废水厌氧生物除磷技术的基础研究
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摘要
我国的水体富营养化问题日益严重，磷元素是导致水体富营养化的主要因素之一，控制磷排放已成为解决水体富营养化问题的重要途径。近十多年来，厌氧生物工艺在有机废水处理上得到广泛应用，其中上流式厌氧污泥床(UpflowAnaerobic Sludge Blanket，简称UASB)已成为厌氧生物工艺的杰出代表而倍受人们青睐。但是，人们对厌氧生物工艺的关注，焦点集中在除碳功能上，对其除磷功能，则迄今未见系统的研究报道。本课题选用UASB反应器作为工作平台，深入系统地探索了厌氧生物工艺的除磷性能，获得了以下结果：
厌氧生物反应器具有良好的除磷效能。在水力停留时间(Hydrulic RetentionTime，简称HRT)为24 h、进水COD和磷酸盐浓度分别为5000～10000 mg/L和5～30 mgP/L的条件下，UASB反应器的容积磷去除率可高达21．4 mgP/L·d，磷酸盐去除率可高达99．0％以上，出水磷浓度低于0．5 mgP/L，达到国家《污水综合排放标准》(GB8978-1996)中的一级排放标准。
厌氧生物反应器的除磷功能主要来自厌氧微生物的同化作用。将废水中的磷酸盐用作营养物质，使之从废水中转移至厌氧微生物体内(磷由水相转移至固相)，再通过泥水分离，使之从废水中去除，这是UASB反应器实现除磷功能的重要途径。
厌氧生物反应器的除磷效能受多种因素的制约。进水COD浓度、磷酸盐浓度以及COD/P值皆为UASB反应器除磷效能的显著影响因子。提高进水COD浓度，有利于提高容积磷去除率和磷酸盐去除率。提高进水磷酸盐浓度，有助于提高容积磷去除率，但会降低磷酸盐去除率。提高进水COD/P值，有利于提高磷酸盐去除率，但会限制容积磷去除率。
厌氧生物反应器的除磷效能与除碳效能密切相关。提高反应器的除碳效能有助于提高除磷效能，但除碳效能受除磷效能的影响较小。在进水COD/P值较高的条件下(1000：1)，依然能够获得较高的除碳效能(10 gCOD/L·d)，碳磷去除比例达1182：1；而在COD/P值较低(1000：2～1000：3)的条件下，碳磷去除比例平均值为655：1，并随容积COD去除率的提高而降低至500：1左右。
厌氧生物反应器的除磷效能与除氮效能联系紧密。在除氮效能较高的运行条件下，除磷效能相应较高，但在除磷效能较低的情况下，除氮效能也受影响。在进水COD/P值较低(1000：2～1000：3)的条件下，氮磷去除比例稳定在8．6左右，基本不受进水N/P值以及容积氮去除率的影响；而在磷酸盐浓度较低的情况下(1000：1)，氮磷去除比例增高，最高达18．8。
厌氧生物反应器的除磷效能与生物相组成相关。PCR-DGGE分析以及扫描电镜观察表明，在UASB反应器的运行过程中，颗粒污泥的微生物组成逐步从以甲酸甲烷杆菌(Methanobacterium formicicum)等杆菌和球菌为主，转变为以理事会鬃毛甲烷菌(Methanosaeta concilii)等丝状菌为主。就出水磷浓度而言，以丝状菌为主的UASB反应器优于以球菌和杆菌为主的UASB反应器。
厌氧生物反应器的生物相变化与进水有机负荷及COD/P值密切相关。在污泥负荷(0．36～0．86 gCOD/gVSS·d)较低、进水COD/P值(1000：1～1000：2)较高的条件下，容易引发颗粒污泥丝状菌膨胀，导致污泥流失而使反应器运行失稳，影响除磷效能。
厌氧生物反应器的除磷效能可受硫酸盐的干扰。当进水COD/SO_4~(2-)值从7．0降低至2．3时，UASB反应器中的产甲烷过程受到抑制，容积磷去除率由9．6mgP/L·d降至2．0 mgP/L·d。硫酸盐还原成为主导反应时，UASB反应器的除磷效能降低。在进水COD、SO_4~(2-)和磷酸盐浓度分别为3500 mg/L、1500 mg/L和15～25mgP/L条件下，容积磷去除率为2．0～4．3 mgP/L·d，磷酸盐去除率为12．3％～26．2％。
Eutrophication has been one of the main water pollution problems in China, andit is important to control phosphorus discharge into waters to relieve the severity asphosphorus is the key factor to cause eutrophication. In recent years, great advanceshave been achieved in anaerobic biotechnology for wastewater treatment. The UASB(Upflow Anaerobic Sludge Blanket) process has become one of the most popularanaerobic treatment processes and has been applied in various wastewaters. Thefunction of UASB reactor for removal of organic pollutants has drawn a lot ofattention, but its function for removal of phosphorus has so far been ignored.
