膜生物反应器及电絮凝—过滤技术在分散式生活污水处理中的应用研究
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摘要
对于生活污水集中收集处理受到限制的地区,建立及推广分散式生活污水处理技术成为解决该类地区水污染问题的可行途径。超滤膜生物反应器(MBR)和电絮凝(EF)-过滤系统均具备占地面积小、出水水质高和稳定可靠等优点,因此本文对膜生物反应器及电絮凝-过滤技术应用于分散式生活污水处理进行了研究。
超滤膜生物反应器的研究采用德国某公司提供的一体化单级MBR。由于单级MBR设计参数固定且德国生活习惯与我国山区存在巨大差异,启动阶段膜生物反应器污泥负荷(F/M)远低于0.05kgCOD/kgMLSS·d,造成了严重的污泥解体。表征污泥活性的指标单位氧气利用率(SOUR)从37.25 mg O2/g MLSS/h降低到20.29 mg O2/g MLSS/h,污泥浓度从4g/L下降并稳定在2g/L,污泥体积平均粒径也从104μm降低到59μm,溶解性微生物产物SMP中蛋白和多糖的比例分别比初始阶段增加了11倍和6.5倍,造成严重的膜污染。针对启动阶段遇到的问题,采用2g/L污泥浓度启动,保证污泥负荷(F/M)在0.05kgCOD/kgMLSS·d以上,并在好氧生物池完成污泥驯化后将膜组件放入系统内进行一体化运行,避免严重的膜污染。
环境温度的变化也是制约单级MBR运行的因素。水温在13℃以上,单级MBR可保持优异的COD以及氨氮的去除效率,同时由于超滤膜组件自身的特性,可保证对于悬浮颗粒物的全部去除。与传统活性污泥系统类似,在水温低于4℃的情况下,MBR反应器内的微生物进入休眠状态,无法对水中污染物质进行分解代谢,对于氨氮和COD的去除均由膜组件的物理截留造成。当水温进一步降低至0℃以下时,污泥出现大面积解体、造成严重膜污染以及出水水质恶化。建议MBR在分散式处理中统一采用埋地式安装,以应对当地的低温天气。
无法高效脱氮除磷是单级MBR的瓶颈。对原有单级MBR进行改良构建两级序批式膜生物反应器(TSBMBR)实现了COD、NH3-N、TN和TP分别达到94%、90%、82%和90%以上的去除率,出水符合景观用水标准。第一级反应器(TSBMBR1)中污泥龄控制在5-7天,并创造适合聚磷菌PAOs生存的条件,系统始终保持高效的除磷效果。在TSBMBR1中形成了颗粒化污泥与絮体污泥共存的现象。在系统运行30天后,污泥SVI值稳定在50ml/g,粒径从84μm增长到300μm。胞外聚合物EPS含量随着颗粒化的进行从接种状态时的40 mg/g MLSS上升至80-100 mg/g MLSS,同时SMP伴随着反应器中污泥颗粒化的过程也从5 mg/g MLSS迅速增加至15-20 mg/g MLSS,随着颗粒化的稳定SMP含量一直保持在较高的水平。同时污泥表面电荷负向增加,相对憎水性增强。
第二级反应器(TSBMBR2)在排泥模式下污泥浓度稳定在6-8g/L,污泥龄控制在25-30天,可保证高效的总氮去除率且膜通量稳定没有出现明显的膜污染。同时由于泥龄长,系统内出现大量原生和后生动物。TSBMBR2进入不排泥模式污泥浓度增长至13g/L,同时SOUR从30 mg O2·g MLSS·h-1下降至10 mg O2·g MLSS·h-1,微生物进入以内源呼吸为主模式,反应器内形成以丝状菌为主体的菌群模式。随着系统运行过程中丝状菌不断大量繁殖,使得污泥表面电荷逐步下降,从接种污泥的-1.6meq./g MLSS下降到-2.6meq./g MLSS,同时污泥絮体的憎水性也显著提高,从45%上升到95%,单位膜通量从最初的750 L?h-1?bar-1下降至400L?h-1?bar-1附近。通过SPSS的相关性分析可以发现,EPS中的蛋白对污泥沉降性能具有明显影响,并且由于EPS中蛋白组分占主导,因此总EPS和污泥沉降性能也有较好的相关性,同时单位膜通量和SMP中的多糖含量有很好的相关性。
两级序批式膜生物反应器优质出水的代价是牺牲了膜单元的处理能力,膜组件处理能力仅为原有单级MBR的40%。同时,两级序批式膜生物反应器无法对已有的单级MBR在现场进行改装,因此在保证膜单元处理能力不变的情况下,使出水满足回用水标准是下一步工作的方向。同时,污水分散式处理技术也要求在保证高效处理能力的同时,具备应对突发性废水如含重金属废水排放的能力。
采用电絮凝-沙滤系统对二级生物处理出水进行深度处理,取得了97%的除磷效率和20-25%的总有机碳TOC去除率。该技术具有模块化、占地面积小以及自动化程度高等特点,具备和其它处理工艺串连的能力。电絮凝-过滤技术可对含重金属废水进行高效去除。选取Ni为目标重金属进行处理发现溶解氧在电絮凝过程中起到非常重要的作用,并对后继的过滤作用产生影响。随着曝气的加入,铁电极释放的铁离子的量并没有增加。通过试验可确定溶解氧耗尽拐点(DOEP)。本系统中1.3 mg/L DO可被认为是DOEP同时是二价铁离子富集的转折点。曝气可以使反应器的溶解氧在DOEP之上,从而保证反应器中三价铁离子占主导。非曝气状态下电絮凝与微滤的结合以及曝气状态下电絮凝与沉淀和滤纸过滤的结合均可完全去除溶液中Ni和Fe离子,使出水达标排放。
本文最后对单级MBR与电絮凝-沙滤联用技术从理论可行性和运行成本的角度进行了分析,认为该组合技术除了具有应对突发重金属废水污染的能力,与两级膜生物反应器相比还具有运行成本低和处理量高的特点,且出水可满足城市生活杂用水排放标准。因此有必要在接下来的工作中通过中试研究对该组合工艺进行验证。
