ASP三元复合驱采出水稳定性研究及处理技术探索
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摘要
我国是水资源短缺和水污染严重的国家之一。随着我国胜利、大庆等各大油田相继进入三次采油阶段,ASP三元复合驱采油技术逐渐应用并推广,以此来提高原油采收率,但随之而来的,ASP驱采出水的量也在不断增加。ASP驱采出水含有大量残余驱油剂组分(聚合物,HPAM、碱,NaOH和表面活性剂,WPS)、原油及一些悬浮杂质,是一个复杂的、稳定的乳化体系,并且很难处理。ASP驱采出水必须经过处理达到规定的标准后才能回注或者排放,但是目前国内外尚无有效的处理该类废水的方法。
本文制备出ASP驱模拟采出水后,研究了残余驱油剂组分对模拟采出水油水分离性能、油滴Zeta电位、油水界面流变性及油滴粒径的影响,并以此对ASP驱采出水的稳定性机理进行了分析探讨；在此基础上,用自制白泥处理剂对ASP驱模拟采出水进行处理,并用红外光谱及扫描电镜对生成的沉淀物进行了表征,以此探讨了白泥处理剂处理采出水的处理条件和反应机理。研究结果如下：
(1)HPAM浓度低时(3.0×106HPAM小于300 mg／L,5.0×106HPAM小于200mg／L,1.2×107HPAM小于200 mg／L),其促进油滴聚并的作用较强,而HPAM浓度较高时,其提高体相粘度和油滴Zeta电位,阻碍油滴聚并的作用增强,所以采出水的稳定性随其浓度增加先减弱后增强；WPS在油水界面的吸附降低了界面张力并提高了油滴Zeta电位,从而使得采出水的稳定性大大增强；NaOH与原油中的酸性组分反应生成界面活性物质,这些物质在油水界面的吸附能够降低界面张力、粘弹性模量,并提高油滴Zeta电位,随其浓度增加,采出水的稳定性先增强后减弱。
(2)白泥处理剂对ASP驱模拟采出水有较好的处理效果,在选定的处理条件下,当初始含油量为300-2700 mg／L时,处理后采出水的含油量都接近国家污水综合排放标准的要求。经试验筛选出的处理条件为：投加量8000-9000 mg／L,pH11-12.5,搅拌强度200-350 r／min,搅拌时间90-180 s,沉降时间20 min以上温度15-40℃。通过透射电镜、红外光谱分析,推断白泥处理剂的处理机理与新生相氢氧化物的性质有关。
Water resource shortage and water pollution are serious in our country. With the oilfield such as Shengli, Daqing in our country entering the period of Enhanced Oil Recovery (EOR), the alkaline/surfactant/polymer (ASP) flooding technology has been successfully used in oilfield in order to increase the crude oil recovery, but more and more ASP produced water is produced. Produced water from ASP flooding containing large quantities of residual chemicals (alkali, surfactant and polymer), crude oil and suspended substances is a complex and stable emulsion system, and it is difficult to treat. Before reinjection and discharge, ASP produced water must be treated and measure up to a given standard. However, now there was no appropriate treatment method for such wastewater at home and abroad.
After the preparation of simulated ASP produced water, the effects of residual oil displacement agents on oil-water separation of simulated produced water, zeta potentail, oil-water interfacial rheology and oil droplet size were investigated, and then the stability mechanism of ASP produced water was analyzed. And on that basis, the treatment on simulated produced water from ASP by using treating-agent of alkaline white mud was studied, and the precipitate was characterized by FTIR and SEM. And then the treatment conditions and reaction mechanism were approached. It was found that:
(1) When HPAM concentration is low (3.0×106 HPAM< 300 mg/L,5.0×106 HPAM<200 mg/L,1.2×107 HPAM<200 mg/L), the flocculation of HPAM is the dominant factor, while the high viscosity of produced water and zeta potential of oil droplet play a significant role at high HPAM concentration, therefore the emulsion stability of produced water is initially degraded and then enhanced with the increase of HPAM concentration. The adsorption of WPS on oil-water interface decreases interfacial tension and increases zeta potential, and thus enhances the emulsion stability remarkably. NaOH can react with acid components of crude oil and form interface active substances, and the adsorption of these substances on oil-water interface can decrease interfacial tension, viscoelastic modulus and increase zeta potential, so the emulsion stability of produced water is enhanced gradually with the increase of NaOH concentration up to 300 mg/L and then weakened with the further increase of NaOH concentration.
