粘度下降。对于CTAB参与的复合溶液,在纯水溶液中,变化趋势同SDS,在盐水溶液中,当加入盐酸时,随着pH值的降低,溶液粘度减小;当加入碱时,pH值在7～9时,粘度下降。0.01 g/dL PAAV在5000 mg/L NaCl盐水溶液中,随着表面活性剂的浓度增加,PAAV溶液的表、界面张力的均先迅速降低,当SDS、SDBS、CTAB、OP-10、BS-12浓度分别为8 mmol/L、1.2 mmol/L、0.8 mmol/L、0.08 mmol/L和7 mmol/L时,表、界面张力趋于一稳定最低值,对应的最低表面张力值分别为28.2 mN/m、26.2 mN/m、25.2 mN/m、37.4 mN/m、29.2 mN/m;对应的最低界面张力值分别为1.01 mN/m、0.07 mN/m、0.011 mN/m、0.11 mN/m、4×10-4 mN/m。PAAV盐水溶液具有较好的表、界面活性。随着聚合物浓度的增加,PAAV溶液的表、界面张力先迅速降低,当聚合物浓度高于0.04 g/dL后,聚合物水溶液的表、界面张力均趋向稳定,分别为29.2 mN/m和3.5 mN/m。一定浓度的表面活性剂条件下,5000 mg/L NaCl盐水溶液中,聚表二元复合溶液随PAAV浓度的增加,表、界面张力先迅速降低,然后均趋向稳定,且都低于单独的聚合物溶液。当SDS、SDBS、CTAB、OP-10、BS-12浓度分别为1 mmol/L、0.3 mmol/L、0.3 mmol/L、0.03 mmol/L和1 mmol/L时,所对应的聚表二元复合盐水溶液在PAAV达到一定浓度后,出现的最低表面张力值分别为27.1 mN/m、24.1 mN/m、22.5 mN/m、28.4 mN/m和26.4 mN/m;出现的最低界面张力值分别为0.75 mN/m、0.42 mN/m、0.076 mN/m、0.57 mN/m和0.38 mN/m。结果表明,五种表面活性剂与共聚物PAAV都发生了不同程度的相互作用,CTAB与PAAV作用最强,能显著降低溶液的表、界面张力,其次是SDBS和BS-12,其中BS-12能很好的降低溶液界面张力,但CTAB和BS-12都带阳离子,在驱油过程中容易产生沉淀,发生相分离,不利于聚表二元体系的应用研究。因此,优选综合性能较好的SDBS作为聚表二元驱油体系的表面活性剂。更多还原

【Abstract】 The interaction between five surfactants with different molecular structures and a grafted associating acrylamide–based copolymer(PAAV) was studied in this paper. The five typical surfactants were surfactant sodium dodecyl sulfate (SDS)、sodium dodecyl benzene sulfonate (SDBS)、cetyltrimethylammonium bromide (CTAB)、alkyl poly (ethylene 10) ether (OP-10) and dodecyl dimethyl amine B lactone (BS-12),respectively. The effects of temperature、salt concentration、shear rate and copolymer concentration on apparent viscosity of solution, and the effects of copolymer concentration on surface tension and interfacial tension of the compound with salt in the solution were studied, the results showed that the polymer PAAV had good thickening properties、salt tolerance、heat resistance、and amphipathy because of the strong association of molecule. What’s more, the writer studied the influence law of the solution tackification performance with five different surfactants concentrations in pure water and brine solution and got the best concentration of compound of each surfactant and grafted associating copolymer. The flow law and the pH influence law of polymer and surfactant system in pure water were researched and got. By studying the influence law of surface tension and interfacial tension with different surfactant concentrations, we revealled the interaction mechanism between grafted associating copolymer and each surfactant.PAAV showed better thickening ability and salt-thickening effect behavior twice in a wide range of NaCl concentration. In the 5000 mg/L NaCl salt solution, 0.20 g/dL PAAV solution viscosity was 693.9 mPa·s; When the NaCl concentration was 30000 mg/L and 90000 mg/L, the solution viscosity was 265.9 mPa·s and 193 mPa·s,respectively in the range of 20 ~ 80℃. 0.20 g / dL PAAV due to the strong intermolecular association showed good heat resistance and thermal thickening behavior twice in the 5000 mg/L NaCl solution, and the highest viscosity of the solution was 889.8 mPa·s at 25℃; After more than 45℃, viscosity decreased slowly with increasing temperature, even at 80℃, viscosity of copolymer brine solution was still up to 510.9 mPa·s.The apparent viscosity of the 0.2 g/dL PAAV polymer increased rapidly and then decreased, and tended to balance lastly by addition of SDS、SDBS、CTAB in pure water and salt solution. The apparent viscosities of the solution were extremely 3443 mPa·s、3521 mPa·s and 2879 mPa·s in pure water, respectively, then the best thickening concentrations were 2 mmol/L, 0.8 mmol/L and 0.5 mmol/L, respectively.The solution viscosities were 869.3 mPa·s、905.1 mPa·s and 1107.8 mPa·s, and the best thickening concentrations were 1 mmol/L、0.3 mmol/L and 0.3 mmol/L in the 5000 mg/L NaCl brine solution, respectively. The polymer apparent viscosity increased firstly and then tended to balance with the increasing of BS-12 concentration. When BS-12 