【作者】 张鹏；

【导师】 郑怀礼；

【作者基本信息】 重庆大学 ， 市政工程， 2011， 博士

【摘要】 邻苯二甲酸酯类化合物（PAEs）作为一种重要的化工原料,广泛应用于各个行业当中,导致了对环境的普遍污染。由于它还具有干扰人类及动物的内分泌系统的功能,能够损害生殖和发育,因此也被称为内分泌干扰物,环境激素。这类化学物质的性质很稳定,且在自然界中具有持久性、累积性、难自然降解的特点。当前作为城市水源水的许多江河、湖泊受到PAEs的普遍污染,如果不能将其控制在适当的浓度以下,将会对人类和动物的健康产生威胁,因此研究去除水体中PAEs的有效方法和技术已经变得十分迫切、必要。腐殖酸类物质（humic acid,HA）是天然水体中一类重要的有机物,也是天然有机物的重要组成成分,由于其特殊的化学结构和性质,也会对人体和水生生物产生影响,因此研究其去除方法、机理对于保障饮用水安全是必不可少的。论文首先对常规絮凝法能否有效去除水体中的PAEs类物质进行了大量探讨实验,从而论证了应用絮凝法能够有效去除环境激素PAEs类物质,进而有针对性的合成了高性能的聚二甲基二烯丙基氯化铵-丙烯酰胺共聚物（PDA）,并对得到的产物进行了表征,分析验证了PDA的性质。采用近红外反射光谱法,通过建立模型提出了测定PDA阳离子度和AM单体残留量的新方法。最后将制得的PDA产物应用于处理水体中PAEs类物质和HA,采用单因素实验对去除条件进行了优化,并研究其去除机理。论文的主要研究结论如下:（1）采用絮凝法去除水体中PAEs类物质时,目标物为邻苯二甲酸二甲酯（DMP）和邻苯二甲酸二乙酯（DEP）,发现有机絮凝剂PDMDAAC和CPAM对其有很好的去除效果,使用PDMDAAC时,对DMP的最大去除率可达到63.8%;使用自制CPAM时,对DMP的最大去除率可达到97.3%;当PDMDAAC与CPAM复合使用时,其中PDMDAAC为主絮凝剂,CPAM为助凝剂,对DMP的最大去除率可达到99.8%;PDMDAAC与CPAM对环境激素DEP也有很好的去除效果,最大去除率分别为49.2%、88.3%。采用主成分分析法得出:絮凝过程中对絮凝剂去除效果的影响依次为絮凝剂投加量> pH >搅拌时间>沉降时间。（2）采用反相乳液聚合法,以二甲基二烯丙基氯化铵（DMDAAC）与丙烯酰胺（AM）单体为原料,研究了引发体系、引发剂用量、引发剂质量比、单体配比、油水体积比、体系pH值、EDTA加入量、反应时间、氮气通入时间对特性粘度的影响,确定了较优的制备工艺条件。优化条件为:选用引发剂NaHSO₃与K₂S₂O₈为引发体系,氧化还原引发剂的最佳用量为0.03%,其中NaHSO₃与K₂S₂O₈质量比为5:3 ,单体DMDAAC与AM质量比为2:8,油水体积比为1:1.2,体系最佳pH值为8.0,1.0mol/L的EDTA加入量为0.6mL,反应时间为4.0h,通氮时间为40.0min。用红外光谱（FTIR）对自制产物的结构进行了表征,差热分析表明,产物常温下较稳定,不易发生分解,扫描电镜分析表明,PDA产物的表面结构具有大量相互交叉的蘑菇状结构,表面凸起较多,具有很强的吸附、架桥能力。（3）利用化学法测定出产物PDA的阳离子度和残留AM单体的含量,再通过对PDA样品进行近红外反射光谱扫描,获得近红外光谱图,对图谱进行分析,采用小波分析法对光谱进行降噪处理,采用RBF神经网络的数学转换方法建立近红外反射光谱（NIRS）定标模型,建立PDA阳离子度的近红外预测模型,采用偏最小二乘法建立PDA中AM单体残留量的预测模型。（4）采用强化絮凝法,将自制的PDA用于处理水体中PAEs时,发现去除效果与PDA投加量、溶液初始pH值、搅拌时间、沉降时间、PDA特性粘度等因素有关,而且自制絮凝剂PDA对PAEs类物质具有较好的去除效果。（5）将PDA用于去除水体中HA,采用单因素分析法研究各个影响条件对去除效果的影响,取出絮凝后的絮体照片,通过显微镜拍摄絮体照片,采用分形维数法研究絮凝机理。更多还原

