烷基芳基磺酸盐分子量及其分布与吸附性能的研究
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摘要
本文以苯及其同系物、脂肪酰氯和α-溴代烷等为主要原料,精细合成了十八种结构明确、单一且高纯度的烷基芳基磺酸盐,经两相滴定法测定其活性物含量均大于95%。确定了液/固界面吸附的液固比为60,饱和吸附时间为32h。测定了五种平均分子量和分子量分布不同的烷基芳基磺酸盐复配体系的吸附等温线,分别考察了平均分子量、分子量分布、温度、无机盐、醇以及碱对复配体系在油砂/石英砂表面的吸附量的影响。结果表明:对五种分子量分布复配体系吸附量依次降低的顺序为递增分布、正态分布、反正态分布、递减分布、均匀分布;复配体系在油砂表面的吸附量随着磺酸盐的平均分子量的增大而增大,随温度的升高而降低,随NaCl浓度的增加而增加,随NaOH和Na2CO_3含量的增加而增加,随着NaHCO_3和KHCO_3含量的增加而降低,随着醇浓度及醇碳链的增加而逐渐降低,另外,在低浓度时MgCl_2、CaCl_2和Na_2SO_4比NaCl对吸附的影响显著。NaCl对油砂表面的吸附比对石英砂表面吸附的影响略大。异丁醇对复配体系在油砂表面吸附的影响依次大于叔丁醇、正丁醇。
采用旋滴法测定了45℃时复配烷基芳基磺酸盐体系与系列正构烷烃、大庆油田采油一厂原油及原油各组分的模拟油相间的界面张力。平均分子量为390的各复配体系的最小烷烃碳数均为9,最小烷烃碳数对应的界面张力值由小到大的复配体系为:反正态分布<递增分布<均匀分布<正态分布<递减分布;平均分子量为404复配体系除递增分布和递减分布复配体系的最小烷烃碳数为11外,其余各复配体系的最小烷烃碳数均为10,且最小烷烃碳数对应的界面张力值由小到大的复配体系为:反正态分布<递增分布<均匀分布<正态分布<递减分布;平均分子量为418的各复配体系的最小烷烃碳数均为10,最小烷烃碳数对应的界面张力值由小到大的复配体系为:反正态分布<递增分布<均匀分布<递减分布<正态分布;平均分子量为432及446的各复配体系的最小烷烃碳数均为11,最小烷烃碳数对应的界面张力值由小到大的复配体系为:反正态分布<递增分布<均匀分布<正态分布<递减分布。随着NaOH浓度的增加,油水动态界面张力最小值逐渐降低,在最佳碱浓度(0.2mol/L)时出现最低值,随后逐渐升高,最终趋于平衡。随着表面活性剂浓度的增加界面张力开始降低,当表面活性剂浓度达到一个值时,界面张力随着表面活性剂浓度的增加而升高。平均分子量为432的复配体系降低油水界面张力的能力最强,与一厂原油的匹配效果最佳。一厂原油及原油各组分与复配烷基芳基磺酸盐的平均分子量404~432最为匹配,油水界面张力可达到超低界面张力值。反正态分布复配体系降低油水界面张力的能力相对较强,与原油各组分的界面关系匹配较好;而递减分布复配体系降低油水界面张力的能力相对较差。
Eighth kinds of alkylaryl sulfonate which had clear structure and high purity were synthesized from benzene and its analogies, acyl chloride and alkyl halide. The content of all the products were all over 95% determined by two-phase titration.
