几种水中典型PPCPs的高级氧化降解及其消毒副产物的生成研究

发布时间：2018-02-10 04:21

本文关键词： 药品及个人护理用品高级氧化消毒副产物影响因素　出处：《江西理工大学》2015年硕士论文　论文类型：学位论文

【摘要】：典型的新型污染物之一——药品及个人护理用品(Pharmaceuticals and Personal Care Products,PPCPs)在环境中的普遍存在使其正以潜移默化的方式影响着生态环境与动植物健康。而饮用水消毒工艺在与病原微生物反应的同时也会与原水中有机物互相反应生成高“三致”风险物质——消毒副产物(Disinfection By-products,DBPs),当PPCPs作为其前体物时,生成的DBPs相较于其本身毒性将大幅度提高。本课题利用UV/PS(Persulfate,PS)与UV/H2O2两种高级氧化工艺对比、阴离子活化PMS(Peroxymonosulfate,PMS)降解水中磺胺类药物增效剂甲氧苄氨嘧啶(Trimethoprim,TMP),采用Fe2+/UV活化PMS去除水中抗癫痫药物卡马西平(Carbamazepine,CBZ)。着重讨论氧化剂浓度、目标污染物浓度、催化剂浓度、p H值、腐殖酸(Humic Acid,HA)与阴离子浓度等影响因素对相应高级氧化方法去除PPCPs的影响并分析其反应机理。以CBZ和TMP,并增设金霉素(Chlorotetracycline,CTC)为前体物,对比并归纳自由氯消毒与氯胺消毒两种方式的DBPs生成规律,最后考察UV/PS、UV/H2O2和Fe2+/UV/PMS三种高级氧化前处理对PPCPs的DBPs生成影响。研究表明:(1)UV/PS、UV/H2O2两种方法对TMP的降解都符合伪一级动力学模型,在室温条件下,前者对TMP的去除率略高于后者。碱性反应条件不利于TMP的去除;共存阴离子对反应的影响作用十分复杂,其中,CO32-与HCO3-始终表现出对反应的抑制作用。(2)五种阴离子(CO32-、Cl-、HPO42-、NO3-、SO42-)中,NO3-和SO42-对PMS基本无活化能力;CO32-、Cl-和HPO42-三种离子活化PMS所产生的强氧化性活性物种分别为HCO4-、HOCl和SO4-·;当反应p H值升至一定程度时,TMP的去除主要是PMS的碱活化作用的结果;不同于其它高级氧化方法,HA不会对阴离子活化PMS反应产生显著影响。(3)通过Fe2+/UV活化PMS法对水中CBZ进行降解时发现,过高的氧化剂与催化剂浓度、减小UV辐照面积、增高反应p H值和增高HA浓度皆不利于降解反应的进行;提高CBZ的去除率可通过分次投加Fe2+和加入适量柠檬酸盐两种方法实现。(4)CBZ、TMP和CTC在氯化后生成了大量的DBPs,其生成量与前体物分子中碳原子数量、培养时间和加氯量成正比,也与前体物本身性质有关;培养过程中会出现不同种类DBPs间的相互转化现象,长时间的培养也会使部分DBPs自身挥发与分解;氯胺消毒能显著控制含碳消毒副产物(C-DBPs)的产量;在所能检测的DBPs中,均表现出在中性条件下生成浓度达到最大的规律。(5)使用高级氧化前处理方法能够大量去除被检出DBPs的前体物,并改变其结构,使其难以再被氯化,从而达到抑制DBPs生成的目的。
[Abstract]:One of the typical new pollutants, and Personal Care products (PPCPs), is affecting the ecological environment and animal and plant health in an imperceptible way because of its widespread presence in the environment. At the same time, the protozoa react with organic matter in raw water to form a high "three cause" risk substance, disinfection By-productsDBPsN, when PPCPs is used as its precursor. The DBPs produced will be much more toxic than its own toxicity. In this study, two advanced oxidation processes, UV / PS / sulfatePSand UV/H2O2, were used to compare the two advanced oxidation processes. Anion activated PMS-PeroxymonosulfatePMSs were used to degrade trimethoprimidine trimethoprimidine trimethoprimidine (trimethoprimidine) in water, and Fe2 / UV activated PMS was used to remove carbamazepine. The concentration of oxidant, the concentration of target pollutants and the concentration of catalyst were discussed. Humic acid acid acid (Humic acid acid) and anion concentration influence the removal of PPCPs by the advanced oxidation method and analyze its reaction mechanism. CBZ and TMP were used as precursors, and chlortetracycline CTC was added as the precursor. The rules of DBPs formation in two ways of free chlorine disinfection and chloramine disinfection were compared and summarized. Finally, the effects of three advanced oxidation pretreatments on the DBPs production of PPCPs were investigated. The results showed that the degradation of TMP by the two methods was in accordance with the pseudo-first-order kinetic model at room temperature. The removal rate of TMP in the former is slightly higher than that in the latter. The basic reaction conditions are not conducive to the removal of TMP, and the influence of coexisting anions on the reaction is very complex. The five anions (CO32-Cl-HPO42-HPO42-NO3-O4-SO42-) and so _ 42- have little ability to activate PMS. The strong oxidizing active species produced by the activation of PMS by the three kinds of ions are HCO4-HHOCl and SO4- 路, respectively, when the reaction p, the active species are HCO4-HHOCl and SO4-, respectively, when the reaction p, the active species of PMS are HCO4-OHCl and SO4- 路, respectively, when the reaction p, the active species are HCO4-HHOCl and so _ 4- 路. When H value rises to a certain extent, the removal of TMP is mainly the result of alkali activation of PMS. Different from other advanced oxidation methods, the anion activated PMS reaction was not significantly affected by HA. (3) when CBZ in water was degraded by Fe2 / UV activated PMS method, it was found that the excessive concentration of oxidant and catalyst reduced the irradiation area of UV. Increasing the pH value of the reaction and increasing the concentration of HA were not conducive to the degradation reaction. Increasing the removal rate of CBZ can be achieved by adding Fe2 and adding appropriate amount of citrate to produce a large amount of DBPs after chlorination, which is directly proportional to the amount of carbon atoms in the precursor molecule, the culture time and the amount of chlorine added. It also has something to do with the properties of precursors, the mutual transformation of different kinds of DBPs will occur in the culture process, the long time culture will also make part of DBPs volatilize and decompose, chloramine disinfection can significantly control the yield of carbon-containing disinfection by-products (C-DBPss). In the DBPs that can be detected, it is shown that the formation concentration reaches the maximum rule under neutral conditions. 5) the advanced oxidation pretreatment method can remove the precursors of the detected DBPs and change its structure so that it is difficult to chlorinate. In order to achieve the purpose of inhibiting the formation of DBPs.
【学位授予单位】：江西理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TU991.25

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