城镇污水改进型UASB工艺处理及后续除氮系统研究
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摘要
近年来,UASB反应器处理城镇污水已有广泛应用,但城镇污水经UASB反应器处理后COD仍较高,难以达到国家城镇污水处理厂排放标准,且出水硫化物浓度较高,研究表明经厌氧处理后出水COD有很大部分由硫化物贡献;再则厌氧生物处理对废水中的氨氮去除较少.设法改进厌氧处理工艺来降低出水COD对促进城镇污水厌氧处理的推广具有很大现实意义,再加上适当后续工艺解决出水中氨氮问题,从而使厌氧处理更好地应用于城镇污水处理。
本研究探讨了加入铁刨花后UASB反应器出水硫化物去除状况和机理以及UASB反应器整体处理性能的改善,并且研究了电化学法和吸附法两种后续工艺对UASB反应器出水氨氮的去除状况及应用可行性。主要研究结果如下:
1.向UASB反应器加入铁刨花后,其出水平均COD值、硫化物、SS分别为47、8和8 mg/L,较加入铁刨花前分别减少了55、12和13 mg/L,均达到国家城镇污水厂污染物排放一级A标准。铁刨花在UASB反应器中形成Fe~(2+),与硫酸还原所产生的S~(2-)反应生成FeS沉淀,从而减少了出水硫化物浓度;溶解铁离子局部形成的水合化合物导致了出水SS、色度、浊度的减小,显著改善了出水表观性状。
2.电化学反应器处理UASB反应器出水,氨氮去除效率随电流密度、氯离子浓度和水力停留时间增加而提高。当电流密度为15.4 mA·cm~(-2)时,采用水力停留时间30、60、90分钟,出水氨氮分别降至17、10、5 mg/L,相应达到国家城镇污水二级、一级B、一级A排放标准;当水力停留时间为90分钟时,采用电流密度为7.6、11.6、15.4 mA·cm~(-2),出水氨氮可分别达到二级、一级B、一级A标准。实际运用中应根据能耗及排放标准等情况选择适合的工艺条件。废水初始COD浓度对氨氮电化学去除有一定影响,COD含量越高,氨氮的去除速率越慢,反之氨氮去除速率越快。
3.静态吸附研究中,沸石、Na-沸石及蛭石、Na-蛭石对氨氮的吸附符合Freundlich、Langmuir等温式,更适用于Langmuir等温式。沸石、Na-沸石的静态饱和吸附量分别为8.09、13.55 mg/g,远高于蛭石。沸石钠型改性显著提高其吸附容量和吸附效果,具有很高的应用价值。动态吸附吸附柱吸附率与进水氨氮浓度有关,氨氮进水浓度增大,沸石吸附达饱和的时间减短。首次提出电化学再生饱和沸石新工艺,采用电化学再生仅需3 h,而采用NaCl再生213 mg/L浓度的氨氮溶液需15 h,采用NaCl+NaOH(重量比为3:7)再生也需要3.5 h,且由于电化学过程将氨氮氧化成氮气,解决了再生废液的处理困难,实现无氨氮排放。
In recent years,domestic treatment using UASB reactor has been widely applied. However,the effluent COD concentrations of domestic sewage from UASB reactor are still high,difficult to reach the national emission standards of domestic sewage treatment plants(level 2) and a higher concentration of effluent sulfide.Studies showed that a large portion of the anaerobic treated effluent COD was contributed to sulphide and the anaerobic biological treatment of waste water in basically did not remove ammonia nitrogen.Therefore,the efforts of improving the anaerobic process in order to reduce effluent COD have great practical significance to promote the anaerobic treatment of domestic sewage.Appropriate follow-up processes are also needed to solve the problem of ammonia nitrogen in effluents,so that anaerobic treatment can be better applied in domestic sewage water treatment.
This study discussed the removal of sulfide and its mechanisms after adding iron particles into UASB reactor,and the overall improved performance of UASB reactor. This study also researched the removal of ammonia nitrogen through two kinds of follow-up process of UASB reactor(electrochemistry and absorption) and their feasibilities.The main results are as follows:
1.After adding iron shavings into UASB reactor,the average COD,sulfide,SS in the effluents were 47,8 and 8 mg/L,respectively,reduced by 55,12 and 13 mg/L, respectively,comparing with the values before adding iron shavings.Both reach the national emission standards of domestic sewage treatment plants(level 1A).Iron shavings formed Fe~(2+) in UASB reactor,and S~(2-) generated by sulfate reduction formed FeS precipitation,thus reducing the effluent sulphide;hydrated compounds formed by dissolved iron in some parts have led to the decreases of effluent SS,color and turbidity,significantly improved the apparent traits of effluents.
