电化学联合臭氧处理阿莫西林废水的作用效能与机理研究

发布时间：2018-03-27 20:22

本文选题：抗生素　切入点：阿莫西林　出处：《哈尔滨工业大学》2015年硕士论文

【摘要】：抗生素广泛用于治疗人类和动物疾病,以及作为饲料添加剂促进动物的生长。然而,由于其对水生生态和人类健康的潜在不利影响,出现在水体等自然环境中的抗生素受到特别的关注。由于抗生素具有抗菌性及生物毒性,传统的生物水处理方法并不能有效的去除环境中的抗生素。因此,有必要开发高效的处理技术,去除水体中的抗生素,减少抗生素对环境的影响。本文选取阿莫西林(AMO)废水进行研究,采用电化学氧化法,臭氧氧化法和电化学联合臭氧氧化对其处理,并分析了臭氧氧化和电化学联合臭氧氧化过程的作用效能及机理。在三种方法中,电化学联合臭氧氧化是对AMO降解最有效的技术。电化学作用6分钟后只有37%的AMO去除率,而在5分钟和4分钟内,AMO可以分别被臭氧和电化学联合臭氧过程完全处理。同时,在矿化度实验中,用电化学联合臭氧氧化处理60分钟后,总有机碳矿化度达到67.8%。相比较而言,使用臭氧氧化和电化学法处理,分别只得到47.3%和3.1%的矿化度。结果发现,电化学联合臭氧的氧化过程中羟基自由基的产量和O3的利用率均得到了提高。为了更加经济有效地控制电化学联合臭氧处理阿莫西林过程,本文系统的研究了电化学联合臭氧处理阿莫西林过程中重要的操作参数,如臭氧浓度,电流,p H等对处理效能的影响。研究表明,在电化学联合臭氧氧化过程增加曝气中臭氧的浓度会增加阿莫西林的降解及TOC矿化度。电流从100毫安增加到300毫安时,阿莫西林的降解和TOC矿化随着所施加电流的增加而变大。然而,进一步增加电流至400毫安时,阿莫西林降解和TOC矿化并未提高甚至出现了一定的下降。本研究发现,p H值对于AMO降解和TOC矿化起重要作用,它不仅影响水溶液中臭氧的分解和羟基自由基的产量,而且还影响到AMO的存在形式。此外,本研究还开展了电化学联合臭氧降解AMO中,电化学引入对该系统的影响机理。结果发现电化学引入后确实促进了羟基自由基的产生,并且提高了O3的利用率。因此,电化学联合臭氧氧化过程相对于臭氧氧化能够更经济和更有效的降解AMO。最后,开展了AMO降解途径的研究。采用UPLC-MS/MS技术鉴定了电化学联合臭氧和臭氧单独氧化处理的中间产物。在电化学联合臭氧氧化中发现了15种不同质荷比的中间产物,在臭氧氧化过程中发现10种不同质荷比的中间产物。证明了在臭氧氧化中引进电化学作用增强了AMO的降解。结合量子化学计算结果提出了AMO的不同降解途径,包括苯甲酸环和氨基的降解,四元β内酰胺环的开环,硫的氧化及其它键裂解反应。
[Abstract]:Antibiotics are widely used to treat human and animal diseases and to promote animal growth as feed additives. However, due to their potentially adverse effects on aquatic ecology and human health, Antibiotics in the natural environment, such as water bodies, are of particular concern. Because antibiotics are antibacterial and biotoxic, traditional biological water treatment methods can not effectively remove antibiotics from the environment. It is necessary to develop efficient treatment technology to remove antibiotics in water and reduce the impact of antibiotics on the environment. In this paper, amoxicillin AMO-wastewater was studied and electrochemical oxidation was used. Ozone oxidation and electrochemical combined ozone oxidation are used to treat them, and the effect and mechanism of ozone oxidation and electrochemical combined ozone oxidation are analyzed. Electrochemical combined ozonation is the most effective technique for AMO degradation. After 6 minutes of electrochemical action, only 37% of AMO can be removed, while in 5 minutes and 4 minutes, AMO can be completely treated by ozone and electrochemical combined ozone processes, respectively. In the salinity experiment, the total organic carbon salinity reached 67.8% after 60 minutes of electrochemical combined ozonation treatment. In comparison, only 47.3% and 3.1% of the total organic carbon mineralization were obtained by ozone oxidation and electrochemical treatment, respectively. The production of hydroxyl radical and the utilization rate of O3 have been improved in the process of electrochemical combined ozone oxidation. In order to control the amoxicillin process of electrochemical combined ozone treatment more economically and effectively. In this paper, the effects of some important operating parameters, such as ozone concentration and current pH, on the treatment efficiency of amoxicillin treated by electrochemical combined ozone are systematically studied. When the concentration of ozone in aeration increases during the electrochemical combined ozone oxidation process, the degradation of amoxicillin and the salinity of TOC are increased. When the current is increased from 100mA to 300mA, The degradation and TOC mineralization of amoxicillin increase with the increase of the applied current. However, when the current is further increased to 400mA, Amoxicillin degradation and TOC mineralization did not increase or even decrease to a certain extent. In this study, we found that H value plays an important role in AMO degradation and TOC mineralization, which not only affects the decomposition of ozone and the production of hydroxyl radical in aqueous solution. In addition, the mechanism of electrochemistry combined with ozone degradation of AMO was carried out. The results showed that the introduction of electrochemistry did promote the production of hydroxyl radicals. Therefore, the electrochemical combined ozonation process can degrade AMOO more economically and efficiently than ozonation. The degradation pathway of AMO was studied. The intermediates of electrochemical combined ozonation and ozonation alone were identified by UPLC-MS/MS technique. Fifteen intermediates with different charge ratios were found in electrochemical combined ozonation. In the process of ozone oxidation, 10 intermediates of different mass charge ratios were found. It was proved that the introduction of electrochemical action in ozone oxidation enhanced the degradation of AMO. Different degradation pathways of AMO were proposed in combination with quantum chemical calculations. These include the degradation of benzoic acid ring and amino group, the ring opening of quaternary 尾 -lactam ring, the oxidation of sulfur and other bond cleavage reactions.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X703

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