二硫代氨基甲酸盐的絮凝机理及对聚合物驱采油污水的处理性能
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摘要
聚合物驱采油污水由于含有大量的残余聚丙烯酰胺(HPAM),污水粘度大,乳化稳定性增强,处理难度增大,出水水质难以达到回注原地层的水质要求。针对聚合物驱采出水的特点,在现有污水处理工艺系统的基础上研制高效的油水分离剂,是目前有效处理含聚污水最为切实可行的方法。
本文首先用端氨基聚醚化合物与二硫化碳反应,合成二硫代氨基甲酸盐(dithiocarbamate,简称DTC),采用红外光谱(IR)、元素分析等现代分析仪器对合成产物进行了分析表征。以高岭土悬浊液为处理对象考察了DTC盐的絮凝特性,结合Zeta电位分析、扫描电镜(SEM)等方法探讨了DTC药剂的絮凝机理。然后用合成的DTC药剂处理模拟聚驱采油污水,考察了投药量、Fe~(2+)浓度、HPAM浓度(0,200,500和900 mg/L)、pH值(4.5～9.5)、无机盐离子等因素对除油效果和絮凝过程的影响。利用透光散射技术(PDA)分析了絮体的生长过程,评价了药剂对胜利油田聚驱采出水的絮凝性能。
研究表明,DTC盐单独使用不具有絮凝的作用,DTC分子中带有CSS~-基团,可与污水中的Fe~(2+)发生配位反应而形成絮体,并在搅拌过程中依靠絮体的网捕和卷扫作用去除水中的胶体颗粒。在对模拟污水的处理中,高浓度HPAM的存在,降低了DTC(T403)与Fe~(2+)碰撞反应的几率,影响絮体的生长和对油珠的网卷作用。Fe~(3+)易与氧原子配位,絮凝搅拌条件下不能与DTC螯合产生絮体。中性和弱酸性条件下DTC药剂的除油效果较好,pH值升高会促使Fe~(2+)的氧化,影响絮凝效果。水样中的HCO_3~-由于水解产生OH~-,也会影响药剂的絮凝作用。DTC盐用以处理胜利油田聚驱采油污水时,在Fe~(2+)配合作用下,20 mg/L的投药量可以使油浓度从70 mg/L降至10 mg/L以下。PDA絮凝动态分析表明,絮凝剂发挥作用快,絮体尺寸较大。
Produced water from polymer flooding is difficult to be treated for its high viscosity and emulsified characteristics owing to containing amount of residual polymer(HPAM).The water quality after treatment by conditional process used in the oilfields couldn't reach the standards for being injected into the stratum.The treatment of wastewater containing HPAM has been an important problem.Developing flocculants that could effectively separate oil and suspended substances(SS) from the polymer solution is an economic and applicable method at present.
Dithiocarbamate flocculants were synthesized with amine-terminated polyoxypropane-ether compounds.The products were analyzed by infrared spectra and element composition.Flocculation activity of DTC agents in treating the kaolite suspensions were investigated,combining with analysis of zeta potential and scanning electron microscope to elucidate flocculation mechanisms.Then flocculating performance on removing oil from simulated polymer flooding produced water was studied.The effect of DTC's dosage,the concentrations of ferrous ions and HPAM(0, 200,500 and 900 mg/L),pH(4.5～9.5) and minearal ions were investigated, respectively.Finally DTC's flocculation performance on actually produced water from polymer flooding in Shengli Oilfield was evaluated.
The results confirmed that there were no flocs growing up when DTC agent was dosed alone.Containing dithiocarbamic groups(CSS),DTC agent coordinated with ferrous ions in the wastewater through which the flocs formed.The net capturing and sweeping of flocs was identified to be the main flocculation mechanism.On treating simulated samples,high concentrations of HPAM decreased chelating rates between DTC and Fe~(2+) and flocs growing,and oil removal.Fe~(3+) couldn't chelate with DTC in the flocculated process since it coordinated with oxygen atom easily.Oil removal effect was better under the condition of neutrality partial to weak acidity due to that Fe~(2+) would be oxided rapidly at basic condition.On treating the actual polymer flooding produced water,20mg/L dosage of DTC was able to decrease the oil concentrations below the 10mg/L combined with Fe~(2+).PDA analyzer showed that the flocs formed and grew up rapidly,the final size being big.
