浸没式金属膜生物反应器处理城市污水性能及膜污染研究
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摘要
随着社会经济的发展、城市化进程的加快和人们环保意识的提高,城市水资源问题日益明显和突出。城市污水作为城市的第二水源,目前已被世界各国广泛回收和再利用。在众多的城市污水处理及回用技术中,膜生物反应器(Membrane Bioreactor, MBR)是将膜分离技术与生物反应器技术相结合的一种新型污水处理工艺,日益受到各国水处理技术研究者的关注。然而,膜污染是当前制约MBR广泛应用的关键问题,膜污染导致系统膜通量下降、膜清洗和更换频率加快,进而增加MBR运行的能耗和成本。
本研究采用浸没板式不锈钢金属膜生物反应器(Metal Membrane Bioreactor, MMBR)处理城市污水,考察不锈钢金属膜应用于城市污水处理可行性的同时,对MMBR运行中的膜污染问题进行深入研究,探讨膜污染控制和膜清洗的各种方法及效果,为MMBR在城市污水和其他工业废水处理中的实际应用与推广提供理论指导和技术支持。
系统的运行参数是MBR运行中膜污染的重要影响因素,因此在MMBR处理城市污水的长期实验前,首先开展了运行参数的优化工作。通过选取抽停时间比、曝气量、反洗频率和反洗水量为控制参数,以跨膜压力(Trans-membrane Pressure, TMP)的日均变化值为评价指标,进行L9(34)正交实验,得出了相应的优化参数值和影响强度顺序。
根据正交实验的优化参数,MMBR在0.4～1m3/(m2·d)的膜通量下进行了270d的连续运行。结果表明：在稳定运行阶段,无论是单一好氧还是缺氧/好氧(Anoxic/Oxic, A/O)模式,系统均具有良好的化学需氧量(Chemical Oxygen Demand, COD)、氨氮、悬浮固体(Suspended Solids, SS)去除能力。金属膜的过滤强化了系统的COD去除能力,较高的混合液悬浮固体(Mixed Liquor Suspended Solids, MLSS)浓度和系统特殊的内循环结构导致的同步硝化反硝化(Simultaneous Nitrification and Denitrification, SND)带来了额外的总氮(Total Nitrogen, TN)去除效果。
通过对膜污染状况、膜过滤阻力组成和膜清洗的研究,发现好氧模式下优势膜过滤阻力为凝胶滤饼层阻力,A/O模式下的优势阻力则为膜内部阻力。好氧模式下膜污染能通过机械清洗和NaOCl在线反洗有效去除,系统在0.8～1m3/(m2·d)的高膜通量下未进行离线清洗连续运行了115d。而A/O模式下单纯膜清洗已不足以控制膜污染的发展,必须对混合液性状进行调控,减小系统中微小粒子的数量,减缓膜内部污染的发展。
为对系统混合液性状进行调控,减缓膜污染的发展,进行了投加粉末活性炭(Powdered Activated Carbon, PAC)的MMBR对比研究。通过对两组MMBR系统中污染物去除率、TMP变化趋势、膜过滤阻力组成以及混合液性状的比较,发现投加PAC能提高MMBR系统的抗冲击负荷能力,并能有效改善混合液性状,增加混合液絮体的平均粒径和强度,降低微粒子、胞外聚合物(Extracellular Polymeric Substance, EPS )、胶体颗粒、溶解物质的浓度及混合液粘度值,进而有效减轻膜污染,减缓TMP的增加速度,延长MMBR系统的运行时间。
考虑到使用NaOCl等化学药剂进行膜清洗带来的环境问题,本研究针对连续运行的MMBR进行了臭氧在线和离线膜清洗实验,考察臭氧水浓度、pH、清洗时间、清洗频率等对膜污染去除效果的影响,并通过寻找优化的臭氧水清洗参数值,建立了一种新型环保有效的膜污染控制和清洗方法。
为考察本研究所用不锈钢金属膜过滤性能与有机膜的差别,最后还进行了不锈钢膜与聚醚砜(Polyethersulfone, PES)膜的对比实验。结果显示不锈钢膜的膜固有阻力和临界通量都优于PES膜。在处理城市污水的连续运行中,二者对污染物的去除效果差别不大,但不锈钢膜TMP增加速度较慢,抗污染能力较强,还具有强度高、耐腐蚀、抗氧化、可干态保存、应用范围广等诸多优点,具有很好的应用前景和发展潜力。
With the development of social economy, rapid urbanization and increasing environmental awareness, water resource stress becomes more evident and serious in city areas recently. Municipal sewage, called "the second water source", is widely reclaimed and reused to meet the growing city water pressure in all over the world. Membrane bioreactor (MBR), combined with membrane separation technology and biological treatment process, has been much respected among numerous municipal sewage reusing technologies by water treatment researchers. However, membrane fouling has been a main obstacle preventing wide utilization of MBRs because it causes a significant decline of permeate flux, requires more cleanings and replacement of fouled membranes, and consequently, increases the energy consumption and operating cost of the treatment process.
