【作者】 张会琴；

【导师】 郑怀礼；

【作者基本信息】 重庆大学 ， 市政工程， 2010， 博士

【摘要】 论文首先对新合成的无机高分子复合混凝剂（PPFS）进行了制备和表征,分析了PPFS的形貌结构和混凝机理。之后以直接深棕印染废水和微污染原水为研究对象,在单因素试验设计、正交试验设计、Box-Behnken设计和中心组合设计等试验设计的基础上,并结合响应面分析,研究了超声波促进类Fenton氧化工艺对直接深棕印染废水的降解效果、试验条件优化及降解机理;同时研究了PPFS/H₂O₂混凝-氧化耦合工艺对直接深棕印染废水和微污染原水的降解效果、试验条件优化及降解机理。旨在探索废水降解的新途径,拓宽高级氧化组合工艺在水处理领域的应用范围,从而为丰富、深化氧化组合工艺的理论研究提供一定的数据和基础。论文的主要研究结论如下:（1）采用红外（FTIR）、X-衍射（XRD）,确定了聚磷硫酸铁（PPFS）的结构组成,PPFS是一种高电荷的多羟基多核络合物,电镜扫描（SEM）表征分析,PPFS具有簇状类珊瑚礁立体网状的形貌结构;混凝烧杯试验说明,PPFS在混凝时不是以电中和机理为主,吸附、架桥和混凝沉淀等作用才是它具有优异混凝效果的主要原因,Zeta电位值证实了该推测;逐时络合比色法显示PPFS混凝剂中Fe（c）形态较多,Fe（a）和Fe（b）含量相对较少,表明PPFS主要以铁磷高聚物形式存在;紫外可见光谱显示,不同pH条件下PPFS混凝剂的光谱曲线变化与其混凝形态有一定的对应关系。PPFS的混凝机理可能是:电中和作用能有效地降低水中胶体的ζ电位致使胶体脱稳,之后PPFS发挥吸附、架桥、混凝沉淀等作用最终有效地去除污水中的各种物质,所以PPFS是电中和、吸附、架桥和混凝沉淀等几种作用的综合体现。（2）超声波促进类Fenton氧化工艺:以模拟直接深棕印染废水为对象,采用低频超声技术,探讨初始pH、H₂O₂投加量及催化剂用量对直接深棕印染废水降解率的影响。应用Box-Behnken中心组合试验和响应面分析法,建立了类Fenton试剂对处理直接深棕印染废水的二次多项式数学模型,确定了超声降解直接深棕印染废水的优化条件:取初始浓度为100.0 mg/L直接深棕印染废水250.0 mL,超声功率为250 W,频率28 kHz,降解150 min,初始pH、H₂O₂投加量及催化剂用量分别为3.79、1.74 mM、1.65 g/L。经试验验证,实际值与模型预测值拟合性良好,偏差仅为1.35%。通过分析降解前后的紫外-可见光谱图,初步推断在超声-Fenton反应下,直接深棕并没有完全降解为CO₂和H₂O,而仅仅是生色基团受到自由基攻击而被破坏。（3）直接深棕印染废水的PPFS/H₂O₂混凝-氧化耦合工艺:从单因素试验分析可知,选择合适的投加量和合适的nPO₄^3-/nFe³⁺,可以提高PPFS对直接深棕色度去除率,在此基础上投加适量H₂O₂,使其与混凝后水体中残余的Fe³⁺构成高级氧化体系（类Fenton试剂）,进一步降低混凝反应后残余的有机物,达到更好的处理效果,pH的应用范围很宽。正交试验分析得出:对于直接深棕印染废水的去除率影响效能较大是H₂O₂的投加量和混凝剂的投加量。分析该工艺机理:在酸性环境中,类Fenton反应机理占主导地位;在碱性环境中,PPFS的混凝作用占主导地位。由此推之,无机高分子混凝剂与H₂O₂的联合使用,可以大大拓宽它们的pH值的应用范围。（4）微污染原水中的UV₂₅₄、COD和TOC的PPFS/H₂O₂混凝-氧化耦合工艺:从单因素试验对微污染原水中的UV₂₅₄去除效果分析中可知,选择合适的nPO₄^3-/nFe³⁺和nOH-/nFe³⁺,可以提高PPFS对UV₂₅₄的去除效果,在此基础上投加适量H₂O₂可进一步降低混凝反应后残余的有机物,达到更好的处理效果。微污染原水宏观指标的正交试验分析得出:对于原水中UV₂₅₄、COD和TOC的去除率影响效能较大的是混凝剂和H₂O₂的投加量。（5）微污染原水中的邻苯二甲酸酯类（PAEs）和多环芳烃（PAHs）检测结果分析:PPFS与H₂O₂耦合使用,邻苯二甲酸二丁酯（DBP）和邻苯二甲酸二（2-乙基己基）酯（DEHP）的去除率均达到90.0%以上,而邻苯二甲酸二甲酯（DMP）和邻苯二甲酸二乙酯（DEP）的去除率相对较低,去除率一般在70.0%-80.0%;菲和芘的去除率基本达到90.0%以上,而萘和荧蒽的去除率分别在60.0%和40.0%左右。更多还原

