间歇曝气式膜生物反应器对养猪沼液中兽用抗生素去除途径和特性的研究
发布时间：2018-10-16 11:27
【摘要】：兽用抗生素因其防病治病、促进生长的双重作用,广泛地应用于规模化的畜牧养殖产业。但是,目前大量使用甚至滥用抗生素的现象十分严重,使得畜牧肉、蛋品中抗生素的残留含量超标。进入生物体内的抗生素只有30%~70%被利用,剩余的都随排泄物一起进入周边水体、土壤等环境介质。与其他污染物相比,抗生素的含量较低。但抗生素暴露时间持久、难生物降解的特性将使其持续对水体、土壤和生物产生潜在的环境风险。含有抗生素的废水通常使用活性碳吸附法、膜过滤法、普通活性污泥法(conventional activated sludge,CAS)和膜生物法(membrane bioreactor,MBR)等常规工艺处理。活性碳法和膜过滤法不能真正分解环境中抗生素。普通活性污泥法对抗生素的去除效果一般。膜生物法是在生物处理的技术结合使用了膜分离技术,通过分开控制水力停留时间(hydraulic retention time,HRT)和污泥停留时间(sludge residence time,SRT)可获得更长的污泥龄及保留世代菌,对抗生素有较好的去除效果。长三角下游地区是重要的生猪养殖基地,受到养殖业和上游排水的双重污染,导致水质很差。目前,我国尚缺少开展膜生物法对兽用抗生素去除效果的研究报道,也未见有抗生素去除途径的研究成果。本文以间歇式膜生素反应器对养猪沼液中兽用抗生素的去除特性为研究目标,开展了以下工作:针对长江三角洲地区大型养猪场中常用的四类11种兽用抗生素(四环素类、磺胺类、喹诺酮类及大环内酯类),开发了同步废水和污泥中抗生素的固相萃取-高效液相色谱串联质谱方法(solid phase extraction-high performance liquid chromatography and mass spectrometry,SPE-HPLC-MS/MS);采用间歇曝气式膜生物反应器(intermittent aeration membrane bioreactor,IAMBR)来处理养猪沼液,并且比较在不同HRT、SRT和碳氮比的运行条件下,IAMBR对废水中抗生素的去除效果及污泥中的积累情况;通过质量衡算来阐明抗生素的主要去除途径和去除比例;使用摇瓶试验来分析受到抗生素污染的活性污泥在降解TOC、氨氮方面是否会存在影响。结果表明:优化后的SPE-HPLC/MS/MS方法检出限低、灵敏度高,能同步检出养猪沼液的水相、污泥相中的11种兽用抗生素;HRT通过改变有机物负荷成为影响水相中抗生素去除的主要因素,SRT、碳氮比不是水相中抗生素去除的重要影响因素。污泥中四环素类、磺胺类抗生素的积累浓度随SRT的延长而增加,污泥中的抗生素含量与组成受进水影响较大;四环素类主要通过吸附和降解去除、磺胺类抗生素的去除主要依靠降解;在目前抗生素污染程度下的活性污泥在降解TOC、氨氮方面没有明显的影响。
[Abstract]:Veterinary antibiotics are widely used in the field of animal husbandry because of their dual functions of preventing and curing diseases and promoting growth. However, the phenomenon of extensive use and even abuse of antibiotics is very serious at present, which makes the residue of antibiotics in livestock meat and egg products exceed the standard. Only 30% of the antibiotics entered into the organism were used, and the rest of the antibiotics entered the surrounding water body, soil and other environmental media with excreta. Compared with other pollutants, the content of antibiotics is lower. However, because antibiotics are exposed for a long time, the characteristics of difficult biodegradation will cause potential environmental risks to water, soil and organisms. Wastewater containing antibiotics is usually treated by conventional processes such as activated carbon adsorption, membrane filtration, conventional activated sludge (conventional activated sludge,CAS) and membrane biological process (membrane bioreactor,MBR). Activated carbon and membrane filtration methods can not really decompose antibiotics in the environment. The removal effect of antibiotics by conventional activated sludge process is general. Membrane biofilm process is the combination of membrane separation technology and biological treatment technology. By separate control of HRT (hydraulic retention time,HRT) and sludge residence time (sludge residence time,SRT), longer sludge age and longer generation bacteria can be obtained. It has better removal effect on antibiotics. The downstream region of Yangtze River Delta is an important pig breeding base, which is polluted by both aquaculture and upstream drainage, resulting in poor water quality. At present, there is no research report on the removal of veterinary antibiotics by membrane biological method in China, nor has there been any research results on the removal pathway of antibiotics. In this paper, the removal characteristics of animal antibiotics in pig biogas liquid by intermittent membrane bioreactor were studied. The following works were carried out: for the four kinds of 11 kinds of animal antibiotics (tetracycline) commonly used in large pig farms in the Yangtze River Delta region, Sulfonamides, Quinolones and macrolides), a solid-phase extraction-high performance liquid chromatography-tandem mass spectrometry (solid phase extraction-high performance liquid chromatography and mass spectrometry,SPE-HPLC-MS/MS) method was developed for simultaneous treatment of antibiotics in wastewater and sludge, and an intermittent aerated membrane bioreactor (intermittent aeration membrane bioreactor,IAMBR) was used to treat pig biogas. The effects of IAMBR on the removal of antibiotics in wastewater and the accumulation of antibiotics in sludge were compared under different operating conditions of HRT,SRT and C / N, and the main removal routes and removal ratio of antibiotics were explained by mass balance calculation. The shaking flask test was used to analyze the influence of antibiotic contaminated activated sludge on the degradation of TOC, ammonia nitrogen. The results showed that the optimized SPE-HPLC/MS/MS method had low detection limit and high sensitivity, and could simultaneously detect the water phase of pig biogas liquid. Eleven kinds of veterinary antibiotics were found in sludge phase, HRT was the main factor affecting the removal of antibiotics in water phase by changing the organic load, and SRT, / C / N ratio was not an important factor in the removal of antibiotics in water phase. The accumulation concentration of tetracycline and sulfanilamide antibiotics in sludge increased with the prolongation of SRT, the content and composition of antibiotics in sludge were greatly affected by influent, and tetracycline was mainly removed by adsorption and degradation. The removal of sulfanilamides mainly depends on the degradation, but the activated sludge has no obvious effect on the degradation of TOC, ammonia nitrogen under the current antibiotic pollution.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X713