The construction and popularization of decentralized municipal wastewater treatment technology is the feasible approach in resolving water pollution problem in the area, where centralized wastewater collection and treatment is restricted. Both the ultra-filtration membrane bioreactor system and Electroflocculation–Filtration system own advantages like small footprint, excellent effluent quality and high reliability. Therefore, Research on membrane bioreactor and electroflocculation-filtration technology in decentralized municipal wastewater treatment has been done in this paper.
The research on ultra-filtration membrane bioreactor is basing on the integrated one-stage MBR supplied by certain German company. Due to fixed design parameters of one-stage MBR and life style diversity between German and Chinese domestic mountain areas, sludge loading rate (F/M) in MBR was much lower than 0.05kgCOD/kgMLSS·d during initiation. Severe sludge disaggregation happened. The SOUR, MLSS and particle size dropped from 37.25 mg O2/g MLSS/h to 20.29 mg O2/g MLSS/h, 4g/L to 2g/L, and 104μm to 59μm separately. Protein and polysaccharide concentration in the soluble microbial products (SMP) increased 11 times and 6.5 times than initiation values and severe membrane fouling occurred. Aiming at resolving the problem during initiation, sludge inoculation concentration was control at 2g/L and F/M was kept above 0.05kgCOD/kgMLSS·d. Membrane module was integrated into system after sludge acclimation to avoid severe membrane fouling during initiation.
The diversity of ambient temperature was also the restriction on one-stage MBR operation. Excellent COD and ammonium removal efficiency could achieve when the water temperature was above 13℃, and suspended solids could be removed by membrane blockage. Similar as traditional activated sludge system, when the water temperature was below 4℃, sludge bacteria went into dominancy phase and metabolism stopped. All the removal of nitrogen and COD was due to membrane blockage. When the water temperature was below zero, sludge disaggregation appeared in large amount, severe membrane fouling existed and deteriorated effluent discharged. It is suggested that MBR system used in decentralized treatment should be constructed underground to face with low temperature.
