【作者】 李春晓；

【导师】 岳钦艳；

【作者基本信息】 山东大学 ， 环境工程， 2009， 硕士

【摘要】 在聚合物驱油技术提高石油采收率的同时,也随之产生了大量的采油污水。聚驱采油污水中含有大量残余的聚合物,粘度大,乳化程度高。用油田现有的采油污水处理剂处理聚驱采油污水,出现了油水分离困难、出水含油率高、废水外排严重污染环境等问题。针对上述问题,本研究以丙烯酰胺（AM）、二甲基二烯丙基氯化铵（DMDAAC）、丙烯酸丁酯（BA）为原料,采用水溶液自由基胶束聚合法,合成得到丙烯酰胺-二甲基二烯丙基氯化铵.丙烯酸丁酯共聚物[P（AM-DMDAAC-BA）],并将其应用于油田含油废水的处理,以提高除油性能。本论文的主要研究内容及结论如下:（1）采用水溶液自由基胶束聚合方式,用复合引发剂引发聚合,得到了具备不同分子量、阳离子度和疏水单体含量的系列有机高分子絮凝剂—二甲基二烯丙基氯化铵-丙烯酰胺-丙烯酸丁酯三元共聚物[P（AM-DMDAAC-BA）]。在研制过程中,系统地考察了不同引发体系、引发体系中各成分的用量、引发剂用量、引发时间、聚合反应时间、聚合单体总质量分数、阳离子单体含量、疏水单体含量、表面活性剂用量等因素对聚合反应的影响。结果表明,使用由氧化还原体系与热分解引发剂组成的复合引发体系,可以提高反应的转化率和聚合物的特性粘度;在保持单体的总质量分数为30.0%、反应单体的物质的量配比为n（AM）:n（DMDAAC）:n（BA）=68.6:29.4:2.0的条件下,合成P（AM-DMDAAC-BA）的最佳条件为:引发剂、CTAB含量分别占单体总质量的0.15%和2.0%,引发体系中各成分质量比为m（Na₂S₂O₃）:m（K₂S₂O₈）:m（AIBN）=1.0:2.0:1.0,引发温度为30℃,聚合反应时间为6 h;合成过程中添加尿素能够明显缩短溶解时间,当尿素用量为反应单体质量的2.5%时,产品溶解时间缩短,极大改善了聚合物的溶解性能。（2）运用红外光谱仪、核磁共振谱仪、透射电镜、同步热分析仪等现代分析仪器对P（AM-DMDAAC-BA）进行了分析表征。结果表明,聚合物已生成,产品具有较好的热稳定性。（3）通过烧杯实验研究了疏水缔合阳离子型聚丙烯酰胺对含油废水的除油效果,考察了聚合物中阳离子度、疏水单体含量、特性粘度、投加量对含油废水除油效果的影响:并与其他不同类型的高分子絮凝剂的除油效果做了比较。结果表明,该产品对含油废水具有很好的除油效果;在投加量为50 mg/L、阳离子度为24.3%～52.8%、疏水单体的含量为2.0%左右、特性粘度为500～700 mL/g时,对含油废水具有较好的除油效果;当絮凝剂的阳离子度为24.3%、BA含量为2.0%、特性粘度为636 mL/g、投加量为50 mg/L时,除油效果最佳,除油率可达93.4%。P（AM-DMDAAC-BA）与非离子型聚丙烯酰胺、阴离子型聚丙烯酰胺、聚环氧氯丙烷胺、聚二甲基二烯丙基氯化铵4种有机高分子絮凝剂相比,在除油方面表现出良好的性能;与阳离子型聚丙烯酰胺相比,可减少污水处理成本。（4）将聚合物与常用的天然高分子助凝剂可溶性淀粉、无机絮凝剂硫酸铝分别配合使用,考察了其协同作用。结果表明,P（AM-DMDAAC-BA）与可溶性淀粉和硫酸铝配合使用时,均具有较好的协同作用,可以减少有机絮凝剂的用量,在保证较好的除油效果下降低了成本;与无机絮凝剂配合使用时,与单独使用无机絮凝剂相比,可以提高沉降速率,减少污泥量;采取先投加无机絮凝剂、后投加有机絮凝剂的投加方式,对含油废水的除油效果较好。综合结果表明,P（AM-DMDAAC-BA）具有良好的性能,是一种适宜于含油废水处理的高效的有机高分子絮凝剂。更多还原

