臭氧—陶瓷膜耦合系统在水产养殖循环水处理中的应用
发布时间：2018-11-21 10:14
【摘要】：催化臭氧氧化同陶瓷膜分离相耦合技术是一种新型、高效的深度废水处理技术,它不仅能够利用膜截留过程浓缩废水中的有毒有害物质,而且还能利用催化臭氧氧化降解膜截留的污染物质。在催化臭氧氧化-陶瓷膜分离耦合技术中,高效、稳定臭氧催化陶瓷分离膜的制备是关键环节之一。本研究旨在筛选出高效的臭氧催化剂,将其负载到陶瓷膜基底上,制备出高效稳定的臭氧催化陶瓷膜,组合成催化臭氧氧化-陶瓷分离膜耦合水处理系统,并应用此系统对实际水产养殖循环水进行处理。初步建立起催化臭氧氧化-陶瓷分离膜耦合工艺处理实际水产养殖循环水的工艺方法,为实际水污染治理和资源化利用提供了一种可实用化的污水处理技术。具体研究内容如下：(1)运用不同的方法制备出不同的臭氧催化剂,比较各种催化剂对臭氧的催化氧化性能,筛选出一种最为有效的处理水中污染物的臭氧催化剂。研究发现,改变氧化铁催化剂的形貌对催化臭氧分解的能力影响不大,去除硝基苯的效果也不佳；纳米棒状氧化锰催化臭氧分解的能力较强,但其降解实际印染废水的效果却不佳；掺杂锰元素钛氧化物对草酸去除率最高,为63.8%,去除草酸的动力学常数绝对值为0.03436 K/min,分别是TiCoxOy、TiCexOy、TiFexOy、TiO2和不加催化剂的1.5、3.4、5.7、10.2和20.6倍。(2)用溶胶-凝胶法将掺杂锰元素的钛氧化物成功负载到陶瓷膜基底上,制备出高效、稳定的臭氧催化陶瓷分离膜。SEM和EDX图谱表明,钛锰氧化物不仅均匀的负载在陶瓷膜的表面,而且部分渗透到陶瓷膜内部；XRD图谱显示,制备的臭氧催化陶瓷膜由三部分构成：基底(Al2O3)、中间层(金红石型TiO2)和催化层(金红石型TiO2,未发现氧化锰的特征峰)；膜通量测试表明,Ti-Mn/TiO2/Al2O3 和 TiO2/Al2O3膜通量分别为269.6L/m2·h·bar 和 340.5 L/m2·h·bar。(3)单独膜分离工艺、臭氧氧化-陶瓷分离膜耦合工艺和催化臭氧氧化-陶瓷分离膜耦合工艺对水产养殖废水的处理效果表明,单独膜分离工艺不能去除水产养殖废水中的总氨氮、亚硝酸盐和溶解性有机污染物,并会发生严重的膜通量下降现象;臭氧氧化-陶瓷膜分离耦合工艺和催化臭氧氧化-陶瓷分离膜耦合工艺对水产养殖废水具有良好的处理效果,两种处理工艺对悬浮物、总氨氮和亚硝酸去除率相近(出水中浊度≈0 NTU,总氨氮≤0.1 mg/L,亚硝酸≤0.005 mg/L),对CODMn的去除率分别为35.7%和52.1%。出水水质达到第二类海水水质标准,也满足渔业水产养殖水质的标准。(4)将催化臭氧氧化-陶瓷膜分离工艺应用到实际水产养殖循环水处理中,长期运行结果显示,此系统出水水质和水量均保持稳定。初步建立起催化臭氧氧化-陶瓷膜分离耦合工艺处理实际水产养殖循环水的工艺方法,此耦合系统具有良好的应用前景。
[Abstract]:The coupling technology of catalytic ozone oxidation and ceramic membrane separation is a new and efficient advanced wastewater treatment technology. It can not only use membrane interception process to concentrate toxic and harmful substances in wastewater. Moreover, catalytic ozone oxidation can also be used to degrade the pollutants intercepted by the membrane. In the coupling technology of catalytic ozone oxidation and ceramic membrane separation, the preparation of efficient and stable ozone catalytic ceramic separation membrane is one of the key links. The purpose of this study was to screen out high efficient ozone catalyst, to load it on ceramic membrane substrate, to prepare high efficient and stable ozone catalytic ceramic membrane, and to combine it into a coupling water treatment system of catalytic ozone oxidation-ceramic separation membrane. The system is applied to the treatment of real aquaculture circulating water. The coupling process of catalytic ozone oxidation and ceramic separation membrane was established for the treatment of real aquaculture circulating water, which provided a practical sewage treatment technology for actual water pollution treatment and utilization. The specific research contents are as follows: (1) different ozone catalysts were prepared by different methods, and the catalytic oxidation performance of different catalysts was compared to select the most effective ozone catalyst for the treatment of pollutants in water. It was found that changing the morphology of ferric oxide catalyst had little effect on the catalytic ability of ozone decomposition and the removal of nitrobenzene was not good. Nano-rod-like manganese oxide can catalyze ozone decomposition, but it is not effective in the degradation of printing and dyeing wastewater. The removal rate of oxalic acid was 63.8%, and the absolute value of kinetic constant of oxalic acid removal was 0.03436 K / min, respectively, which was TiCoxOy,TiCexOy,TiFexOy,. TiO2 and 1.5N 3.4N 5.710. 2 and 20.6 times without catalyst. (2) the manganese doped titanium oxide was successfully loaded on the ceramic membrane substrate by sol-gel method, and the high efficiency was obtained. The stable ozone catalytic ceramic separation membrane. SEM and EDX spectra show that the titanomanganese oxide is not only loaded on the surface of the ceramic membrane, but also partially permeated into the ceramic membrane. The XRD spectra showed that the prepared ozone catalytic ceramic membrane was composed of three parts: substrate (Al2O3), intermediate layer (rutile type TiO2) and catalytic layer (rutile type TiO2, did not find the characteristic peak of manganese oxide). The membrane fluxes of Ti-Mn/TiO2/Al2O3 and TiO2/Al2O3 were 269.6L/m2 h bar and 340.5 L/m2 h bar. (3, respectively. The effects of ozone oxidation-ceramic separation membrane coupling process and catalytic ozonation-ceramic separation membrane coupling process on the treatment of aquaculture wastewater showed that the membrane separation process could not remove total ammonia nitrogen from aquaculture wastewater. Nitrite and dissolved organic pollutants, and serious membrane flux decline; The coupling process of ozone oxidation-ceramic membrane separation and catalytic ozonation-ceramic separation membrane has a good effect on the treatment of aquaculture wastewater. The removal rates of total ammonia nitrogen and nitrite were similar (turbidity 鈮，
