基于亚硝化和厌氧氨氧化的新型生物脱氮技术的应用研究
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摘要
传统的生物技术广泛应用于废水脱氮处理。随着可持续发展理念的提出,对高能耗和药耗的传统生物脱氮技术提出了挑战。开发应用新型高效、低耗的生物脱氮工艺显得尤为重要。亚硝化、厌氧氨氧化、全程自养脱氮、同步硝化反硝化以及好氧反氨化等新型生物脱氮技术的研究成为当前的研究热点。然而,目前的研究成果大多数仅在实验室配水研究阶段,对于实际工业废水的应用研究相当缺乏,特别是新型生物脱氮工艺运行稳定性和可控性还需深入研究。本研究是采用基于亚硝化和厌氧氨氧化技术的新型生物脱氮技术对实际工业废水进行脱氮处理,研究结果如下:
1.采用常温半亚硝化—厌氧氨氧化联合工艺对淀粉废水好氧处理出水进行脱氮处理,在技术上、经济上是可行的。全流程总氮的去除率维持在80%左右,最高达85.5%。亚硝化单元平均总氮进水负荷0.20kgN/m~3d。厌氧氨氧化单元平均总氮进水负荷和去除负荷分别为1.11kgN/m~3d和0.83kgN/m~3d,最高分别达到1.61kgN/m~3d和1.29kgN/m~3d。
2.采用常温半亚硝化—厌氧氨氧化联合工艺处理污泥压滤液取得良好的脱氮效果。在稳定运行期间全流程总氮去除率平均为79.15%,最高达88.58%。亚硝化反应器总氮平均进水负荷为1.87kgN/m~3d,最高3.95 kgN/m~3d,最小水力停留时间0.094d。厌氧氨氧化反应器的总氮平均进水负荷和去除负荷分别为0.88kgN/m~3d和0.59kgN/m~3d,最高分别达到1.79 kgN/m~3d、1.34 kgN/m~3d,最小水力停留时间0.15d。
3.常温半亚硝化—厌氧氨氧化工艺稳定性研究表明:水力冲击与基质浓度冲击对亚硝化反应器稳定运行的影响较小,最高进水总氮负荷分别达到6.06kgN/m~3d和7.44kgN/m~3d,平均亚硝化率仍有42~50%。但基质浓度冲击对厌氧氨氧化反应的影响较大。原水中有机物、pH值和碱度对亚硝化—厌氧氨氧化工艺运行影响较小,但原水中悬浮物和表面活性物质的影响较大。
4.常温半亚硝化反应器稳定运行期间,发现了显著的自养脱氮现象,平均总氮去除率和去除负荷分别为40.05%、0.65kgN/m~3d,最高分别为72.18%、1.01kgN/m~3d。自养脱氮率随进水总氮负荷的提高而降低,亚硝化性能随进水总氮负荷的提高而提高。亚硝化反应器中自发形成了亚硝化菌与厌氧氨氧化菌共生的棕褐色细小颗粒污泥,其与反应器内壁附着生长红色的自养脱氮生物膜共同对自养脱氮起主要贡献。
5.单级自养脱氮反应器处理污泥压滤液试验表明:采用原生颗粒污泥启动,处理污泥压滤液可取得良好的效果。在进水平均总氮浓度为355.22mg/L时,进水总氮平均负荷为0.91kgN/m~3d,最高达1.37kgN/m~3d;总氮去除率平均为74.81%,最高86.92%;总氮平均去除负荷为0.68kgN/m~3d,最高达0.90kgN/m~3d。投加粉末活性炭强化单级自养脱氮反应,总氮去除率与总氮去除负荷都得到提高,且运行稳定性得到提高,总氮最高进水负荷与去除负荷分别为1.53kgN/m~3d、1.14kgN/m~3d。
6.亚硝化反应器的运行条件是自发形成颗粒污泥的关键。细小无机颗粒、水流剪切力以及适量有机物存在有利于颗粒污泥的形成。长污泥龄和低溶解氧使颗粒污泥中生物呈现出多样性,有助于自养脱氮的发生。
7.光学显微镜和电镜观察结果表明,亚硝化污泥为结构完整、表面光滑的颗粒污泥,以丝状菌为骨架、分布着大量的球菌、椭球菌、杆菌、长杆菌和螺旋菌。而在较低负荷下长期运行的厌氧氨氧化颗粒污泥的结构完全性较差,颗粒表面十分粗糙,没有规则的形态,以长杆菌和球菌为主,大量的丝状菌丝在颗粒中交织;实验后期反应器上部悬浮污泥中出现了较多的原生动物。
8.污泥龄和溶解氧是实现亚硝化反应稳定运行的关键因素。实验所得到的稳定亚硝化反应的控制条件为:污泥龄SRT≥100d,溶解氧浓度DO≤0.10mg/L,出水剩余碱度200~300mg/L。在SBR反应器中,可以根据pH、ORP值以及dpH/dt、dORP/dt值进行半亚硝化反应的过程控制。
9.基于亚硝化和厌氧氨氧化的生物脱氮单元可以与现有的废水处理单元组合成多种形式的生物脱氮工艺,根据含氨废水的浓度可以选择不同的适用工艺形式,以实现高效低耗脱氮。新型生物脱氮技术较传统硝化反硝化以及短程硝化反硝化工艺有着明显的经济性。
The classical biotechnology has been widely applied in biological nitrogen removel process of wastewater. But the concept of continuable development has challenged the classical biotechnology of removel nitrogen which energy and motivity consume is very high. Therefore it is important that researching and delevoping new nitrogen removal biotechnology.In resent years,the new biotechnologies such as ANAMMOX,SHARON—ANAMMOX,CANON process have been the focus of research all around the world.Whereas the most new nitrogen removal processes have been limited in laboratory scale,it has been many problems in those processes when it was applied in practical wastewater.The problems include lower stability and the difficulty of controlling.This report adopted the new biotechnology of nitrogen removal based on the nitrosation technology to treatment the actual wastewater.The conculsion are as follows:
1. It’s possible on technological as well as economic that biological nitrogen removal treat the efflux of aerobic biological treatment of starch wastewater with Semi-Nitrosation—ANAMMOX process at normal temperature , and the process has excellent treatment ability of nitrogen . The average remavol rate of totle nitrogen achieved 80% in the integration process, and the maximum removal rate of total nitrogen was 85.5%. Volumetric total nitrogen load of inflow in airlift nitrosation bioreactor was 0.20kgN/m~3d.In ANAMMOX reactor, the volumetric total nitrogen load of inflow and the volumetric total nitrogen removal load were 1.11kgN/m~3d and 0.83kg/m~3d,and the maximum loads were 1.61kgN/m~3d and 1.29kgN/m~3d.
2.It has been obtained sastisfactory result that biological nitrogen removal treat the sludge dewatering effluent with Semi-Nitrosation—ANAMMOX process at normal temperature.During the stable experiment,the average remavol rate of totle nitrogen was 79.15% in the whole process,and the maximum removal rate was 88.58%. In Semi-Nitrosation reactor, the volumetric total nitrogen load of inflow and the maximum load were 1.87 kgN/m~3d and 3.95kgN/m~3d ,it’s minimum HRT was 0.094d.In ANAMMOX reactor , the volumetric total nitrogen load of inflow and the total nitrogen removal load were 0.88 kgN/m~3d and 0.59kgN/m~3d , the maximum load were 1.79 kgN/m~3d and 1.34kgN/m~3d ,it’s minimum HRT was 0.094d.
3.The influence of the impact of hydraulic load and the matrix concentration load to Semi-Nitrosation reactor were acceptable.In those conditions ,the maximum total nitrogen removal load of inflow in Semi-Nitrosation reactor achieved 6.06 kgN/m~3d and 7.44kgN/m~3d,and the drgree of nitrosation still were 42~50%.However the impact of matrix concentration load was obviously influented the ANAMMOX reactor.
4.During the stable operating of the Semi-Nitrosation reactor, it has been found that the the phenomenon of autotrophic nitrogen removal significant generated, the average total nitrogen removal rate and the volumetric total nitrogen removal load were 40.05% and 0.65 kgN/m~3d,the maximum rate and load were 72.18% and 1.01 kgN/m~3d.At the same time, it has been found that the autotrophic nitrogen removal rate reduced as the total nitrogen load of inflow.However the performance of nitrosation increased as the total nitrogen load of inflow.The brown small granule sludge which spontaneous formatted in the Semi-Nitrosation reactor which consisted of the nitrosobacteria and the anammox bacterias as well as the red biomembrane which adhered to inwall of reactor contributed the autotrophic nitrogen removal.
