臭氧催化氧化处理废水的催化剂适配
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摘要
为了探究不同臭氧催化氧化体系对工业废水中有机污染物的去除效果,以分子筛为载体,以Mn、Cu、Ni的乙酸盐溶液为前驱液,采用浸渍-焙烧法制备负载型催化剂.通过不同催化剂的适配研究,进行催化剂体系的优化筛选,从而获得适用于工业废水处理的多相臭氧催化氧化体系.结果表明:3种催化剂体系中,三元催化剂体系的负载率最高,为6.5%;催化剂/O3体系能显著提高废水的COD去除率,其中三元催化剂体系的COD去除率高于二元、一元催化剂体系,浸渍液中Mn、Cu、Ni摩尔比为1∶1∶3时,COD去除率高达59%;催化剂/O3体系处理工业废水后pH值明显降低,也证明催化剂与臭氧结合对废水有机物有显著的降解效果.
In order to investigate the removal efficiency of organic pollutants in industrial wastewater by different ozone catalytic oxidation systems, the different supported catalyst systems were prepared by the dipping-calcination method using molecular sieve as carrier and acetate solution of Mn, Cu and Ni as the precursor. Through the adaptation of different catalysts, the catalyst system was optimized and screened to obtain the heterogeneous ozone catalytic oxidation system suitable for industrial wastewater treatment. The results showed that the loading rate of three component catalytic system was optimal, up to 6.5%. The catalyst/O3 system can significantly improve the COD removal rate of wastewater. The removal rate of COD in the three component catalytic system was highest among three catalytic systems and that was up to 59% when the molar ratio of Mn, Cu and Ni was 1 ∶ 1 ∶3. The pH value of wastewater was dramatically decreased by treatment of catalyst/O3 system, which also proved that the combination of catalyst and ozone had a significant degradation effect on the organic compounds in wastewater.
In order to investigate the removal efficiency of organic pollutants in industrial wastewater by different ozone catalytic oxidation systems, the different supported catalyst systems were prepared by the dipping-calcination method using molecular sieve as carrier and acetate solution of Mn, Cu and Ni as the precursor. Through the adaptation of different catalysts, the catalyst system was optimized and screened to obtain the heterogeneous ozone catalytic oxidation system suitable for industrial wastewater treatment. The results showed that the loading rate of three component catalytic system was optimal, up to 6.5%. The catalyst/O3 system can significantly improve the COD removal rate of wastewater. The removal rate of COD in the three component catalytic system was highest among three catalytic systems and that was up to 59% when the molar ratio of Mn, Cu and Ni was 1 ∶ 1 ∶3. The pH value of wastewater was dramatically decreased by treatment of catalyst/O3 system, which also proved that the combination of catalyst and ozone had a significant degradation effect on the organic compounds in wastewater.
引文
[1]王维业.非均相臭氧催化氧化系统研究及其对印染废水的深度处理[D].哈尔滨:哈尔滨工业大学,2016.WANG W Y,Research on the systerm of heterogeneous catalytic ozonation and its′advanced treatment of dyeing wastewater[D].Harbin:Harbin Institute of Technology,2016(in Chinese).
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[3]JUDITH S,SUSANA C,PENA O,et al.Studyof the aromatic by-products formed from ozonation of ani-lines in aqueous solution[J].Water Research,2002,36(12):3035-3044.
[4]NAYDENOV A,KONOVA P,NIKOLOV P,et al.Decomposition of ozone on Ag/Si O2catalyst for abatement of wastegases emissions[J].Catalysis Today,2007,137(2/3/4):471-474.
[5]ESPLUGA S S,BILA D M,KRAUSE L G,et al,Ozonation and advanced oxidation technologies to remove endocrine disrupting chemical(EDCs)and pharmaceuticals and personal care products(PPCPs)in water effluents[J].Journal of Hazardous Materials,2007,149(3):631-642.
[6]KREETACHAT T,DAMRONGSRI D,PUNSUWON V,et al,Effects of ozonation process on lignin-derived compounds in pulp and paper mill effluents[J].Journal of Hazardous Materials,2007,142(1/2):250-257.