本文编号：2346672
[Abstract]:The coupling technology of catalytic ozone oxidation and ceramic membrane separation is a new and efficient advanced wastewater treatment technology. It can not only use membrane interception process to concentrate toxic and harmful substances in wastewater. Moreover, catalytic ozone oxidation can also be used to degrade the pollutants intercepted by the membrane. In the coupling technology of catalytic ozone oxidation and ceramic membrane separation, the preparation of efficient and stable ozone catalytic ceramic separation membrane is one of the key links. The purpose of this study was to screen out high efficient ozone catalyst, to load it on ceramic membrane substrate, to prepare high efficient and stable ozone catalytic ceramic membrane, and to combine it into a coupling water treatment system of catalytic ozone oxidation-ceramic separation membrane. The system is applied to the treatment of real aquaculture circulating water. The coupling process of catalytic ozone oxidation and ceramic separation membrane was established for the treatment of real aquaculture circulating water, which provided a practical sewage treatment technology for actual water pollution treatment and utilization. The specific research contents are as follows: (1) different ozone catalysts were prepared by different methods, and the catalytic oxidation performance of different catalysts was compared to select the most effective ozone catalyst for the treatment of pollutants in water. It was found that changing the morphology of ferric oxide catalyst had little effect on the catalytic ability of ozone decomposition and the removal of nitrobenzene was not good. Nano-rod-like manganese oxide can catalyze ozone decomposition, but it is not effective in the degradation of printing and dyeing wastewater. The removal rate of oxalic acid was 63.8%, and the absolute value of kinetic constant of oxalic acid removal was 0.03436 K / min, respectively, which was TiCoxOy,TiCexOy,TiFexOy,. TiO2 and 1.5N 3.4N 5.710. 2 and 20.6 times without catalyst. (2) the manganese doped titanium oxide was successfully loaded on the ceramic membrane substrate by sol-gel method, and the high efficiency was obtained. The stable ozone catalytic ceramic separation membrane. SEM and EDX spectra show that the titanomanganese oxide is not only loaded on the surface of the ceramic membrane, but also partially permeated into the ceramic membrane. The XRD spectra showed that the prepared ozone catalytic ceramic membrane was composed of three parts: substrate (Al2O3), intermediate layer (rutile type TiO2) and catalytic layer (rutile type TiO2, did not find the characteristic peak of manganese oxide). The membrane fluxes of Ti-Mn/TiO2/Al2O3 and TiO2/Al2O3 were 269.6L/m2 h bar and 340.5 L/m2 h bar. (3, respectively. The effects of ozone oxidation-ceramic separation membrane coupling process and catalytic ozonation-ceramic separation membrane coupling process on the treatment of aquaculture wastewater showed that the membrane separation process could not remove total ammonia nitrogen from aquaculture wastewater. Nitrite and dissolved organic pollutants, and serious membrane flux decline; The coupling process of ozone oxidation-ceramic membrane separation and catalytic ozonation-ceramic separation membrane has a good effect on the treatment of aquaculture wastewater. The removal rates of total ammonia nitrogen and nitrite were similar (turbidity 鈮，
本文编号：2346672
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