本文首先用端氨基聚醚化合物与二硫化碳反应,合成二硫代氨基甲酸盐(dithiocarbamate,简称DTC),采用红外光谱(IR)、元素分析等现代分析仪器对合成产物进行了分析表征。以高岭土悬浊液为处理对象考察了DTC盐的絮凝特性,结合Zeta电位分析、扫描电镜(SEM)等方法探讨了DTC药剂的絮凝机理。然后用合成的DTC药剂处理模拟聚驱采油污水,考察了投药量、Fe~(2+)浓度、HPAM浓度(0,200,500和900 mg/L)、pH值(4.5～9.5)、无机盐离子等因素对除油效果和絮凝过程的影响。利用透光散射技术(PDA)分析了絮体的生长过程,评价了药剂对胜利油田聚驱采出水的絮凝性能。
研究表明,DTC盐单独使用不具有絮凝的作用,DTC分子中带有CSS~-基团,可与污水中的Fe~(2+)发生配位反应而形成絮体,并在搅拌过程中依靠絮体的网捕和卷扫作用去除水中的胶体颗粒。在对模拟污水的处理中,高浓度HPAM的存在,降低了DTC(T403)与Fe~(2+)碰撞反应的几率,影响絮体的生长和对油珠的网卷作用。Fe~(3+)易与氧原子配位,絮凝搅拌条件下不能与DTC螯合产生絮体。中性和弱酸性条件下DTC药剂的除油效果较好,pH值升高会促使Fe~(2+)的氧化,影响絮凝效果。水样中的HCO_3~-由于水解产生OH~-,也会影响药剂的絮凝作用。DTC盐用以处理胜利油田聚驱采油污水时,在Fe~(2+)配合作用下,20 mg/L的投药量可以使油浓度从70 mg/L降至10 mg/L以下。PDA絮凝动态分析表明,絮凝剂发挥作用快,絮体尺寸较大。
Produced water from polymer flooding is difficult to be treated for its high viscosity and emulsified characteristics owing to containing amount of residual polymer(HPAM).The water quality after treatment by conditional process used in the oilfields couldn't reach the standards for being injected into the stratum.The treatment of wastewater containing HPAM has been an important problem.Developing flocculants that could effectively separate oil and suspended substances(SS) from the polymer solution is an economic and applicable method at present.
Dithiocarbamate flocculants were synthesized with amine-terminated polyoxypropane-ether compounds.The products were analyzed by infrared spectra and element composition.Flocculation activity of DTC agents in treating the kaolite suspensions were investigated,combining with analysis of zeta potential and scanning electron microscope to elucidate flocculation mechanisms.Then flocculating performance on removing oil from simulated polymer flooding produced water was studied.The effect of DTC's dosage,the concentrations of ferrous ions and HPAM(0, 200,500 and 900 mg/L),pH(4.5～9.5) and minearal ions were investigated, respectively.Finally DTC's flocculation performance on actually produced water from polymer flooding in Shengli Oilfield was evaluated.
The results confirmed that there were no flocs growing up when DTC agent was dosed alone.Containing dithiocarbamic groups(CSS),DTC agent coordinated with ferrous ions in the wastewater through which the flocs formed.The net capturing and sweeping of flocs was identified to be the main flocculation mechanism.On treating simulated samples,high concentrations of HPAM decreased chelating rates between DTC and Fe~(2+) and flocs growing,and oil removal.Fe~(3+) couldn't chelate with DTC in the flocculated process since it coordinated with oxygen atom easily.Oil removal effect was better under the condition of neutrality partial to weak acidity due to that Fe~(2+) would be oxided rapidly at basic condition.On treating the actual polymer flooding produced water,20mg/L dosage of DTC was able to decrease the oil concentrations below the 10mg/L combined with Fe~(2+).PDA analyzer showed that the flocs formed and grew up rapidly,the final size being big.
引文
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