concentration was 1 mmol/L, the apparent viscosity of 0.2 g/dL PAAV pure water was 1036 mPa·s, The apparent viscosity of brine solution decreased to 753.5 mPa·s at the same BS-12 concentration. The apparent viscosity of the polymer solution drastically reduced, and then tended to a stable figure with increasing the concentration of OP-10; when OP-10 concentration was 1 mmol/L, the apparent viscosity in pure solution was 84 mPa·s. the apparent viscosity in brine solution was 12 mPa·s at the same OP-10 concentration. The results showed that the thickening ability of OP-10 was the weakest. The thickening ability of the composite solution by addition of SDBS was greater, but the thickening ability as the increasing of CTAB was stronger in salt water.The influence law of the apparent viscosity in complex solution of different pH showed: For the composite solution by addition of SDS or SDBS, the pH value lowered and the solution viscosity decreased with the adding of hydrochloric acid in pure water solution; when the pH value was 7 to 9 as the induction of alkali the viscosity decreased.With the induction of hydrochloric acid, the viscosity of the solution increased firstly and then decreased according to the lower of pH value in brine solution; when the pH value was 7 to 9 as the induction of alkali the, the viscosity decreased. The apparent viscosity of composite solution in pure water solution by addition of CTAB had the same change trend with SDS. The pH value lowered and the solution viscosity decreased with the adding of hydrochloric acid in brine solution; when the pH value was 7 to 9 as the induction of alkali the, the viscosity decreased. With increasing concentration of surfactant, the surface tension and interfacial tension of 0.01 g/dL PAAV solution in 5000 mg/L NaCl brine solution first rapidly reduced,when the concentration of SDS、SDBS、CTAB、OP-10、BS-12 respectively were 8 mmol/L、1.2 mmol/L、0.8 mmol/L、0.08 mmol/L and 7 mmol/L, and then tended to a stable minimum, the corresponding lowest surface tension values were 28.2 mN/m、26.2 mN/m、25.2 mN/m、37.4 mN/m、29.2 mN/m, and the corresponding values for minimum interfacial tension were 1.01 mN/m、0.07 mN/m、0.011 mN/m、0.11 mN/m、4×10-4mN/m, respectively.PAAV brine solution had good surface and interface activity. with the increase of polymer concentration, the Surface and interfacial tension of PAAV solution rapidly reduced and then all tended to stable, Separately for 29.2 mN/m and 3.5 mN/m when the concentration of polymer exceeded 0.04 g/dL. On the certain concentration of surfactant conditions, the Surface and interfacial tension reduced quickly with the increase of composite solution polymer PAAV concentration in 5000 mg/L NaCl brine solution. Then all tended to stability and were lower than those of polymer solution. When the concentration of SDS、SDBS、CTAB、OP-10、BS-12 were 1 mmol/L, 0.3 mmol/L, 0.3 mmol/L, 0.03 mmol/L and 1 mmol/L, the corresponding minimum surface tension value are were respectively 27.1 mN/m、24.1 mN/m、22.5 mN/m、28.4 mN/m and 26.4 mN/m;and minimum interfacial tension were respectively 0.75 mN/m、0.42 mN/m、0.076 mN/m、0.57 mN/m and 0.38 mN/m after PAAV reached a certain concentration in composite brine solution. These results showed that, varying degrees of interaction occurred between five kinds of surfactants and copolymer PAAV. The strongest effect between PAAV and CTAB, could significantly reduce the surface and interfacial tension, the second were SDBS and BS -12, BS-12 could well reduced solution interfacial tension. However, as the molecule structure of CTAB and BS-12 contained cation, precipitation and phase separation all easily emerged during the polymer flooding process, which was disadvantageous to application research of Polymer and surfactants system. So, SDBS, due to the better overall performance, was choosed for polymer flooding systems of polymer and surfactant.更多还原