2.In Electrochemical treatment of UASB reactor effluents,the ammonia nitrogen removal efficiency increased with the raises of current density,chloride ion concentration and HRT.If the current density was 15.4 mA·cm~(-2),the effluent ammonia nitrogen reduced to 17,10,5 mg/L,when HRT was 30,60,90 minutes, respectively,reaching the national emission standards of domestic sewage treatment plants(level 2,level 1B and level 1A,respectively).If HRT was 90 minutes,the effluent ammonia nitrogen could reach the national emission standards of domestic sewage treatment plants(level 2,level 1B and level 1A,respectively),when the current density was 7.6,11.6,15.4 mA·cm~(-2),respectively.In accordance with the actual use of energy consumption and emission standards,appropriate process conditions were chosen.The initial COD concentration in wastewater had influence on electrochemical removal of ammonia nitrogen,to a certain extent.The higher the COD content was,the slower the removal rate of ammonia nitrogen was,and vice versa.
3.In the static adsorption study,the adsorptions of ammonia nitrogen by four kinds of materials followed Freundlich or Langmuir isotherm,especially Langrnuir isotherm.The static saturated adsorption capacity of Zeolite and Na-zeolite was 8.09 and 13.55 mg/g,respectively,much higher than that of vermiculite.Na-modification of Zeolite significantly increased its adsorption capacity and adsorption effect,which is of high value.In the dynamic adsorption study,the adsorption rate of adsorption column had relationship with influent concentration of ammonia nitrogen.The higher the influent concentration was,the shorter the time of zeolite reaching saturated adsorption was.The new technique of electrochemical regeneration of saturated zeolite was proposed for the first time.Zeolite was used in 213 mg/L ammonia nitrogen solution.The regeneration of zeolite by electrochemistry cost only 3 h,while it would cost around 15 h using NaCl,and 3.5 h using NaCl + NaOH(weight ratio of 3:7).In electrochemical process,ammonia nitrogen could be oxidized into nitrogen, resolving the difficulties of renewable liquid treatment,and realizing no ammonia nitrogen emissions.
本研究探讨了加入铁刨花后UASB反应器出水硫化物去除状况和机理以及UASB反应器整体处理性能的改善,并且研究了电化学法和吸附法两种后续工艺对UASB反应器出水氨氮的去除状况及应用可行性。主要研究结果如下:
1.向UASB反应器加入铁刨花后,其出水平均COD值、硫化物、SS分别为47、8和8 mg/L,较加入铁刨花前分别减少了55、12和13 mg/L,均达到国家城镇污水厂污染物排放一级A标准。铁刨花在UASB反应器中形成Fe~(2+),与硫酸还原所产生的S~(2-)反应生成FeS沉淀,从而减少了出水硫化物浓度;溶解铁离子局部形成的水合化合物导致了出水SS、色度、浊度的减小,显著改善了出水表观性状。
2.电化学反应器处理UASB反应器出水,氨氮去除效率随电流密度、氯离子浓度和水力停留时间增加而提高。当电流密度为15.4 mA·cm~(-2)时,采用水力停留时间30、60、90分钟,出水氨氮分别降至17、10、5 mg/L,相应达到国家城镇污水二级、一级B、一级A排放标准;当水力停留时间为90分钟时,采用电流密度为7.6、11.6、15.4 mA·cm~(-2),出水氨氮可分别达到二级、一级B、一级A标准。实际运用中应根据能耗及排放标准等情况选择适合的工艺条件。废水初始COD浓度对氨氮电化学去除有一定影响,COD含量越高,氨氮的去除速率越慢,反之氨氮去除速率越快。
3.静态吸附研究中,沸石、Na-沸石及蛭石、Na-蛭石对氨氮的吸附符合Freundlich、Langmuir等温式,更适用于Langmuir等温式。沸石、Na-沸石的静态饱和吸附量分别为8.09、13.55 mg/g,远高于蛭石。沸石钠型改性显著提高其吸附容量和吸附效果,具有很高的应用价值。动态吸附吸附柱吸附率与进水氨氮浓度有关,氨氮进水浓度增大,沸石吸附达饱和的时间减短。首次提出电化学再生饱和沸石新工艺,采用电化学再生仅需3 h,而采用NaCl再生213 mg/L浓度的氨氮溶液需15 h,采用NaCl+NaOH(重量比为3:7)再生也需要3.5 h,且由于电化学过程将氨氮氧化成氮气,解决了再生废液的处理困难,实现无氨氮排放。
In recent years,domestic treatment using UASB reactor has been widely applied. However,the effluent COD concentrations of domestic sewage from UASB reactor are still high,difficult to reach the national emission standards of domestic sewage treatment plants(level 2) and a higher concentration of effluent sulfide.Studies showed that a large portion of the anaerobic treated effluent COD was contributed to sulphide and the anaerobic biological treatment of waste water in basically did not remove ammonia nitrogen.Therefore,the efforts of improving the anaerobic process in order to reduce effluent COD have great practical significance to promote the anaerobic treatment of domestic sewage.Appropriate follow-up processes are also needed to solve the problem of ammonia nitrogen in effluents,so that anaerobic treatment can be better applied in domestic sewage water treatment.