One-stage MBR itself could not reach high nitrogen and phosphorous removal efficiency. Two-stage sequencing batch membrane bioreactor (TSBMBR) could reach above 94%,90%,82% and 90% removal efficiency of COD,NH3-N,TN and TP after the modification of one-stage MBR, and the effluent could reach scenic environment use water quality criteria. Sludge age was controlled at 5 to 7 days in the first stage of TSBMBR (TSBMBR1). Favorable living conditions for phosphorous accumulating organisms (PAOs) were provided and high phosphorous removal efficiency could be kept in this stage. Granular sludge and sludge flocs co-existed in TSBMBR1. After 30 days operation, SVI reached 50ml/g, and sludge particle size increased from 84μm to 300μm. The amount of extracellular polymer substances (EPS) also increased from 40 mg/g MLSS to 80-100 mg/g MLSS, meanwhile, the amount of soluble microbial products (SMP) also increased from 5 mg/g MLSS to 15-20 mg/g MLSS during sludge granulation period and stabilized at a high level after granulation achieved. Sludge surface charge increased negatively and the relative hydrophobicity increased.
Sludge concentration in the second stage of TSBMBR (TSBMBR2) was kept at 6-8g/L during sludge-discharging mode, and the sludge age was controlled at 25-30 days. High TN removal efficiency could be achieved. No severe membrane fouling happened and the trans-membrane flux kept stable. Meanwhile, a large amount of Protozoa and metazoan appeared in the system due to long sludge age. In sludge non-discharging mode, sludge concentration in TSBMBR2 reached 13g/L and SOUR dropped from 30 mg O2·g MLSS·h-1 to 10 mg O2·g MLSS·h-1. Sludge bacteria went into endogenous respiration. Filamentous bacteria were dominant in the reactor at that time. With the multiplication of filamentous bacteria, sludge surface charge dropped gradually from -1.6meq./g MLSS to -2.6meq./g MLSS. Meanwhile, sludge relative hydrophobicity increased from 45% to 95%, and the specific membrane flux dropped from 750 L?h-1?bar-1 to 400L?h-1?bar-1. After SPSS analysis, the protein proportion in EPS owned obvious correlation with sludge settling ability. The total EPS also owned good correlation with sludge settling ability due to the large dominance of protein proportion in EPS. Meanwhile, the specific membrane flux was correlated with SMP polysaccharides concentration.
The excellent effluent quality from TSBMBR is at the cost of the deduction of membrane module treatment quantity, which is only 40% of original one-stage MBR. Meanwhile, the modification of one-stage MBR into TSBMBR could not be accomplished in the field. So the next step is to meet recycled water criteria and keep membrane module treatment quantity at the same time. Meanwhile, decentralized treatment technology should keep high treatment efficiency and have the ability to face with emergent wastewater, i.e., wastewater with high concentration of heavy metal.
Electroflocculation (EF)-Granular Filtration (GF) system was used as tertiary treatment of secondary biological treatment effluent. The phosphorous and TOC removal rate could reach 97% and 20-25%. This technology owns advantages like integrated module configuration, small footprint, automatic control and etc, which enables this technology to be combined with other treatment process. Research has also been done by electroflocculation-filtration in heavy metal removal, and Nickel was chosen as the target pollutant in this paper. It was noted that dissolved oxygen (DO) played an important role in electroflocculation and thereafter filtration. The adding of aeration did not generate extra iron releasing from the electrodes. The dissolved oxygen exhaust point (DOEP) could be obtained by experiment. In this experiment system, 1.3 mg/L DO was regarded as DOEP, at which point ferrous iron accumulation appeared. Aeration could enable the DO above DOEP in the reactor to make sure the dominance of ferric iron in the reactor. The combination of EF and micro-filtration without aeration and EF plus sedimentation and paper filtration with aeration could both completely remove Ni and iron in the bulk water reach the water discharged criteria.