In this study a submerged metal membrane bioreactor (MMBR) coupled with stainless steel flat membranes was performed for treating municipal sewage. The feasibility of MMBR in treating municipal sewage was investigated. Membrane fouling behaviors were also investigated to discuss the effect of membrane fouling control and membrane cleaning. This study will provide theoretical foundation and technical support for the wide utilization of MMBR in municipal sewage and industrial waste treatment.
Operationc parameters affected membrane fouling greatly. Therefore, an orthogonal optimization experiment of operational parameters was carried out before long period running. Four parameters including the ratio of suction time to non-suction time, aeration rate, backwashing frequency and backwashing flux were chosen as the factors. Average daily change rate of trans-membrane pressure (TMP) was used as the evaluate index. Lastly the optimal operational parameters and its influence intensity sequence were obtained by the L9(34) orthogonal experiment.
According to the optimal operational parameters, continued experiment was carried out for 270 days at the permeate flux of 0.4～1m/(m2·d). The results indicated that MMBR had good removal efficiencies of chemical oxygen demand (COD), ammonium and suspended solids (SS) under both oxic and anoxic/oxic (A/O) mode in stable state. COD removal efficiency was improved by the fine filtration of stainless steel membrane. Simultaneous nitrification and denitrification (SND) due to high mixed liquor suspended solids (MLSS) concentration and special inner circulation structure resulted in additional total nitrogen (TN) removal.
The study on membrane fouling, composition of filtration resistance and membrane cleaning showed that the predominate filtration resistances under oxic mode and A/O mode were cake layer resistance and internal resistance, respectively. Membrane fouling under oxic mode was alleviated effectively by mechanical cleaning or on-line NaOCl back washing and MMBR ran stably for 115 days at the permeate flux of 0.8～1m3/(m2·d) without off-line cleaning. But membrane fouling could not be controlled only by membrane cleaning under A/O mode. Mixed liquor characteristics must be controlled to reduce the amount of fine particles and slow down the worsening rate of internal fouling.
Comparative experiments on effect of dosing powdered activated carbon (PAC) to mixed liquor characteristics were performed. The influence of PAC on contamination removal efficiencies, mixed liquor characteristics, filtration resistance and membrane fouling was investigated. The results showed that the anti-shock loading capability was improved by PAC in MMBR. The mixed liquor characteristics was also modified by PAC as increased mean particle size, enhanced intensity of floc, lower concentrations of fine particles, soluble substance and extracellular polymeric substance (EPS), and lower viscosity. Therefore membrane fouling was well controlled, which resulted in slower increasing rate of TMP and long operation life of MMBR.
Because of the environmental damage due to NaOCl used in membrane cleaning, green and safe membrane cleaning reagents were needed. Ozone was used as a new membrane cleaning reagent to control and remove membrane fouling in the study. On-line back washing and off-line washing with ozone solution under different concentration, pH, washing time and washing frequency were conducted. At last an effective membrane cleaning method with ozone solution was established.