A laboratory scale UASB reactor was operated to investigate its performance onphosphorus removal, and the feasibility of its applications in treating phosphoruscontaining wastewater was assessed as well. The main results of the research weresummarized as follows:
High performance on phosphorus removal was shown in the laboratory scaleUASB reactor. The volumetric phosphorus removal rate of 21.4 mgP/L·d, the removalrate efficiency above 99 % and the effluent PO_4~(3-)-P concentration below 0.5 mg/L(the requirement in the general discharge standards of wastewater)could be achieved during the operation, when the influent COD and PO_4~(3-)-Pconcentrations were 5000～10000 mg/L and 5～30 mg/L, respectively.
The microbial assimilation was supposed to be the most important pathway forphosphorus removal in UASB reactor. The microorganisms in the sludge uptake thephosphate as nutrient during their growth (the phosphorus was transferred from theliquid phase to the solid phase), then phosphorus was removed by separating thesludge from the effluent.
The influent concentration of COD and phosphate and the COD/P ratio were themain factors affecting phosphorus removal efficiency. Higher volumetric phosphorusremoval rate was achieved at higher influent COD and phosphate concentrations. Theincrease in influent phosphorus concentration could result in lower phosphorusremoval efficiency but higher volumetric phosphorus removal rate. Larger COD/Pratio ensured higher phosphorus removal efficiency, but limited the furtherimprovement in volumetric phosphorus removal rate.
The volumetric removal rates of COD and phosphorus were highly correlated.The volumetric phosphorus removal rate increased as the COD removal rate elevated,while the volumetric COD removal rate was hardly affected by volumetricphosphorus removal rate. With the influent COD/P ratio of 1000:1, a volumetric CODremoval rate of 10 gCOD/L·d was achieved, meanwhile, the ratio of the consumedCOD to phosphorus reached a relatively high value of 1182:1. The ratio of consumedCOD to phosphorus was about 655:1 when the influent COD/P ratio was between1000:2 and 1000:3, and it decreased to about 500:1 as the volumetric COD removalrate increased.
The removal rate of ammonia nitrogen was proportional to that of phosphorus,but it was limited by the phosphorus concentration. At the high influent COD/P ratio(1000:1), the ratio of the consumed nitrogen to phosphorus was increased to 18.8:1,otherwise the ratio was relatively steady at 8.0:1 (with influent COD/P ratio of1000:2～1000:3), which was not affected by influent N/P ratio or volumetric nitrogenremoval rate under most conditions.
The performance of the phosphorus removal in UASB reactor had relationshipwith the microbial community in its granular sludge. The results of PCR-DGGE(Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis) and SEM(Scanning Electronic Microscope) showed that the microbial community in thegranular sludge shifted during the operation of the UASB reactor. The dominantmicroorganisms in the granules were rod-shaped and coccus in the early stage of theoperation, one of which was identified as Methanobacterium formicicum, while thefilaments became the predominant microorganisms in the latter stage, one of whichwas identified as Methanosaeta concilii. Lower effluent phosphorus concentrationcould be achieved when the granules was dominated by filaments in the UASBreactor.
The structure of the granular sludge was affected by the operational condition ofthe UASB reactor. Higher COD/P ratio (1000:1～1000:2) in influent and lower sludgeorganic loading rate (0.36～0.86 gCOD/gVSS·d) were prone to cause the granules todisaggregate and to be washed out.