【Abstract】 Characterization of polymeric phosphate ferric sulfate （PPFS） and its topography structure in this research were measured. In order to investigate the performance of this coagulate, Direct Dark Brown MM dye wastewater and micro-polluted raw water were considerably thought as the object of water treatment. In this experiment, many methods such as single parameter design, orthogonal design, Box-Behnken design and central composite design and response surface analysis were used in the investigation of the degradation efficiency, conditions optimization. In addition, the degradation mechanism of Direct Dark Brown MM by the ultrasonic-promoted heterogeneous Fenton-like process and PPFS/H₂O₂ coupled flocculation and oxidation process and micro-polluted raw water by PPFS/H₂O₂ coupled flocculation and oxidation process were detail analysised in various conditions. The purpose of this study was to expand the application range of combined AOPs in the field of wastewater treatment. At the same time, it would provide a new method to degrade the dye wastewater and micro-polluted raw water and the experimental results would provide a theoretical guidance in the treatment of the dye wastewater and micro-polluted raw water and the study of the mechanism of combined AOPs. The main conclusions in this research were summarized as follows:（1） Characteristics of PPFS were investigated using FTIR （fourier transform infrared spectrometer）, XRD （x-ray diffraction） and SEM （scanning electron microscope） in this paper. The formed PPFS structure and morphology were stereo meshwork, which was clustered and closely to coral reef, synthesis of high charge density, bioactive polyhydroxy and mixed polynuclear complex PPFS. The results showed that charge neutralization of PPFS had not played a decisive role on the coagulation beaker test and the Zeta potential proved that PPFS was largely affected by bridging and coagulation and sedimentation. Fe-ferron complexation timed spectrophotometry showed that the amount of Fe（c） in Polymeric Phosphate Ferric Sulfate （PPFS） flocculants was the most in the three species, while the amount of Fe（a） and Fe（b） was small, that was PPFS mainly exists in the form of phosphate ferric polymer. Ultraviolet-visible spectrum showed that the change in the spectral curve of the different pH polymer ferric sulfate flocculants was corresponding to the flocculation morphology. Therefore, the coagulation mechanisms of PPFS were mainly composed of charge neutralization, adsorption bridging, coagulation and sedimentation mechanisms.（2） Ultrasonic-promoted heterogeneous Fenton-like process of Direct Dark Brown MM: the effects of initial pH of Direct Dark Brown MM dye solution, H₂O₂ concentration and dosage of Fe-Ni-Mn/Al2O3 on the degradation ratio of Direct Dark Brown MM were studied by using low frequency ultrasound. By the Box-Behnken centre-united experiment design and response surface methodology, a predictive polynomial quadratic model was set up and the optimum extraction conditions were developed, which were pH of dye wastewater 3.79, dosage of H₂O₂ 1.74 mM, dosage of Fe-Ni-Mn/Al2O3 1.65 g/L on the initial dye concentration 100.0 mg/L. 91.09 % of Direct Dark Brown MM was degraded under the optimal conditions. The experimental values agreed with the predicted values of the model equation with 1.35 % deviation. The UV-Vis spectra of Direct Dark Brown MM before and after degradation were analyzed and the following conclusions cound be drawn: Direct Dark Brown MM was not completely mineralized to CO2 and H2O by ultrasonic irradiation and Fenton reaction, instead, the chromophore in Direct Dark Brown MM molecular structure was just destroyed under the attack of radicals.（3） PPFS/H₂O₂ coupled flocculation and oxidation process of Direct Dark Brown MM: based on single factor experiments, the degradation degree of Direct Dark Brown MM were enhanced significantly under the optimum nPO₄^3-/nFe³⁺ and nOH-/nFe³⁺ molar ratio. Also, the results showed that the addition of H₂O₂ facilitated the degradation of Direct Dark Brown MM, which was caused by the generated Fenton-like process with H₂O₂ and Fe³⁺ after flocculation. The orthogonal experiment showed that the removal efficiency was largely affected by the PPFS dosage and H₂O₂ dosage. The results showed that in an acidic environment, Fenton-like mechanism played a key role. On the contrary, the flocculation mechanism would do in the alkaline environment. Therefore, the pH range would be greatly extended using PPFS/H₂O₂ coupled flocculation and oxidation process（4） PPFS/H₂O₂ coupled flocculation and oxidation process of micro-polluted raw water of UV₂₅₄, COD and TOC: based on the single factor experiments, the effect of UV₂₅₄ of micro-polluted raw water was investigated. The optimum conditions were as follows: the treatment efficiency would be improved in terms of the suitable nPO₄^3-/nFe³⁺ and nOH-/nFe³⁺. At the above determined optimum conditions, the removal efficiency would be enhanced in presence of H₂O₂. At the same time, the orthogonal experiment to treat UV₂₅₄ of micro-polluted raw water was carried out and the results showed that PPFS dosage, H₂O₂ dosage had a better effect on the removal of UV₂₅₄, COD and TOC.（5） PPFS/H₂O₂ coupled flocculation and oxidation process of micro-polluted raw water of PAEs and PAHs: a comparison was made between the testing of PAEs and PAHs. The results showed that PPFS/H₂O₂ had the same effect on the removal of DBP and DEHP with the PPFS alone and the removal efficiency were all over 90.0%. However, the removal rate of DMP and DEP compared with above materials had a lower efficiency of 70.0%-80.0%; Furthermore, the removal of phenanthrene and pyrene were almost 90.0%, that of the naphthalene and fluoranthene were 60.0% and 40.0%, respectively.更多还原