基于铁基质高效催化还原污水中硝酸盐氮的实验研究
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摘要
污水厂排水中硝酸盐氮(NO_3~–-N)浓度偏高,难利用常规生物脱氮工艺实现NO_3~–-N的深度脱除。以铁基质高效催化脱氮载体为污水中NO_3~–-N的脱除材料,探究不同铁基质催化活性、pH和NO_3~–-N浓度等对污水中NO_3~–-N去除的影响及机制。研究结果表明:添加催化剂D的铁基质高效催化脱氮载体可脱除92.23%的NO_3~–-N,调节污水为酸性至中性条件时,其NO_3~–-N去除率均可达到92.09%以上,且氨氮(NH_4~+-N)积累量先升高后降低;当污水为碱性条件时,NO_3~–-N的去除率亦可达86.13%以上,且在碱性条件时无NH_4~+-N积累;原水中NO_3~–-N的浓度变化(20～70 mg·L~(-1))对铁基质高效催化脱氮载体的脱氮性能影响较小,NO_3~–-N去除率均达到96.11%以上。与催化剂A、B和C相比,添加催化剂D的铁基质高效催化脱氮载体脱氮速率最快,NO_3~–-N降解反应过程符合一级反应动力学方程,反应速率常数k=0.0170 min~(-1)。
It remains difficult to achieve effective nitrate removal with conventional biological nitrogen removal processes, for the high NO_3~--N concentration and low organic carbon in tail water from WWTP. Thus, ZVI-based catalyzed reduction was developed and applied in this study. The influence of catalytic activity of the catalysts, pH and NO_3~--N concentration on nitrate reduction by ZVI-based catalyzed reduction was studied, and the reaction mechanisms was investigated. The results show that the high-catalytic catalytic denitrification carrier with catalyst D can remove 92.23% of NO_3~--N, and the NO_3~--N removal rate can reach 92.09% when the wastewater is acidic to neutral. The NO_3~--N removal efficiency of above 86.13% was also achieved even under alkaline conditions, and no NH_4~-N accumulation was found. Increasing in NO_3~--N concentration(20-70 mg · L~(-1)) showed little impact on nitrate reduction efficiency(remaining ≥96.11%). The nitrogen removal efficiency by ZVI-based catalyzed reduction in the presence of catalyst D obtained the highest speed when compared to catalysts A, B and C, and the reduction reaction was in keeping with the first-order kinetics equation with a calculated reaction rate constant of k=0.0170 min~(-1).
It remains difficult to achieve effective nitrate removal with conventional biological nitrogen removal processes, for the high NO_3~--N concentration and low organic carbon in tail water from WWTP. Thus, ZVI-based catalyzed reduction was developed and applied in this study. The influence of catalytic activity of the catalysts, pH and NO_3~--N concentration on nitrate reduction by ZVI-based catalyzed reduction was studied, and the reaction mechanisms was investigated. The results show that the high-catalytic catalytic denitrification carrier with catalyst D can remove 92.23% of NO_3~--N, and the NO_3~--N removal rate can reach 92.09% when the wastewater is acidic to neutral. The NO_3~--N removal efficiency of above 86.13% was also achieved even under alkaline conditions, and no NH_4~-N accumulation was found. Increasing in NO_3~--N concentration(20-70 mg · L~(-1)) showed little impact on nitrate reduction efficiency(remaining ≥96.11%). The nitrogen removal efficiency by ZVI-based catalyzed reduction in the presence of catalyst D obtained the highest speed when compared to catalysts A, B and C, and the reduction reaction was in keeping with the first-order kinetics equation with a calculated reaction rate constant of k=0.0170 min~(-1).
引文
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[11]俞勇,方建,喻盛华.硝化/反硝化滤池用于反渗透浓水处理的设计和调试[J].中国给水排水,2017,33(18):135-138.Yu Y,Fang J,Yu S H.Design and commissioning of nitrification/denitrification filter in reverse osmosis brine treatment[J].China Water&Wastewater,2017,33(18):135-138.
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[13]范潇梦,关小红,马军.零价铁还原水中硝酸盐的机理及影响因素[J].中国给水排水,2008,24(14):5-9.Fan X M,Guan X H,Ma J.Mechanisms and affecting factors of nitrate reduction by zero-valent iron.[J].China Water&Wastewater,2008,24(14):5-9.