5.The single autotrophic nitrogen removal reactor (SANR) was successfully stated up with the protogenesis granule sludge.It has been obtain very well result that removal nitrogen of the sludge dewatering effluent with the SANR . when the total nitrogen concentration was 355.22mg/L and the average total nitrogen load of inflow was 0.91 kgN/m~3d,the maximum total nitrogen loads of inflow achieved 1.37 kgN/m~3d, the SANR’s average total nitrogen removal rate was 74.81% and the maximum rate achieved 86.92%; the average total nitrogen removal load and the maximum load were 0.68 kgN/m~3d and 0.90 kgN/m~3d.The performance of SANR was been reinforced through add powder activated carbon.The total nitrogen removal rate and load were increased and the operation stability was improved, the maximum total nitrogen load of inflow and the removal load achieved 1.53 kgN/m~3d and 1.14 kgN/m~3d.
6.The operation conditions of the Semi-Nitrosation reactor were the keys of the spontaneous formation of the granule sludge.It was in favor of the formation of granule sludge that small inorganic granule, the current shearing force and organic matter moderately existed.Longer SRT and lower DO were in favor of biological multiplicity in the granule sludge which helped to occurrence of autotrophic nitrogen removal.
7. The observation results of optical microscope and SEM showed that, the nitrosation sludge was all the small granule sludge which structure was completed and which surface was smooth, and in those granules, many filamentous bacteric growed as the granules’frame, there were so many coccuse, ellipsoidal bacteric, bacillus and spiral bacteric on the granules. Howere the structure of anammox granule sludge was uncompleted, and the surface of the granule was coarseness.There were many bacillus and coccuse on the granules,and many filamentous bacteric existed in the granule.At the end of the experiment, many potozans appeared in the suspension sludge of the ANAMMOX which related to the long term lower nitrogen load.
8.SRT and DO were the keys of the stability of nitrosation. According to the experiment, the operating conditions of stability of nitrosation were SRT≥100d, DO≤0.10mg/L,ALK of effluent= 200~300mg/L。The process control of semi-nitrosation could be realized in SBR which based on the variation of pH, ORP,dpH/dt and dORP/dt.
9.To achieve properer operation of biological nitrogen removal process, different process would be adopted according to the different concentrate of nitrogen.The new biotechnologies of nitrogen removal were more economical than traditional nitrification and denitrification and short nitrification and denitrification.
1.采用常温半亚硝化—厌氧氨氧化联合工艺对淀粉废水好氧处理出水进行脱氮处理,在技术上、经济上是可行的。全流程总氮的去除率维持在80%左右,最高达85.5%。亚硝化单元平均总氮进水负荷0.20kgN/m~3d。厌氧氨氧化单元平均总氮进水负荷和去除负荷分别为1.11kgN/m~3d和0.83kgN/m~3d,最高分别达到1.61kgN/m~3d和1.29kgN/m~3d。