In the last part, from theoretical feasibility and cost points of view, analysis has been made on the hybrid of one-stage MBR and EF-GF technology. This combination owns characters like lower energy consumption and higher treatment efficiency than TSBMBR and the effluent could reach Water quality standard for urban miscellaneous water consumption. Therefore, it is necessary to do pilot operation in the next step to validate this technology hybridization.
超滤膜生物反应器的研究采用德国某公司提供的一体化单级MBR。由于单级MBR设计参数固定且德国生活习惯与我国山区存在巨大差异,启动阶段膜生物反应器污泥负荷(F/M)远低于0.05kgCOD/kgMLSS·d,造成了严重的污泥解体。表征污泥活性的指标单位氧气利用率(SOUR)从37.25 mg O2/g MLSS/h降低到20.29 mg O2/g MLSS/h,污泥浓度从4g/L下降并稳定在2g/L,污泥体积平均粒径也从104μm降低到59μm,溶解性微生物产物SMP中蛋白和多糖的比例分别比初始阶段增加了11倍和6.5倍,造成严重的膜污染。针对启动阶段遇到的问题,采用2g/L污泥浓度启动,保证污泥负荷(F/M)在0.05kgCOD/kgMLSS·d以上,并在好氧生物池完成污泥驯化后将膜组件放入系统内进行一体化运行,避免严重的膜污染。
环境温度的变化也是制约单级MBR运行的因素。水温在13℃以上,单级MBR可保持优异的COD以及氨氮的去除效率,同时由于超滤膜组件自身的特性,可保证对于悬浮颗粒物的全部去除。与传统活性污泥系统类似,在水温低于4℃的情况下,MBR反应器内的微生物进入休眠状态,无法对水中污染物质进行分解代谢,对于氨氮和COD的去除均由膜组件的物理截留造成。当水温进一步降低至0℃以下时,污泥出现大面积解体、造成严重膜污染以及出水水质恶化。建议MBR在分散式处理中统一采用埋地式安装,以应对当地的低温天气。
无法高效脱氮除磷是单级MBR的瓶颈。对原有单级MBR进行改良构建两级序批式膜生物反应器(TSBMBR)实现了COD、NH3-N、TN和TP分别达到94%、90%、82%和90%以上的去除率,出水符合景观用水标准。第一级反应器(TSBMBR1)中污泥龄控制在5-7天,并创造适合聚磷菌PAOs生存的条件,系统始终保持高效的除磷效果。在TSBMBR1中形成了颗粒化污泥与絮体污泥共存的现象。在系统运行30天后,污泥SVI值稳定在50ml/g,粒径从84μm增长到300μm。胞外聚合物EPS含量随着颗粒化的进行从接种状态时的40 mg/g MLSS上升至80-100 mg/g MLSS,同时SMP伴随着反应器中污泥颗粒化的过程也从5 mg/g MLSS迅速增加至15-20 mg/g MLSS,随着颗粒化的稳定SMP含量一直保持在较高的水平。同时污泥表面电荷负向增加,相对憎水性增强。
第二级反应器(TSBMBR2)在排泥模式下污泥浓度稳定在6-8g/L,污泥龄控制在25-30天,可保证高效的总氮去除率且膜通量稳定没有出现明显的膜污染。同时由于泥龄长,系统内出现大量原生和后生动物。TSBMBR2进入不排泥模式污泥浓度增长至13g/L,同时SOUR从30 mg O2·g MLSS·h-1下降至10 mg O2·g MLSS·h-1,微生物进入以内源呼吸为主模式,反应器内形成以丝状菌为主体的菌群模式。随着系统运行过程中丝状菌不断大量繁殖,使得污泥表面电荷逐步下降,从接种污泥的-1.6meq./g MLSS下降到-2.6meq./g MLSS,同时污泥絮体的憎水性也显著提高,从45%上升到95%,单位膜通量从最初的750 L?h-1?bar-1下降至400L?h-1?bar-1附近。通过SPSS的相关性分析可以发现,EPS中的蛋白对污泥沉降性能具有明显影响,并且由于EPS中蛋白组分占主导,因此总EPS和污泥沉降性能也有较好的相关性,同时单位膜通量和SMP中的多糖含量有很好的相关性。
两级序批式膜生物反应器优质出水的代价是牺牲了膜单元的处理能力,膜组件处理能力仅为原有单级MBR的40%。同时,两级序批式膜生物反应器无法对已有的单级MBR在现场进行改装,因此在保证膜单元处理能力不变的情况下,使出水满足回用水标准是下一步工作的方向。同时,污水分散式处理技术也要求在保证高效处理能力的同时,具备应对突发性废水如含重金属废水排放的能力。
采用电絮凝-沙滤系统对二级生物处理出水进行深度处理,取得了97%的除磷效率和20-25%的总有机碳TOC去除率。该技术具有模块化、占地面积小以及自动化程度高等特点,具备和其它处理工艺串连的能力。电絮凝-过滤技术可对含重金属废水进行高效去除。选取Ni为目标重金属进行处理发现溶解氧在电絮凝过程中起到非常重要的作用,并对后继的过滤作用产生影响。随着曝气的加入,铁电极释放的铁离子的量并没有增加。通过试验可确定溶解氧耗尽拐点(DOEP)。本系统中1.3 mg/L DO可被认为是DOEP同时是二价铁离子富集的转折点。曝气可以使反应器的溶解氧在DOEP之上,从而保证反应器中三价铁离子占主导。非曝气状态下电絮凝与微滤的结合以及曝气状态下电絮凝与沉淀和滤纸过滤的结合均可完全去除溶液中Ni和Fe离子,使出水达标排放。