[14]Chen Y M,Li C W,Chen S S.Fluidized zero valent iron bed reactor for nitrate removal[J].Chemosphere,2005,59(6):753-759.
[15]Choe S,Liljestrand H M,Khim J.Nitrate reduction by zero-valent iron under different pH regimes[J].Applied Geochemistry,2004,19(3):335-342.
[16]肖晶晶,郭萍,霍炜洁,等.反硝化微生物在污水脱氮中的研究及应用进展[J].环境科学与技术,2009,32(12):97-102.Xiao J J,Guo P,Huo W J,et al.Application of denitrifying microbes to wastewater denitrification[J].Environmental Science&Technology,2009,32(12):97-102.
[17]李铁龙,刘海水,金朝晖,等.纳米铁去除水中硝酸盐氮的批实验[J].吉林大学学报,2006,36(2):264-268.Li T L,Liu H S,Jin Z H,et al.Batch experiment on reduction of nitrate in water by nanoscale zero valent iron carriers[J].Journal of Jilin University,2006,36(2):264-268.
[18]郑西来,唐凤琳,辛佳,等.污染地下水零价铁原位反应带修复技术:理论·应用·展望[J].环境科学研究,2016,29(2):155-163.Zheng X L,Tang F L,Xin J,et al.Development of a zero-valent iron-based in-situ reactive zones technique for remediation of contaminated groundwater[J].Research of Environmental Sciences,2016,29(2):155-163.
[19]Liao C H,Kang S F,Hsu Y W.Zero-valent iron reduction of nitrate in the presence of ultraviolet light,organic matter and hydrogen peroxide[J].Water Research,2003,37(17):4109-4118.
[20]Zhou J,Duan S H,Chen Y,et al.Nitrogen removal efficiency of iron-carbon micro-electrolysis system treating high nitrate nitrogen organic pharmaceutical wastewater[J].Journal of Central South University,2009,16(s1):368-373.
[21]Keum Y S,Li Q X.Reduction of nitroaromatic pesticides with zero-valent iron[J].Chemosphere,2004,54(3):255-263.
[22]李德生.好氧低碳氮比污水氨氮直接脱氮生物载体及制备方法:103145234A[P].2013-06-12.Li D S.Biological particulate carrier and its preparation method directly disposing ammonia nitrogen fromaerobic low carbon nitrogen ratio wastewater:103145234A[P].2013-06-12.
[23]国家环境保护总局.水和废水监测分析方法[M].4版.北京:中国环境科学出版社,2002:258-284.The Environmental Protection Agency of State.The Monitoring and Analysis Methods of Water and Wastewater[M].4th ed.Beijing:China Environmental Science Press,2002:258-284.
[24]Huang Y H,Zhang T C.Nitrite reduction and formation of corrosion coatings in zerovalent iron systems[J].Chemosphere,2006,64(6):937-943.
[25]邓时海,李德生,卢阳阳,等.集成模块系统同步硝化反硝化处理低碳氮比污水的试验[J].中国环境科学,2014,34(9):2259-2265.Deng S H,Li D S,Lu Y Y,et al.Performance characteristics of simultaneous nitrification and denitrification(SND)for low carbon to nitrogen(C/N)ratio wastewater in an integrated device[J]China Environmental Science,2014,34(9):2259-2265.
[26]刘新超,贾磊,俞勤,等.零价铁还原脱氮技术研究进展[J].四川环境,2016,35(4):118-122.Liu X C,Jia L,Yu Q,et al.Review of reductive denitrification by zero-valent iron[J].Sichuan Environment,2016,35(4):118-122.
[27]王迪.还原铁粉去除地下水中硝酸盐及亚硝酸盐的研究[D].哈尔滨:东北林业大学,2013.Wang D.Study on removal of nitrate and nitrite in the groundwater ofreduced iron powder[D].Harbin:Northeast Forestry University,2013.
[28]Choe S,Chang Y Y,Hwang K Y,et al.Kinetics of reductive denitrification by nanoscale zero-valent iron[J].Chemosphere,2000,41(8):1307-1311.
[29]Li X Q,Elliott D W,Zhang W X.Zero-valent iron nanocarriers for abatement of environmental pollutants:materials and engineering aspects[J].Critical Reviews in Solid State&Materials Sciences,2006,31(4):111-122.