The performance of the UASB reactor in phosphorus removal decreased with theaddition of sulfate. The volumetric phosphorus removal rate decreased from 9.6mgP/L·d to 2.0 mgP/L·d when the COD/sulfate ratio in influent decreased from 7.0 to2.3. The volumetric phosphorus removal rate was in the range of 2.0～4.3 mgP/L, and its phosphorus removal efficiency was 12.3 %～26.2 %, with the influent containing3500 mg/L COD, 1500 mg/L SO_4~(2-) and 15～25 mg/L PO_4~(3-).
厌氧生物反应器具有良好的除磷效能。在水力停留时间(Hydrulic RetentionTime，简称HRT)为24 h、进水COD和磷酸盐浓度分别为5000～10000 mg/L和5～30 mgP/L的条件下，UASB反应器的容积磷去除率可高达21．4 mgP/L·d，磷酸盐去除率可高达99．0％以上，出水磷浓度低于0．5 mgP/L，达到国家《污水综合排放标准》(GB8978-1996)中的一级排放标准。
厌氧生物反应器的除磷功能主要来自厌氧微生物的同化作用。将废水中的磷酸盐用作营养物质，使之从废水中转移至厌氧微生物体内(磷由水相转移至固相)，再通过泥水分离，使之从废水中去除，这是UASB反应器实现除磷功能的重要途径。
厌氧生物反应器的除磷效能受多种因素的制约。进水COD浓度、磷酸盐浓度以及COD/P值皆为UASB反应器除磷效能的显著影响因子。提高进水COD浓度，有利于提高容积磷去除率和磷酸盐去除率。提高进水磷酸盐浓度，有助于提高容积磷去除率，但会降低磷酸盐去除率。提高进水COD/P值，有利于提高磷酸盐去除率，但会限制容积磷去除率。
厌氧生物反应器的除磷效能与除碳效能密切相关。提高反应器的除碳效能有助于提高除磷效能，但除碳效能受除磷效能的影响较小。在进水COD/P值较高的条件下(1000：1)，依然能够获得较高的除碳效能(10 gCOD/L·d)，碳磷去除比例达1182：1；而在COD/P值较低(1000：2～1000：3)的条件下，碳磷去除比例平均值为655：1，并随容积COD去除率的提高而降低至500：1左右。
厌氧生物反应器的除磷效能与除氮效能联系紧密。在除氮效能较高的运行条件下，除磷效能相应较高，但在除磷效能较低的情况下，除氮效能也受影响。在进水COD/P值较低(1000：2～1000：3)的条件下，氮磷去除比例稳定在8．6左右，基本不受进水N/P值以及容积氮去除率的影响；而在磷酸盐浓度较低的情况下(1000：1)，氮磷去除比例增高，最高达18．8。
厌氧生物反应器的除磷效能与生物相组成相关。PCR-DGGE分析以及扫描电镜观察表明，在UASB反应器的运行过程中，颗粒污泥的微生物组成逐步从以甲酸甲烷杆菌(Methanobacterium formicicum)等杆菌和球菌为主，转变为以理事会鬃毛甲烷菌(Methanosaeta concilii)等丝状菌为主。就出水磷浓度而言，以丝状菌为主的UASB反应器优于以球菌和杆菌为主的UASB反应器。
厌氧生物反应器的生物相变化与进水有机负荷及COD/P值密切相关。在污泥负荷(0．36～0．86 gCOD/gVSS·d)较低、进水COD/P值(1000：1～1000：2)较高的条件下，容易引发颗粒污泥丝状菌膨胀，导致污泥流失而使反应器运行失稳，影响除磷效能。
厌氧生物反应器的除磷效能可受硫酸盐的干扰。当进水COD/SO_4~(2-)值从7．0降低至2．3时，UASB反应器中的产甲烷过程受到抑制，容积磷去除率由9．6mgP/L·d降至2．0 mgP/L·d。硫酸盐还原成为主导反应时，UASB反应器的除磷效能降低。在进水COD、SO_4~(2-)和磷酸盐浓度分别为3500 mg/L、1500 mg/L和15～25mgP/L条件下，容积磷去除率为2．0～4．3 mgP/L·d，磷酸盐去除率为12．3％～26．2％。
Eutrophication has been one of the main water pollution problems in China, andit is important to control phosphorus discharge into waters to relieve the severity asphosphorus is the key factor to cause eutrophication. In recent years, great advanceshave been achieved in anaerobic biotechnology for wastewater treatment. The UASB(Upflow Anaerobic Sludge Blanket) process has become one of the most popularanaerobic treatment processes and has been applied in various wastewaters. Thefunction of UASB reactor for removal of organic pollutants has drawn a lot ofattention, but its function for removal of phosphorus has so far been ignored.