Liquid-solid ratio of solid/liquid interface adsorption was 60, and saturation adsorption time was 32 hours. The isotherms and the adsorption amount of five types of molecular weight distribution formed from the mixture of five molecular weight alkyl aryl sulfonates on solid-liquid interface were measured. The impacts of the molecular weight, molecular weight distribution, adsorption temperature, the inorganic salt , alkalis and alcohols on the adsorption of alkyl aryl sulfonates compound on the oil sand / quartz sand surface were discussed, respectively. The results showed that the adsorption amount of five types of molecular weight distribution formed from alkyl aryl sulfonate compounds were in turn decreased reduce in the following order, i.e., the incremental distribution, normal distribution, reverse normal distribution, decreasing distribution, uniform distribution; while the adsorption amount of alkyl aryl sulfonate compound on the oil sands surface increased with their molecular weights, decreased with the adsorption temperature, increased with the NaCl concentration, increases with the increasing NaOH and NaCO_3 concentration , decreases with increasing NaHCO_3 and KHCO_3 concentration, and gradually decreases with the increasing alcohols concentration and alcohols carbon chain.. The effect of NaCl on the adsorption of the alkyl aryl sulfonate compound on the oil sands surface was slightly larger than on the quartz sand surface.Moreover, it was found that the effect of addition of CaCl_2, MgCl_2, Na_2SO_4 etc. on the adsorption amount was more significant than NaCl. The effect of the isobutanol on the adsorption of complex systems was in turn bigger than tertiary butanol and n-butyl alcohol.
The interface tension of alkyl aryl sulfonates compound with series of n-alkanes, the simulation oil phase of crude oil and its various components in 1th plant of Daqing oilfield was measured by spin-drop method at 45℃.The nmin of alkyl aryl sulfonates compound system which average molecular weight were 390, 432 and 446, were 9 ,11 and 11, and the nmin corresponding to the minimum interfacial tension value from small to large complex systems were showed as: reverse normal distribution< incremental distribution< uniform distribution< normal distribution< descending distribution. The nmin of 404 molecular weight complex systems were 10 except incremental distribution and descending distribution were 11, and then the nmin corresponding to the minimum interfacial tension value from small to large complex systems were showed as: reverse normal distribution< incremental distribution< uniform distribution< normal distribution< descending distribution. The nmin of 418 molecular weight complex systems were 10 , and the nmin corresponding to the minimum interfacial tension value from small to large complex systems were showed as: reverse normal distribution< incremental distribution< uniform distribution< descending distribution < normal distribution. The minimum dynamic interfacial tension was decreased with the increasing NaOH concentration, and it was lowest When best caustic concentration (0.2mol/L), then it was increased, finally, it tended to be balanced. The interfacial tension was decreased with the increasing alkyl benzene sulfonate compound concentration, When the surfactant concentration reached a value, the interfacial tension was increased with the increasing concentration. The 432 molecular weight complex systems were the best to increase the Oil-water interfacial tension ,and they matched best with the crude oil of 1th plant of Daqing oilfield. The crude oil of 1th plant and its various components matched best with the 404~432 molecular weight complex systems, and the Oil-water interfacial tension can reach ultra-low interfacial tension values. Reverse normal distribution complex systems the ability to reduce the interfacial tension was relatively strong, and the interface between the components of crude oil matched best. Descending distribution complex systems the ability to reduce the interfacial tension was relatively poor.
采用旋滴法测定了45℃时复配烷基芳基磺酸盐体系与系列正构烷烃、大庆油田采油一厂原油及原油各组分的模拟油相间的界面张力。平均分子量为390的各复配体系的最小烷烃碳数均为9,最小烷烃碳数对应的界面张力值由小到大的复配体系为:反正态分布<递增分布<均匀分布<正态分布<递减分布;平均分子量为404复配体系除递增分布和递减分布复配体系的最小烷烃碳数为11外,其余各复配体系的最小烷烃碳数均为10,且最小烷烃碳数对应的界面张力值由小到大的复配体系为:反正态分布<递增分布<均匀分布<正态分布<递减分布;平均分子量为418的各复配体系的最小烷烃碳数均为10,最小烷烃碳数对应的界面张力值由小到大的复配体系为:反正态分布<递增分布<均匀分布<递减分布<正态分布;平均分子量为432及446的各复配体系的最小烷烃碳数均为11,最小烷烃碳数对应的界面张力值由小到大的复配体系为:反正态分布<递增分布<均匀分布<正态分布<递减分布。随着NaOH浓度的增加,油水动态界面张力最小值逐渐降低,在最佳碱浓度(0.2mol/L)时出现最低值,随后逐渐升高,最终趋于平衡。随着表面活性剂浓度的增加界面张力开始降低,当表面活性剂浓度达到一个值时,界面张力随着表面活性剂浓度的增加而升高。平均分子量为432的复配体系降低油水界面张力的能力最强,与一厂原油的匹配效果最佳。一厂原油及原油各组分与复配烷基芳基磺酸盐的平均分子量404~432最为匹配,油水界面张力可达到超低界面张力值。反正态分布复配体系降低油水界面张力的能力相对较强,与原油各组分的界面关系匹配较好;而递减分布复配体系降低油水界面张力的能力相对较差。
Eighth kinds of alkylaryl sulfonate which had clear structure and high purity were synthesized from benzene and its analogies, acyl chloride and alkyl halide. The content of all the products were all over 95% determined by two-phase titration.