[30]郝志伟,李亮,马鲁铭.零价铁还原法脱除地下水中硝酸盐的研究[J].中国给水排水,2008,24(17):36-39.Hao Z W,Li L,Ma L M.Study on removal of nitrate from groundwater by zero-valent iron reduction process[J].China Water&Wastewater,2008,24(17):36-39.
[2]李德生,胡倩怡,崔玉玮,等.化学催化法脱除模拟地下水中硝酸盐氮[J].化工学报,2015,66(6):2288-2294.Li D S,Hu Q Y,Cui Y W,et al.Chemical catalytic method for removal of nitrate nitrogen in simulated groundwater[J].CIESCJournal,2015,66(6):2288-2294.
[3]Bertin A,Inostroza P A,Qui?ones R A.A theoretical estimation of the concentration of steroid estrogens in effluents released from municipal sewage treatment plants into aquatic ecosystems of central-southern Chile[J].Science of the Total Environment,2009,407(17):4965-4971.
[4]孙向辉,李力.水体富营养化及其植物修复技术研究进展[J].安徽农业科学,2014,42(18):5902-5905.Sun X H,Li L.Research progress on eutrofication of water system and phytoremediation[J].Journal of Anhui Agricultural Sciences,2014,42(18):5902-5905.
[5]张自杰.排水工程:下册[M].4版.北京:中国建筑工业出版社,2000:308-312.Zhang Z J.Drainage Engineering:VolumeⅡ[M].4th ed.Beijing:China Architecture&Building Press,2000:308-312.
[6]谢荣,赵博玮,李建政,等.木质填料床A/O系统处理低C/N比养猪废水的效能与脱氮机制[J].化工学报,2015,66(11):4661-4668.Xie R,Zhao B W,Li J Z,et al.Treatment of piggery wastewater with low C/N ratio and mechanism for denitrification in woodpacked-bed A/O process[J].CIESC Journal,2015,66(11):4661-4668.
[7]Wisniewski C,Persin F,Cherif T,et al.Denitrification of drinking water by the association of an electrodialysis process and a membrane bioreactor:feasibility and application[J].Desalination,2001,139(1):199-205.
[8]杨朗,李志丰.低浓度氨氮废水的离子交换法脱氮[J].环境工程学报,2012,6(8):2715-2719.Yang L,Li Z F.Ammonia-nitrogen removal from low concentration wastewater by ion exchange[J].Chinese Journal of Environmental Engineering,2012,6(8):2715-2719.
[9]迟峰.反渗透法脱除地下水中硝酸盐的研究[D].上海:华东理工大学,2011.Chi F.The research on nitrate removal from groundwater by reverse osmosis[D].Shanghai:East China University of Science and Technology,2011.
[10]张立辉,曹国民,盛梅,等.地下水硝酸盐去除技术进展[J].净水技术,2010,29(5):4-10.Zhang L H,Cao G M,Sheng M,et al.Progress of the technological processes for nitrate removal in groundwater[J].Water Purification Technology,2010,29(5):4-10.
[11]俞勇,方建,喻盛华.硝化/反硝化滤池用于反渗透浓水处理的设计和调试[J].中国给水排水,2017,33(18):135-138.Yu Y,Fang J,Yu S H.Design and commissioning of nitrification/denitrification filter in reverse osmosis brine treatment[J].China Water&Wastewater,2017,33(18):135-138.
[12]张星星,孟凡生,王业耀,等.零价铁修复硝酸盐污染地下水的影响因素[J].环境工程,2010,28(s1):70-73.Zhang X X,Meng F S,Wang Y Y,et al.Research on influencing factors of nitrate removal of groundwater by ZVI[J].Environmental Engineering,2010,28(s1):70-73.
[13]范潇梦,关小红,马军.零价铁还原水中硝酸盐的机理及影响因素[J].中国给水排水,2008,24(14):5-9.Fan X M,Guan X H,Ma J.Mechanisms and affecting factors of nitrate reduction by zero-valent iron.[J].China Water&Wastewater,2008,24(14):5-9.
[14]Chen Y M,Li C W,Chen S S.Fluidized zero valent iron bed reactor for nitrate removal[J].Chemosphere,2005,59(6):753-759.
[15]Choe S,Liljestrand H M,Khim J.Nitrate reduction by zero-valent iron under different pH regimes[J].Applied Geochemistry,2004,19(3):335-342.