Finally a comparative study between stainless steel membrane and polyethersulfone (PES) membrane was carried out. The stainless steel membrane showed lower membrane intrinsic resistance and higher critical flux. In the treatment of municipal sewage, stainless steel membrane and PES membrane showed almost the same contaminant removal efficiencies, but the stainless steel membrane indicated higher anti-fouling ability and slower TMP increasing rate. Combined with other advantages such as high intensity, strong corrosion resistance, good antioxidation, convenient preservation at dry state and wide utilization scope, the stainless steel membrane must have a promising future in wastewater treatment.
本研究采用浸没板式不锈钢金属膜生物反应器(Metal Membrane Bioreactor, MMBR)处理城市污水,考察不锈钢金属膜应用于城市污水处理可行性的同时,对MMBR运行中的膜污染问题进行深入研究,探讨膜污染控制和膜清洗的各种方法及效果,为MMBR在城市污水和其他工业废水处理中的实际应用与推广提供理论指导和技术支持。
系统的运行参数是MBR运行中膜污染的重要影响因素,因此在MMBR处理城市污水的长期实验前,首先开展了运行参数的优化工作。通过选取抽停时间比、曝气量、反洗频率和反洗水量为控制参数,以跨膜压力(Trans-membrane Pressure, TMP)的日均变化值为评价指标,进行L9(34)正交实验,得出了相应的优化参数值和影响强度顺序。
根据正交实验的优化参数,MMBR在0.4～1m3/(m2·d)的膜通量下进行了270d的连续运行。结果表明：在稳定运行阶段,无论是单一好氧还是缺氧/好氧(Anoxic/Oxic, A/O)模式,系统均具有良好的化学需氧量(Chemical Oxygen Demand, COD)、氨氮、悬浮固体(Suspended Solids, SS)去除能力。金属膜的过滤强化了系统的COD去除能力,较高的混合液悬浮固体(Mixed Liquor Suspended Solids, MLSS)浓度和系统特殊的内循环结构导致的同步硝化反硝化(Simultaneous Nitrification and Denitrification, SND)带来了额外的总氮(Total Nitrogen, TN)去除效果。
通过对膜污染状况、膜过滤阻力组成和膜清洗的研究,发现好氧模式下优势膜过滤阻力为凝胶滤饼层阻力,A/O模式下的优势阻力则为膜内部阻力。好氧模式下膜污染能通过机械清洗和NaOCl在线反洗有效去除,系统在0.8～1m3/(m2·d)的高膜通量下未进行离线清洗连续运行了115d。而A/O模式下单纯膜清洗已不足以控制膜污染的发展,必须对混合液性状进行调控,减小系统中微小粒子的数量,减缓膜内部污染的发展。
为对系统混合液性状进行调控,减缓膜污染的发展,进行了投加粉末活性炭(Powdered Activated Carbon, PAC)的MMBR对比研究。通过对两组MMBR系统中污染物去除率、TMP变化趋势、膜过滤阻力组成以及混合液性状的比较,发现投加PAC能提高MMBR系统的抗冲击负荷能力,并能有效改善混合液性状,增加混合液絮体的平均粒径和强度,降低微粒子、胞外聚合物(Extracellular Polymeric Substance, EPS )、胶体颗粒、溶解物质的浓度及混合液粘度值,进而有效减轻膜污染,减缓TMP的增加速度,延长MMBR系统的运行时间。
考虑到使用NaOCl等化学药剂进行膜清洗带来的环境问题,本研究针对连续运行的MMBR进行了臭氧在线和离线膜清洗实验,考察臭氧水浓度、pH、清洗时间、清洗频率等对膜污染去除效果的影响,并通过寻找优化的臭氧水清洗参数值,建立了一种新型环保有效的膜污染控制和清洗方法。
为考察本研究所用不锈钢金属膜过滤性能与有机膜的差别,最后还进行了不锈钢膜与聚醚砜(Polyethersulfone, PES)膜的对比实验。结果显示不锈钢膜的膜固有阻力和临界通量都优于PES膜。在处理城市污水的连续运行中,二者对污染物的去除效果差别不大,但不锈钢膜TMP增加速度较慢,抗污染能力较强,还具有强度高、耐腐蚀、抗氧化、可干态保存、应用范围广等诸多优点,具有很好的应用前景和发展潜力。
With the development of social economy, rapid urbanization and increasing environmental awareness, water resource stress becomes more evident and serious in city areas recently. Municipal sewage, called "the second water source", is widely reclaimed and reused to meet the growing city water pressure in all over the world. Membrane bioreactor (MBR), combined with membrane separation technology and biological treatment process, has been much respected among numerous municipal sewage reusing technologies by water treatment researchers. However, membrane fouling has been a main obstacle preventing wide utilization of MBRs because it causes a significant decline of permeate flux, requires more cleanings and replacement of fouled membranes, and consequently, increases the energy consumption and operating cost of the treatment process.