A laboratory scale UASB reactor was operated to investigate its performance onphosphorus removal, and the feasibility of its applications in treating phosphoruscontaining wastewater was assessed as well. The main results of the research weresummarized as follows:
High performance on phosphorus removal was shown in the laboratory scaleUASB reactor. The volumetric phosphorus removal rate of 21.4 mgP/L·d, the removalrate efficiency above 99 % and the effluent PO_4~(3-)-P concentration below 0.5 mg/L(the requirement in the general discharge standards of wastewater
The microbial assimilation was supposed to be the most important pathway forphosphorus removal in UASB reactor. The microorganisms in the sludge uptake thephosphate as nutrient during their growth (the phosphorus was transferred from theliquid phase to the solid phase), then phosphorus was removed by separating thesludge from the effluent.
The influent concentration of COD and phosphate and the COD/P ratio were themain factors affecting phosphorus removal efficiency. Higher volumetric phosphorusremoval rate was achieved at higher influent COD and phosphate concentrations. Theincrease in influent phosphorus concentration could result in lower phosphorusremoval efficiency but higher volumetric phosphorus removal rate. Larger COD/Pratio ensured higher phosphorus removal efficiency, but limited the furtherimprovement in volumetric phosphorus removal rate.
The volumetric removal rates of COD and phosphorus were highly correlated.The volumetric phosphorus removal rate increased as the COD removal rate elevated,while the volumetric COD removal rate was hardly affected by volumetricphosphorus removal rate. With the influent COD/P ratio of 1000:1, a volumetric CODremoval rate of 10 gCOD/L·d was achieved, meanwhile, the ratio of the consumedCOD to phosphorus reached a relatively high value of 1182:1. The ratio of consumedCOD to phosphorus was about 655:1 when the influent COD/P ratio was between1000:2 and 1000:3, and it decreased to about 500:1 as the volumetric COD removalrate increased.
The removal rate of ammonia nitrogen was proportional to that of phosphorus,but it was limited by the phosphorus concentration. At the high influent COD/P ratio(1000:1), the ratio of the consumed nitrogen to phosphorus was increased to 18.8:1,otherwise the ratio was relatively steady at 8.0:1 (with influent COD/P ratio of1000:2～1000:3), which was not affected by influent N/P ratio or volumetric nitrogenremoval rate under most conditions.
The performance of the phosphorus removal in UASB reactor had relationshipwith the microbial community in its granular sludge. The results of PCR-DGGE(Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis) and SEM(Scanning Electronic Microscope) showed that the microbial community in thegranular sludge shifted during the operation of the UASB reactor. The dominantmicroorganisms in the granules were rod-shaped and coccus in the early stage of theoperation, one of which was identified as Methanobacterium formicicum, while thefilaments became the predominant microorganisms in the latter stage, one of whichwas identified as Methanosaeta concilii. Lower effluent phosphorus concentrationcould be achieved when the granules was dominated by filaments in the UASBreactor.
The structure of the granular sludge was affected by the operational condition ofthe UASB reactor. Higher COD/P ratio (1000:1～1000:2) in influent and lower sludgeorganic loading rate (0.36～0.86 gCOD/gVSS·d) were prone to cause the granules todisaggregate and to be washed out.
The performance of the UASB reactor in phosphorus removal decreased with theaddition of sulfate. The volumetric phosphorus removal rate decreased from 9.6mgP/L·d to 2.0 mgP/L·d when the COD/sulfate ratio in influent decreased from 7.0 to2.3. The volumetric phosphorus removal rate was in the range of 2.0～4.3 mgP/L, and its phosphorus removal efficiency was 12.3 %～26.2 %, with the influent containing3500 mg/L COD, 1500 mg/L SO_4~(2-) and 15～25 mg/L PO_4~(3-).
引文
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