本文编号：2274213
[Abstract]:Veterinary antibiotics are widely used in the field of animal husbandry because of their dual functions of preventing and curing diseases and promoting growth. However, the phenomenon of extensive use and even abuse of antibiotics is very serious at present, which makes the residue of antibiotics in livestock meat and egg products exceed the standard. Only 30% of the antibiotics entered into the organism were used, and the rest of the antibiotics entered the surrounding water body, soil and other environmental media with excreta. Compared with other pollutants, the content of antibiotics is lower. However, because antibiotics are exposed for a long time, the characteristics of difficult biodegradation will cause potential environmental risks to water, soil and organisms. Wastewater containing antibiotics is usually treated by conventional processes such as activated carbon adsorption, membrane filtration, conventional activated sludge (conventional activated sludge,CAS) and membrane biological process (membrane bioreactor,MBR). Activated carbon and membrane filtration methods can not really decompose antibiotics in the environment. The removal effect of antibiotics by conventional activated sludge process is general. Membrane biofilm process is the combination of membrane separation technology and biological treatment technology. By separate control of HRT (hydraulic retention time,HRT) and sludge residence time (sludge residence time,SRT), longer sludge age and longer generation bacteria can be obtained. It has better removal effect on antibiotics. The downstream region of Yangtze River Delta is an important pig breeding base, which is polluted by both aquaculture and upstream drainage, resulting in poor water quality. At present, there is no research report on the removal of veterinary antibiotics by membrane biological method in China, nor has there been any research results on the removal pathway of antibiotics. In this paper, the removal characteristics of animal antibiotics in pig biogas liquid by intermittent membrane bioreactor were studied. The following works were carried out: for the four kinds of 11 kinds of animal antibiotics (tetracycline) commonly used in large pig farms in the Yangtze River Delta region, Sulfonamides, Quinolones and macrolides), a solid-phase extraction-high performance liquid chromatography-tandem mass spectrometry (solid phase extraction-high performance liquid chromatography and mass spectrometry,SPE-HPLC-MS/MS) method was developed for simultaneous treatment of antibiotics in wastewater and sludge, and an intermittent aerated membrane bioreactor (intermittent aeration membrane bioreactor,IAMBR) was used to treat pig biogas. The effects of IAMBR on the removal of antibiotics in wastewater and the accumulation of antibiotics in sludge were compared under different operating conditions of HRT,SRT and C / N, and the main removal routes and removal ratio of antibiotics were explained by mass balance calculation. The shaking flask test was used to analyze the influence of antibiotic contaminated activated sludge on the degradation of TOC, ammonia nitrogen. The results showed that the optimized SPE-HPLC/MS/MS method had low detection limit and high sensitivity, and could simultaneously detect the water phase of pig biogas liquid. Eleven kinds of veterinary antibiotics were found in sludge phase, HRT was the main factor affecting the removal of antibiotics in water phase by changing the organic load, and SRT, / C / N ratio was not an important factor in the removal of antibiotics in water phase. The accumulation concentration of tetracycline and sulfanilamide antibiotics in sludge increased with the prolongation of SRT, the content and composition of antibiotics in sludge were greatly affected by influent, and tetracycline was mainly removed by adsorption and degradation. The removal of sulfanilamides mainly depends on the degradation, but the activated sludge has no obvious effect on the degradation of TOC, ammonia nitrogen under the current antibiotic pollution.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X713
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