Liquid-solid ratio of solid/liquid interface adsorption was 60, and saturation adsorption time was 32 hours. The isotherms and the adsorption amount of five types of molecular weight distribution formed from the mixture of five molecular weight alkyl aryl sulfonates on solid-liquid interface were measured. The impacts of the molecular weight, molecular weight distribution, adsorption temperature, the inorganic salt , alkalis and alcohols on the adsorption of alkyl aryl sulfonates compound on the oil sand / quartz sand surface were discussed, respectively. The results showed that the adsorption amount of five types of molecular weight distribution formed from alkyl aryl sulfonate compounds were in turn decreased reduce in the following order, i.e., the incremental distribution, normal distribution, reverse normal distribution, decreasing distribution, uniform distribution; while the adsorption amount of alkyl aryl sulfonate compound on the oil sands surface increased with their molecular weights, decreased with the adsorption temperature, increased with the NaCl concentration, increases with the increasing NaOH and NaCO_3 concentration , decreases with increasing NaHCO_3 and KHCO_3 concentration, and gradually decreases with the increasing alcohols concentration and alcohols carbon chain.. The effect of NaCl on the adsorption of the alkyl aryl sulfonate compound on the oil sands surface was slightly larger than on the quartz sand surface.Moreover, it was found that the effect of addition of CaCl_2, MgCl_2, Na_2SO_4 etc. on the adsorption amount was more significant than NaCl. The effect of the isobutanol on the adsorption of complex systems was in turn bigger than tertiary butanol and n-butyl alcohol.
The interface tension of alkyl aryl sulfonates compound with series of n-alkanes, the simulation oil phase of crude oil and its various components in 1th plant of Daqing oilfield was measured by spin-drop method at 45℃.The nmin of alkyl aryl sulfonates compound system which average molecular weight were 390, 432 and 446, were 9 ,11 and 11, and the nmin corresponding to the minimum interfacial tension value from small to large complex systems were showed as: reverse normal distribution< incremental distribution< uniform distribution< normal distribution< descending distribution. The nmin of 404 molecular weight complex systems were 10 except incremental distribution and descending distribution were 11, and then the nmin corresponding to the minimum interfacial tension value from small to large complex systems were showed as: reverse normal distribution< incremental distribution< uniform distribution< normal distribution< descending distribution. The nmin of 418 molecular weight complex systems were 10 , and the nmin corresponding to the minimum interfacial tension value from small to large complex systems were showed as: reverse normal distribution< incremental distribution< uniform distribution< descending distribution < normal distribution. The minimum dynamic interfacial tension was decreased with the increasing NaOH concentration, and it was lowest When best caustic concentration (0.2mol/L), then it was increased, finally, it tended to be balanced. The interfacial tension was decreased with the increasing alkyl benzene sulfonate compound concentration, When the surfactant concentration reached a value, the interfacial tension was increased with the increasing concentration. The 432 molecular weight complex systems were the best to increase the Oil-water interfacial tension ,and they matched best with the crude oil of 1th plant of Daqing oilfield. The crude oil of 1th plant and its various components matched best with the 404~432 molecular weight complex systems, and the Oil-water interfacial tension can reach ultra-low interfacial tension values. Reverse normal distribution complex systems the ability to reduce the interfacial tension was relatively strong, and the interface between the components of crude oil matched best. Descending distribution complex systems the ability to reduce the interfacial tension was relatively poor.
引文
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