(2) It is effective to treat simulated produced water from ASP by using alkaline white mud treating-agent. When initial oil concentrations of produced water are between 300 mg/L and 2700 mg/L and under the selected treatment conditions, the oil concentrations after treatment are close to the demand of national integrated wastewater discharge standard. And the selected treatment conditions through tests are as follows:dosage is 8000-9000 mg/L, pH is 11-12.5, stirring intensity is 200-350 r/min, stirring time is 90-180 s, settling time is above 20 min and temperature is 15-40℃. And the treatment mechanism of alkaline white mud treating-agent is maybe related to the property of new phase hydroxide by surmising.
本文制备出ASP驱模拟采出水后,研究了残余驱油剂组分对模拟采出水油水分离性能、油滴Zeta电位、油水界面流变性及油滴粒径的影响,并以此对ASP驱采出水的稳定性机理进行了分析探讨；在此基础上,用自制白泥处理剂对ASP驱模拟采出水进行处理,并用红外光谱及扫描电镜对生成的沉淀物进行了表征,以此探讨了白泥处理剂处理采出水的处理条件和反应机理。研究结果如下：
(1)HPAM浓度低时(3.0×106HPAM小于300 mg／L,5.0×106HPAM小于200mg／L,1.2×107HPAM小于200 mg／L),其促进油滴聚并的作用较强,而HPAM浓度较高时,其提高体相粘度和油滴Zeta电位,阻碍油滴聚并的作用增强,所以采出水的稳定性随其浓度增加先减弱后增强；WPS在油水界面的吸附降低了界面张力并提高了油滴Zeta电位,从而使得采出水的稳定性大大增强；NaOH与原油中的酸性组分反应生成界面活性物质,这些物质在油水界面的吸附能够降低界面张力、粘弹性模量,并提高油滴Zeta电位,随其浓度增加,采出水的稳定性先增强后减弱。
(2)白泥处理剂对ASP驱模拟采出水有较好的处理效果,在选定的处理条件下,当初始含油量为300-2700 mg／L时,处理后采出水的含油量都接近国家污水综合排放标准的要求。经试验筛选出的处理条件为：投加量8000-9000 mg／L,pH11-12.5,搅拌强度200-350 r／min,搅拌时间90-180 s,沉降时间20 min以上温度15-40℃。通过透射电镜、红外光谱分析,推断白泥处理剂的处理机理与新生相氢氧化物的性质有关。
Water resource shortage and water pollution are serious in our country. With the oilfield such as Shengli, Daqing in our country entering the period of Enhanced Oil Recovery (EOR), the alkaline/surfactant/polymer (ASP) flooding technology has been successfully used in oilfield in order to increase the crude oil recovery, but more and more ASP produced water is produced. Produced water from ASP flooding containing large quantities of residual chemicals (alkali, surfactant and polymer), crude oil and suspended substances is a complex and stable emulsion system, and it is difficult to treat. Before reinjection and discharge, ASP produced water must be treated and measure up to a given standard. However, now there was no appropriate treatment method for such wastewater at home and abroad.
After the preparation of simulated ASP produced water, the effects of residual oil displacement agents on oil-water separation of simulated produced water, zeta potentail, oil-water interfacial rheology and oil droplet size were investigated, and then the stability mechanism of ASP produced water was analyzed. And on that basis, the treatment on simulated produced water from ASP by using treating-agent of alkaline white mud was studied, and the precipitate was characterized by FTIR and SEM. And then the treatment conditions and reaction mechanism were approached. It was found that:
(1) When HPAM concentration is low (3.0×106 HPAM< 300 mg/L,5.0×106 HPAM<200 mg/L,1.2×107 HPAM<200 mg/L), the flocculation of HPAM is the dominant factor, while the high viscosity of produced water and zeta potential of oil droplet play a significant role at high HPAM concentration, therefore the emulsion stability of produced water is initially degraded and then enhanced with the increase of HPAM concentration. The adsorption of WPS on oil-water interface decreases interfacial tension and increases zeta potential, and thus enhances the emulsion stability remarkably. NaOH can react with acid components of crude oil and form interface active substances, and the adsorption of these substances on oil-water interface can decrease interfacial tension, viscoelastic modulus and increase zeta potential, so the emulsion stability of produced water is enhanced gradually with the increase of NaOH concentration up to 300 mg/L and then weakened with the further increase of NaOH concentration.
(2) It is effective to treat simulated produced water from ASP by using alkaline white mud treating-agent. When initial oil concentrations of produced water are between 300 mg/L and 2700 mg/L and under the selected treatment conditions, the oil concentrations after treatment are close to the demand of national integrated wastewater discharge standard. And the selected treatment conditions through tests are as follows:dosage is 8000-9000 mg/L, pH is 11-12.5, stirring intensity is 200-350 r/min, stirring time is 90-180 s, settling time is above 20 min and temperature is 15-40℃. And the treatment mechanism of alkaline white mud treating-agent is maybe related to the property of new phase hydroxide by surmising.
引文
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