[16]肖晶晶,郭萍,霍炜洁,等.反硝化微生物在污水脱氮中的研究及应用进展[J].环境科学与技术,2009,32(12):97-102.Xiao J J,Guo P,Huo W J,et al.Application of denitrifying microbes to wastewater denitrification[J].Environmental Science&Technology,2009,32(12):97-102.
[17]李铁龙,刘海水,金朝晖,等.纳米铁去除水中硝酸盐氮的批实验[J].吉林大学学报,2006,36(2):264-268.Li T L,Liu H S,Jin Z H,et al.Batch experiment on reduction of nitrate in water by nanoscale zero valent iron carriers[J].Journal of Jilin University,2006,36(2):264-268.
[18]郑西来,唐凤琳,辛佳,等.污染地下水零价铁原位反应带修复技术:理论·应用·展望[J].环境科学研究,2016,29(2):155-163.Zheng X L,Tang F L,Xin J,et al.Development of a zero-valent iron-based in-situ reactive zones technique for remediation of contaminated groundwater[J].Research of Environmental Sciences,2016,29(2):155-163.
[19]Liao C H,Kang S F,Hsu Y W.Zero-valent iron reduction of nitrate in the presence of ultraviolet light,organic matter and hydrogen peroxide[J].Water Research,2003,37(17):4109-4118.
[20]Zhou J,Duan S H,Chen Y,et al.Nitrogen removal efficiency of iron-carbon micro-electrolysis system treating high nitrate nitrogen organic pharmaceutical wastewater[J].Journal of Central South University,2009,16(s1):368-373.
[21]Keum Y S,Li Q X.Reduction of nitroaromatic pesticides with zero-valent iron[J].Chemosphere,2004,54(3):255-263.
[22]李德生.好氧低碳氮比污水氨氮直接脱氮生物载体及制备方法:103145234A[P].2013-06-12.Li D S.Biological particulate carrier and its preparation method directly disposing ammonia nitrogen fromaerobic low carbon nitrogen ratio wastewater:103145234A[P].2013-06-12.
[23]国家环境保护总局.水和废水监测分析方法[M].4版.北京:中国环境科学出版社,2002:258-284.The Environmental Protection Agency of State.The Monitoring and Analysis Methods of Water and Wastewater[M].4th ed.Beijing:China Environmental Science Press,2002:258-284.
[24]Huang Y H,Zhang T C.Nitrite reduction and formation of corrosion coatings in zerovalent iron systems[J].Chemosphere,2006,64(6):937-943.
[25]邓时海,李德生,卢阳阳,等.集成模块系统同步硝化反硝化处理低碳氮比污水的试验[J].中国环境科学,2014,34(9):2259-2265.Deng S H,Li D S,Lu Y Y,et al.Performance characteristics of simultaneous nitrification and denitrification(SND)for low carbon to nitrogen(C/N)ratio wastewater in an integrated device[J]China Environmental Science,2014,34(9):2259-2265.
[26]刘新超,贾磊,俞勤,等.零价铁还原脱氮技术研究进展[J].四川环境,2016,35(4):118-122.Liu X C,Jia L,Yu Q,et al.Review of reductive denitrification by zero-valent iron[J].Sichuan Environment,2016,35(4):118-122.
[27]王迪.还原铁粉去除地下水中硝酸盐及亚硝酸盐的研究[D].哈尔滨:东北林业大学,2013.Wang D.Study on removal of nitrate and nitrite in the groundwater ofreduced iron powder[D].Harbin:Northeast Forestry University,2013.
[28]Choe S,Chang Y Y,Hwang K Y,et al.Kinetics of reductive denitrification by nanoscale zero-valent iron[J].Chemosphere,2000,41(8):1307-1311.
[29]Li X Q,Elliott D W,Zhang W X.Zero-valent iron nanocarriers for abatement of environmental pollutants:materials and engineering aspects[J].Critical Reviews in Solid State&Materials Sciences,2006,31(4):111-122.
[30]郝志伟,李亮,马鲁铭.零价铁还原法脱除地下水中硝酸盐的研究[J].中国给水排水,2008,24(17):36-39.Hao Z W,Li L,Ma L M.Study on removal of nitrate from groundwater by zero-valent iron reduction process[J].China Water&Wastewater,2008,24(17):36-39.