【Abstract】 With the applying of polymer flooding to increase oil production in many oilfields,large amount of wastewater,which is much more difficult to treat than that from water flooding,has been produced.The produced water from polymer flooding contains a quantity of residual hydrolyzed polyacrylamide.As a result,the wastewater is of high viscosity and emulsion stability.The present wastewater treatment agent in the oilfield fails to treat the wastewater from polymer flooding properly.Therefore,it is difficult for the oil-water separation,and serious environment pollution would also be caused if the wastewater was discharged to land surface.It has high application value and environment benefits to develop effective water treatment agent for the oil field wastewater.Considering the properties of oil field wastewater and the weakness in the oil field wastewater treatment,a series of hydrophobically associating cationic copolymers,namely,poly（AM-DMDAAC-BA）,were synthesized with acrylamide （AM）,dimethyldially- ammonium chloride（DMDAAC） and butylacrylate（BA） by the micellar free radical copolymerization technique.The main contents and results are following:（1） Copolymerization was initiated by a complex initiation system,which was composed of redox initiator（K₂S₂O₈-Na₂S₂O₃） and thermal decomposition initiator （azobisisobutyronitrile）.The effects of synthesis conditions,such as various initiation systems,initiator concentration,initiation temperature,polymerization time, monomers concentration,monomer ratio and surfactant concentration on properties of polymers were studied.The results showed that conversion and molecular weight of polymer could be raised with the use of the complex initiation system.The optimum conditions of copolymerization were as follows:the initiation temperature was 30℃; polymerization time was 6 h;monomers concentration was 30.0%;molar ratio of AM, DMDAAC and BA was 68.6,29.4 and 2.0,respectively;percentages of initiator and surfactant by weight in the monomers were 0.15%and 2.0%,respectively; compositions ratio in the initiation system was m（Na₂S₂O₃）:m（K₂S₂O₈）: m（AIBN）=1.0:2.0:1.0.Dissolution time was shorten by the addition of urea.When the percentage of urea by weight in the monomers was 2.5%,the solubility of polymer could be improved effectively.（2） IR,NMR,TEM and DSC-TGA were used to characterize the polymer.The results proved the formation of hydrophobically associating cationic copolymers,and showed that the polymer had good thermo-stability.（3） Deoiling property of P（AM-DMDAAC-BA） was studied by jar tests.The effects of cationic degree,hydrophobic group content,intrinsic viscosity,flocculant dosage on oil removal rate were studied.The results showed that,the a good deoiling effect could be obtained when the cationic degree,hydrophobic group content and intrinsic viscosity of flocculant were 24.3～52.8%,2.0%and 500～700 mL/g, respectively.The best oil removal rate was 93.4%when cationic degree was 24.3%, hydrophobic group content was 2.0%,intrinsic viscosity was 636 mL/g and flocculant dosage was 50 mg/L.The deoiling effect was superior to other traditional organic polymer flocculants including PAM,APAM,EPI-DMA and PDMDAAC.It could reduce the water treatment cost compared with CPAM.（4） Combining P（AM-DMDAAC-BA） with natural polymer coagulator（soluble starch） or inorganic flocculant（Al₂SO₄） in the treatment of oil field wastewater were applied to investigate the synergistic effect of different flocculants.The result indicated that the effect of oil removal by using combining flocculants could even be better than that of P（AM-DMDAAC-BA） alone,and the amount of P（AM-DMDAAC-BA） could be reduced.And also,settlement velocity could be accelerated and the amount of sludge was smaller than using inorganic flocculant alone.To achieve superior deoiling effect,the inorganic flocculant should be added before the organic flocculant.The results above showed that,P（AM-DMDAAC-BA） exhibited good performance of coagulation.It was suitable for the treatment of oil field wastewater.更多还原