【Abstract】 Phthalate esters （PAEs） is such an important chemical raw material that is commonly present in environmental medium, which is also called endocrine disruptors or environmental hormones. Although the PAEs has been widely used in many fields, the material has posed a potential threat to human or animal endocrine systems, and thus a toxic to reproduction and development. Furthermore, continuing pollution of the urban source water from PAEs has also posed a lot of attention. Because PAEs was generally characterized by stability, cumulative, durability and resistant to degradation under common condition, we should carry out more effective measures on preventing the urban source water from PAEs pollution. Humic acid is an important class of natural organic matter in water, and also an important component of natural organic matter, due to its unique physical and chemical properties, It could affect Human and aquatic life, so it is essential to do the research for removing it.In this study, firstly, coagulation-flocculation experiments were carried out in an attempt to obtain higher removal efficiency of phthalate esters in water. Secondly, the organic coagulant diallyl dimethyl ammonium chloride and acrylamide （PDA） was grafted by free radical polymerisation of acrylamide monomer （AM） onto the cationic monomer dimethyl diallyl ammonium chloride （DMDAAC）. Thirdly, the synthesized PDA was characterized and the properties of which were analyzed. Fourthly, a new method to detect the residual monomers AM concentration in PDA was proposed using PDA near infrared spectroscopy. Lastly, coagulation-flocculation process was applied to the removal of PAEs and Hunic Acid in water with the prepared product, which also included the investigation of the coagulation-flocculation mechanism, and parameters affecting the coagulation-flocculation behavior.The main conclusions and contents in the study were as following:（1） Coagulation-flocculation process was carried out for the removal of the PAEs containing dimethyl phthalate （DMP） and diethyl phthalate （DEP） in water, and a comparison was made using the polymeric aluminum chloride （PAC）, polymeric ferric sulfate（PFS）, poly diallyl dimethyl ammonium chloride（PDMDAAC） and industry CPAM. In addition, parameters affecting the coagulation-flocculation process such as coagulant dosage, pH, mixing and settling time, were investigated. The results showed that the organic coagulant PDMDAAC, industry CPAM and self-made CPAM exhibited higher coagulation efficiency than inorganic coagulant: PAC and PFS. In addition, the composite coagulant （PDMDAAC/CPAM） presented better coagulation effect on treatment efficiency than individual coagulant （PDMDAAC）. Effects of the operational variables on the treatment efficiency follow dosage were > pH > mixing time > settling time order using the principal component analysis.（2） Cationic polyacrylamide （PDA） was prepared by the copolymerization of a cationic monomer dimethyldiallylammonium chloride （DMDAAC） with acrylamide （AM） through inverse emulsion polymerization, where Span-80 and Tween-80 were used as emulsifier and liquid paraffin respectively with stage addition into the reaction system. The effect of reaction variables such as oxidant/reductant （NaHSO₃/K₂S₂O₈） and DMDAAC /AM mass ratio, pH value, dosage of EDTA, temperature, reaction time, nitrogen blowing time were investigated in detail. The optimum conditions used as followed: the NaHSO₃/K₂S₂O₈ mass ratio was 5:3, the DMDAAC /AM was 2:8, the pH value was was 8.0, the dosage of EDTA was 0.6mL, the reaction time was 5.0h, nitrogen blowing time was 40.0min.（3） Near infrared reflectance spectroscopy（NIRS） was used as a rapid and accurate method to determine the residul of acrylamide monomer in the product of diallyl dimethyl ammonium chloride and acrylamide. 38 of samples were self-prepared in the laboratory and their near infrared spectroscopy were scanned, among which, seven bands were investigated and the characteristic peak intensity in each band was as the independent variables, where the residual AM concentration was considered as the dependent variable. Also, partial least squares （PLS） method was used to establish the NIRS calibration modeling. The characteristic peaks and the entire spectrum segment as the input layer neurons in radical basis function （RBF） were investigated for establishing the mathematical conversion NIRS calibration modeling. For reducing the NIRS spectrum noise, the wavelet analysis was used as pre-treatment process. The measured value was determined by using precipitation titration and a comparison was made between the simulated and measured value. The result showed that the calibration model: PLS modeling and （RBF neural network） established in this paper exhibited a remarkable feasibility to predict the cationic degree of PDA based on the near infrared spectroscopy.（4） Coagulation-flocculation was carried out for treatment of water containing the phthalic acid ester（PAEs） using the organic coagulant PDA. Parameters affecting the coagulation-flocculation process such as coagulant dosage, pH value, mixing and settling time, were measured. The result showed that PDA has better flocculation efficiency in comparison to inorganic coagulant.（5） Humic acid in water was treated with PDA. The results suggested the impact of some factors on the treatment efficiency of humic acid. In addition, the fractal dimension of the flocs generated after the coagulation-flocculation was investigated. In general, the fractal dimension ranges from 1.10 1.55. The flocs’ structure presented the same fractal characteristics with strong self-similarity. It showed a positive correlation between the humic acid removal and the fractal dimension of the formed flocs.更多还原