In this study a submerged metal membrane bioreactor (MMBR) coupled with stainless steel flat membranes was performed for treating municipal sewage. The feasibility of MMBR in treating municipal sewage was investigated. Membrane fouling behaviors were also investigated to discuss the effect of membrane fouling control and membrane cleaning. This study will provide theoretical foundation and technical support for the wide utilization of MMBR in municipal sewage and industrial waste treatment.
Operationc parameters affected membrane fouling greatly. Therefore, an orthogonal optimization experiment of operational parameters was carried out before long period running. Four parameters including the ratio of suction time to non-suction time, aeration rate, backwashing frequency and backwashing flux were chosen as the factors. Average daily change rate of trans-membrane pressure (TMP) was used as the evaluate index. Lastly the optimal operational parameters and its influence intensity sequence were obtained by the L9(34) orthogonal experiment.
According to the optimal operational parameters, continued experiment was carried out for 270 days at the permeate flux of 0.4～1m/(m2·d). The results indicated that MMBR had good removal efficiencies of chemical oxygen demand (COD), ammonium and suspended solids (SS) under both oxic and anoxic/oxic (A/O) mode in stable state. COD removal efficiency was improved by the fine filtration of stainless steel membrane. Simultaneous nitrification and denitrification (SND) due to high mixed liquor suspended solids (MLSS) concentration and special inner circulation structure resulted in additional total nitrogen (TN) removal.
The study on membrane fouling, composition of filtration resistance and membrane cleaning showed that the predominate filtration resistances under oxic mode and A/O mode were cake layer resistance and internal resistance, respectively. Membrane fouling under oxic mode was alleviated effectively by mechanical cleaning or on-line NaOCl back washing and MMBR ran stably for 115 days at the permeate flux of 0.8～1m3/(m2·d) without off-line cleaning. But membrane fouling could not be controlled only by membrane cleaning under A/O mode. Mixed liquor characteristics must be controlled to reduce the amount of fine particles and slow down the worsening rate of internal fouling.
Comparative experiments on effect of dosing powdered activated carbon (PAC) to mixed liquor characteristics were performed. The influence of PAC on contamination removal efficiencies, mixed liquor characteristics, filtration resistance and membrane fouling was investigated. The results showed that the anti-shock loading capability was improved by PAC in MMBR. The mixed liquor characteristics was also modified by PAC as increased mean particle size, enhanced intensity of floc, lower concentrations of fine particles, soluble substance and extracellular polymeric substance (EPS), and lower viscosity. Therefore membrane fouling was well controlled, which resulted in slower increasing rate of TMP and long operation life of MMBR.
Because of the environmental damage due to NaOCl used in membrane cleaning, green and safe membrane cleaning reagents were needed. Ozone was used as a new membrane cleaning reagent to control and remove membrane fouling in the study. On-line back washing and off-line washing with ozone solution under different concentration, pH, washing time and washing frequency were conducted. At last an effective membrane cleaning method with ozone solution was established.
Finally a comparative study between stainless steel membrane and polyethersulfone (PES) membrane was carried out. The stainless steel membrane showed lower membrane intrinsic resistance and higher critical flux. In the treatment of municipal sewage, stainless steel membrane and PES membrane showed almost the same contaminant removal efficiencies, but the stainless steel membrane indicated higher anti-fouling ability and slower TMP increasing rate. Combined with other advantages such as high intensity, strong corrosion resistance, good antioxidation, convenient preservation at dry state and wide utilization scope, the stainless steel membrane must have a promising future in wastewater treatment.
引文
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