2.采用常温半亚硝化—厌氧氨氧化联合工艺处理污泥压滤液取得良好的脱氮效果。在稳定运行期间全流程总氮去除率平均为79.15%,最高达88.58%。亚硝化反应器总氮平均进水负荷为1.87kgN/m~3d,最高3.95 kgN/m~3d,最小水力停留时间0.094d。厌氧氨氧化反应器的总氮平均进水负荷和去除负荷分别为0.88kgN/m~3d和0.59kgN/m~3d,最高分别达到1.79 kgN/m~3d、1.34 kgN/m~3d,最小水力停留时间0.15d。
3.常温半亚硝化—厌氧氨氧化工艺稳定性研究表明:水力冲击与基质浓度冲击对亚硝化反应器稳定运行的影响较小,最高进水总氮负荷分别达到6.06kgN/m~3d和7.44kgN/m~3d,平均亚硝化率仍有42~50%。但基质浓度冲击对厌氧氨氧化反应的影响较大。原水中有机物、pH值和碱度对亚硝化—厌氧氨氧化工艺运行影响较小,但原水中悬浮物和表面活性物质的影响较大。
4.常温半亚硝化反应器稳定运行期间,发现了显著的自养脱氮现象,平均总氮去除率和去除负荷分别为40.05%、0.65kgN/m~3d,最高分别为72.18%、1.01kgN/m~3d。自养脱氮率随进水总氮负荷的提高而降低,亚硝化性能随进水总氮负荷的提高而提高。亚硝化反应器中自发形成了亚硝化菌与厌氧氨氧化菌共生的棕褐色细小颗粒污泥,其与反应器内壁附着生长红色的自养脱氮生物膜共同对自养脱氮起主要贡献。
5.单级自养脱氮反应器处理污泥压滤液试验表明:采用原生颗粒污泥启动,处理污泥压滤液可取得良好的效果。在进水平均总氮浓度为355.22mg/L时,进水总氮平均负荷为0.91kgN/m~3d,最高达1.37kgN/m~3d;总氮去除率平均为74.81%,最高86.92%;总氮平均去除负荷为0.68kgN/m~3d,最高达0.90kgN/m~3d。投加粉末活性炭强化单级自养脱氮反应,总氮去除率与总氮去除负荷都得到提高,且运行稳定性得到提高,总氮最高进水负荷与去除负荷分别为1.53kgN/m~3d、1.14kgN/m~3d。
6.亚硝化反应器的运行条件是自发形成颗粒污泥的关键。细小无机颗粒、水流剪切力以及适量有机物存在有利于颗粒污泥的形成。长污泥龄和低溶解氧使颗粒污泥中生物呈现出多样性,有助于自养脱氮的发生。
7.光学显微镜和电镜观察结果表明,亚硝化污泥为结构完整、表面光滑的颗粒污泥,以丝状菌为骨架、分布着大量的球菌、椭球菌、杆菌、长杆菌和螺旋菌。而在较低负荷下长期运行的厌氧氨氧化颗粒污泥的结构完全性较差,颗粒表面十分粗糙,没有规则的形态,以长杆菌和球菌为主,大量的丝状菌丝在颗粒中交织;实验后期反应器上部悬浮污泥中出现了较多的原生动物。
8.污泥龄和溶解氧是实现亚硝化反应稳定运行的关键因素。实验所得到的稳定亚硝化反应的控制条件为:污泥龄SRT≥100d,溶解氧浓度DO≤0.10mg/L,出水剩余碱度200~300mg/L。在SBR反应器中,可以根据pH、ORP值以及dpH/dt、dORP/dt值进行半亚硝化反应的过程控制。
9.基于亚硝化和厌氧氨氧化的生物脱氮单元可以与现有的废水处理单元组合成多种形式的生物脱氮工艺,根据含氨废水的浓度可以选择不同的适用工艺形式,以实现高效低耗脱氮。新型生物脱氮技术较传统硝化反硝化以及短程硝化反硝化工艺有着明显的经济性。
The classical biotechnology has been widely applied in biological nitrogen removel process of wastewater. But the concept of continuable development has challenged the classical biotechnology of removel nitrogen which energy and motivity consume is very high. Therefore it is important that researching and delevoping new nitrogen removal biotechnology.In resent years,the new biotechnologies such as ANAMMOX,SHARON—ANAMMOX,CANON process have been the focus of research all around the world.Whereas the most new nitrogen removal processes have been limited in laboratory scale,it has been many problems in those processes when it was applied in practical wastewater.The problems include lower stability and the difficulty of controlling.This report adopted the new biotechnology of nitrogen removal based on the nitrosation technology to treatment the actual wastewater.The conculsion are as follows:
1. It’s possible on technological as well as economic that biological nitrogen removal treat the efflux of aerobic biological treatment of starch wastewater with Semi-Nitrosation—ANAMMOX process at normal temperature , and the process has excellent treatment ability of nitrogen . The average remavol rate of totle nitrogen achieved 80% in the integration process, and the maximum removal rate of total nitrogen was 85.5%. Volumetric total nitrogen load of inflow in airlift nitrosation bioreactor was 0.20kgN/m~3d.In ANAMMOX reactor, the volumetric total nitrogen load of inflow and the volumetric total nitrogen removal load were 1.11kgN/m~3d and 0.83kg/m~3d,and the maximum loads were 1.61kgN/m~3d and 1.29kgN/m~3d.