This study discussed the removal of sulfide and its mechanisms after adding iron particles into UASB reactor,and the overall improved performance of UASB reactor. This study also researched the removal of ammonia nitrogen through two kinds of follow-up process of UASB reactor(electrochemistry and absorption) and their feasibilities.The main results are as follows:
1.After adding iron shavings into UASB reactor,the average COD,sulfide,SS in the effluents were 47,8 and 8 mg/L,respectively,reduced by 55,12 and 13 mg/L, respectively,comparing with the values before adding iron shavings.Both reach the national emission standards of domestic sewage treatment plants(level 1A).Iron shavings formed Fe~(2+) in UASB reactor,and S~(2-) generated by sulfate reduction formed FeS precipitation,thus reducing the effluent sulphide;hydrated compounds formed by dissolved iron in some parts have led to the decreases of effluent SS,color and turbidity,significantly improved the apparent traits of effluents.
2.In Electrochemical treatment of UASB reactor effluents,the ammonia nitrogen removal efficiency increased with the raises of current density,chloride ion concentration and HRT.If the current density was 15.4 mA·cm~(-2),the effluent ammonia nitrogen reduced to 17,10,5 mg/L,when HRT was 30,60,90 minutes, respectively,reaching the national emission standards of domestic sewage treatment plants(level 2,level 1B and level 1A,respectively).If HRT was 90 minutes,the effluent ammonia nitrogen could reach the national emission standards of domestic sewage treatment plants(level 2,level 1B and level 1A,respectively),when the current density was 7.6,11.6,15.4 mA·cm~(-2),respectively.In accordance with the actual use of energy consumption and emission standards,appropriate process conditions were chosen.The initial COD concentration in wastewater had influence on electrochemical removal of ammonia nitrogen,to a certain extent.The higher the COD content was,the slower the removal rate of ammonia nitrogen was,and vice versa.
3.In the static adsorption study,the adsorptions of ammonia nitrogen by four kinds of materials followed Freundlich or Langmuir isotherm,especially Langrnuir isotherm.The static saturated adsorption capacity of Zeolite and Na-zeolite was 8.09 and 13.55 mg/g,respectively,much higher than that of vermiculite.Na-modification of Zeolite significantly increased its adsorption capacity and adsorption effect,which is of high value.In the dynamic adsorption study,the adsorption rate of adsorption column had relationship with influent concentration of ammonia nitrogen.The higher the influent concentration was,the shorter the time of zeolite reaching saturated adsorption was.The new technique of electrochemical regeneration of saturated zeolite was proposed for the first time.Zeolite was used in 213 mg/L ammonia nitrogen solution.The regeneration of zeolite by electrochemistry cost only 3 h,while it would cost around 15 h using NaCl,and 3.5 h using NaCl + NaOH(weight ratio of 3:7).In electrochemical process,ammonia nitrogen could be oxidized into nitrogen, resolving the difficulties of renewable liquid treatment,and realizing no ammonia nitrogen emissions.
引文
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