本文最后对单级MBR与电絮凝-沙滤联用技术从理论可行性和运行成本的角度进行了分析,认为该组合技术除了具有应对突发重金属废水污染的能力,与两级膜生物反应器相比还具有运行成本低和处理量高的特点,且出水可满足城市生活杂用水排放标准。因此有必要在接下来的工作中通过中试研究对该组合工艺进行验证。
The construction and popularization of decentralized municipal wastewater treatment technology is the feasible approach in resolving water pollution problem in the area, where centralized wastewater collection and treatment is restricted. Both the ultra-filtration membrane bioreactor system and Electroflocculation–Filtration system own advantages like small footprint, excellent effluent quality and high reliability. Therefore, Research on membrane bioreactor and electroflocculation-filtration technology in decentralized municipal wastewater treatment has been done in this paper.
The research on ultra-filtration membrane bioreactor is basing on the integrated one-stage MBR supplied by certain German company. Due to fixed design parameters of one-stage MBR and life style diversity between German and Chinese domestic mountain areas, sludge loading rate (F/M) in MBR was much lower than 0.05kgCOD/kgMLSS·d during initiation. Severe sludge disaggregation happened. The SOUR, MLSS and particle size dropped from 37.25 mg O2/g MLSS/h to 20.29 mg O2/g MLSS/h, 4g/L to 2g/L, and 104μm to 59μm separately. Protein and polysaccharide concentration in the soluble microbial products (SMP) increased 11 times and 6.5 times than initiation values and severe membrane fouling occurred. Aiming at resolving the problem during initiation, sludge inoculation concentration was control at 2g/L and F/M was kept above 0.05kgCOD/kgMLSS·d. Membrane module was integrated into system after sludge acclimation to avoid severe membrane fouling during initiation.
The diversity of ambient temperature was also the restriction on one-stage MBR operation. Excellent COD and ammonium removal efficiency could achieve when the water temperature was above 13℃, and suspended solids could be removed by membrane blockage. Similar as traditional activated sludge system, when the water temperature was below 4℃, sludge bacteria went into dominancy phase and metabolism stopped. All the removal of nitrogen and COD was due to membrane blockage. When the water temperature was below zero, sludge disaggregation appeared in large amount, severe membrane fouling existed and deteriorated effluent discharged. It is suggested that MBR system used in decentralized treatment should be constructed underground to face with low temperature.