2.It has been obtained sastisfactory result that biological nitrogen removal treat the sludge dewatering effluent with Semi-Nitrosation—ANAMMOX process at normal temperature.During the stable experiment,the average remavol rate of totle nitrogen was 79.15% in the whole process,and the maximum removal rate was 88.58%. In Semi-Nitrosation reactor, the volumetric total nitrogen load of inflow and the maximum load were 1.87 kgN/m~3d and 3.95kgN/m~3d ,it’s minimum HRT was 0.094d.In ANAMMOX reactor , the volumetric total nitrogen load of inflow and the total nitrogen removal load were 0.88 kgN/m~3d and 0.59kgN/m~3d , the maximum load were 1.79 kgN/m~3d and 1.34kgN/m~3d ,it’s minimum HRT was 0.094d.
3.The influence of the impact of hydraulic load and the matrix concentration load to Semi-Nitrosation reactor were acceptable.In those conditions ,the maximum total nitrogen removal load of inflow in Semi-Nitrosation reactor achieved 6.06 kgN/m~3d and 7.44kgN/m~3d,and the drgree of nitrosation still were 42~50%.However the impact of matrix concentration load was obviously influented the ANAMMOX reactor.
4.During the stable operating of the Semi-Nitrosation reactor, it has been found that the the phenomenon of autotrophic nitrogen removal significant generated, the average total nitrogen removal rate and the volumetric total nitrogen removal load were 40.05% and 0.65 kgN/m~3d,the maximum rate and load were 72.18% and 1.01 kgN/m~3d.At the same time, it has been found that the autotrophic nitrogen removal rate reduced as the total nitrogen load of inflow.However the performance of nitrosation increased as the total nitrogen load of inflow.The brown small granule sludge which spontaneous formatted in the Semi-Nitrosation reactor which consisted of the nitrosobacteria and the anammox bacterias as well as the red biomembrane which adhered to inwall of reactor contributed the autotrophic nitrogen removal.
5.The single autotrophic nitrogen removal reactor (SANR) was successfully stated up with the protogenesis granule sludge.It has been obtain very well result that removal nitrogen of the sludge dewatering effluent with the SANR . when the total nitrogen concentration was 355.22mg/L and the average total nitrogen load of inflow was 0.91 kgN/m~3d,the maximum total nitrogen loads of inflow achieved 1.37 kgN/m~3d, the SANR’s average total nitrogen removal rate was 74.81% and the maximum rate achieved 86.92%; the average total nitrogen removal load and the maximum load were 0.68 kgN/m~3d and 0.90 kgN/m~3d.The performance of SANR was been reinforced through add powder activated carbon.The total nitrogen removal rate and load were increased and the operation stability was improved, the maximum total nitrogen load of inflow and the removal load achieved 1.53 kgN/m~3d and 1.14 kgN/m~3d.
6.The operation conditions of the Semi-Nitrosation reactor were the keys of the spontaneous formation of the granule sludge.It was in favor of the formation of granule sludge that small inorganic granule, the current shearing force and organic matter moderately existed.Longer SRT and lower DO were in favor of biological multiplicity in the granule sludge which helped to occurrence of autotrophic nitrogen removal.
7. The observation results of optical microscope and SEM showed that, the nitrosation sludge was all the small granule sludge which structure was completed and which surface was smooth, and in those granules, many filamentous bacteric growed as the granules’frame, there were so many coccuse, ellipsoidal bacteric, bacillus and spiral bacteric on the granules. Howere the structure of anammox granule sludge was uncompleted, and the surface of the granule was coarseness.There were many bacillus and coccuse on the granules,and many filamentous bacteric existed in the granule.At the end of the experiment, many potozans appeared in the suspension sludge of the ANAMMOX which related to the long term lower nitrogen load.
8.SRT and DO were the keys of the stability of nitrosation. According to the experiment, the operating conditions of stability of nitrosation were SRT≥100d, DO≤0.10mg/L,ALK of effluent= 200~300mg/L。The process control of semi-nitrosation could be realized in SBR which based on the variation of pH, ORP,dpH/dt and dORP/dt.
9.To achieve properer operation of biological nitrogen removal process, different process would be adopted according to the different concentrate of nitrogen.The new biotechnologies of nitrogen removal were more economical than traditional nitrification and denitrification and short nitrification and denitrification.
引文
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