One-stage MBR itself could not reach high nitrogen and phosphorous removal efficiency. Two-stage sequencing batch membrane bioreactor (TSBMBR) could reach above 94%,90%,82% and 90% removal efficiency of COD,NH3-N,TN and TP after the modification of one-stage MBR, and the effluent could reach scenic environment use water quality criteria. Sludge age was controlled at 5 to 7 days in the first stage of TSBMBR (TSBMBR1). Favorable living conditions for phosphorous accumulating organisms (PAOs) were provided and high phosphorous removal efficiency could be kept in this stage. Granular sludge and sludge flocs co-existed in TSBMBR1. After 30 days operation, SVI reached 50ml/g, and sludge particle size increased from 84μm to 300μm. The amount of extracellular polymer substances (EPS) also increased from 40 mg/g MLSS to 80-100 mg/g MLSS, meanwhile, the amount of soluble microbial products (SMP) also increased from 5 mg/g MLSS to 15-20 mg/g MLSS during sludge granulation period and stabilized at a high level after granulation achieved. Sludge surface charge increased negatively and the relative hydrophobicity increased.
Sludge concentration in the second stage of TSBMBR (TSBMBR2) was kept at 6-8g/L during sludge-discharging mode, and the sludge age was controlled at 25-30 days. High TN removal efficiency could be achieved. No severe membrane fouling happened and the trans-membrane flux kept stable. Meanwhile, a large amount of Protozoa and metazoan appeared in the system due to long sludge age. In sludge non-discharging mode, sludge concentration in TSBMBR2 reached 13g/L and SOUR dropped from 30 mg O2·g MLSS·h-1 to 10 mg O2·g MLSS·h-1. Sludge bacteria went into endogenous respiration. Filamentous bacteria were dominant in the reactor at that time. With the multiplication of filamentous bacteria, sludge surface charge dropped gradually from -1.6meq./g MLSS to -2.6meq./g MLSS. Meanwhile, sludge relative hydrophobicity increased from 45% to 95%, and the specific membrane flux dropped from 750 L?h-1?bar-1 to 400L?h-1?bar-1. After SPSS analysis, the protein proportion in EPS owned obvious correlation with sludge settling ability. The total EPS also owned good correlation with sludge settling ability due to the large dominance of protein proportion in EPS. Meanwhile, the specific membrane flux was correlated with SMP polysaccharides concentration.
The excellent effluent quality from TSBMBR is at the cost of the deduction of membrane module treatment quantity, which is only 40% of original one-stage MBR. Meanwhile, the modification of one-stage MBR into TSBMBR could not be accomplished in the field. So the next step is to meet recycled water criteria and keep membrane module treatment quantity at the same time. Meanwhile, decentralized treatment technology should keep high treatment efficiency and have the ability to face with emergent wastewater, i.e., wastewater with high concentration of heavy metal.
Electroflocculation (EF)-Granular Filtration (GF) system was used as tertiary treatment of secondary biological treatment effluent. The phosphorous and TOC removal rate could reach 97% and 20-25%. This technology owns advantages like integrated module configuration, small footprint, automatic control and etc, which enables this technology to be combined with other treatment process. Research has also been done by electroflocculation-filtration in heavy metal removal, and Nickel was chosen as the target pollutant in this paper. It was noted that dissolved oxygen (DO) played an important role in electroflocculation and thereafter filtration. The adding of aeration did not generate extra iron releasing from the electrodes. The dissolved oxygen exhaust point (DOEP) could be obtained by experiment. In this experiment system, 1.3 mg/L DO was regarded as DOEP, at which point ferrous iron accumulation appeared. Aeration could enable the DO above DOEP in the reactor to make sure the dominance of ferric iron in the reactor. The combination of EF and micro-filtration without aeration and EF plus sedimentation and paper filtration with aeration could both completely remove Ni and iron in the bulk water reach the water discharged criteria.
In the last part, from theoretical feasibility and cost points of view, analysis has been made on the hybrid of one-stage MBR and EF-GF technology. This combination owns characters like lower energy consumption and higher treatment efficiency than TSBMBR and the effluent could reach Water quality standard for urban miscellaneous water consumption. Therefore, it is necessary to do pilot operation in the next step to validate this technology hybridization.
引文
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