[7]BALCIOGLUA L A,TARLANB E,KIVICIMDANC C,et al.Merits of ozonation and catalytic ozonation pretreatment in the algal treatment of pulp and paper mill effluents[J].Journal of Environmental Management,2007,85(4):918-926.
[8]马宁,刘操,黄涛,等.多相催化臭氧氧化-纳滤工艺污水深度净化研究[J].环境科学与技术,2014(12):182-186,198.MA N,LIU C,HUANG T,et al.Wastewater advanced purification by integrating heterogeneous catalytic ozonation and nanofiltration process[J].Environment Science&Technology,2014(12):182-186,198(in Chinese).
[9]朱秋实,陈进富,姜海涛,等.臭氧催化氧化机理及其技术研究进展[J].化工进展,2014,33(4):1010-1014,1034.ZHU Q S,CHEN J F,JIANG H T,et al.A view of catalytic ozonation:Mechanisms and efficiency[J].Chemical In dustry and Engineering Progress,2014,33(4):1010-1014,1034(in Chinese).
[10]尤特,唐运平.Photo-Fenton技术处理难降解有机废水的研究进展[J].天津工业大学学报,2010,29(4):68-73.YOU T,TANG Y P.Progress of research with Photo-Fenton technology in treatment of non-degradable organic wastewater[J].Journal of Tianjin Polytechnic University,2010,29(4):68-73(in Chinese).
[11]金星龙,马俊华,刘勇,等.Fe-Ni/ZSM-5分子筛催化H2O2降解硝基苯[J].天津工业大学学报,2016,35(6):45-49.JIN X L,MA J H,LIU Y,et al.Fe-Ni/ZSM-5 catalyzing degradation of nitrobenzene by H2O2[J].Journal of Tianjin Polytechnic University,2016,35(6):45-49(in Chinese).
[12]KIM H C,CHOI W J,MAENG S K,et al.Ozonation of piggery wastewater for enhanced removal of contaminants by S.quadricauda and the impact on organic characteristics[J].Bioresource Technology,2014,159:128-135.
[13]苏金钰.活性炭负载Ti O2催化臭氧氧化去除水中的酚[D].湘潭:湘潭大学,2005:9-15.SU J Y.Catalytic ozonation of phenol by Ti O2nano-immobilized on activated carbon[D].Xiangtan:Xiangtan University,2005:9-15(in Chinese).
[14]WANG M,ZHANG P,LI J,et al.The effects of Mn loading on the structure and ozone decomposition activity of Mn Ox supported on activated carbon[J].Chinese Journal of Catalysis,2014,35(3):335-341.
[15]向罗京.非均相Fenton反应催化剂的制备及其在难降解有机物处理中的应用[D].武汉:武汉大学,2009:11-13.XIANG L J.Preparation of heterogeneous Fenton-type catalysts and their application in the treatment of refractory organic pollutants[D].Wuhan:Wuhan University,2009:11-13(in Chinese).
[16]沈悦欣.负载型钯基催化剂的制备及对CO低温氧化的催化性能研究[D].上海:华东理工大学,2011:16-29.SHEN Y X.Praparation and catalytic performance of supported Pd-based catalysts for low-temperature CO oxidation[D].Shanghai:East China University of Science and Technology,2011:16-29(in Chinese).
[17]逯瑶.臭氧催化氧化垃圾渗滤技术研究[D].长春:吉林建筑大学,2014.LU Y.Study on the technology of landfill leachate by catalytic ozonation[D].Changchun:Jilin Jianzhu University,2014(in Chinese).
[18]李绍英,任风兰,于令第.高氯废水中COD的测定[J].哈尔滨师范大学自然科学学报,1991(4):51-55.LI S Y,REN F L,YU L D.The determination of COD in wastewater containing high density of chloride[J].Natural Sciences Journal of Harbin Normal University,1991(4):51-55(in Chinese).
[19]李生,张晓霞,褚彬.高氯废水中COD测定方法探讨[J].周口师范学院学报,2007(5):85-86.LI S,ZHANG X X,CHU B.Discussion on the methods for COD measurement in high-chlorine wastewater[J].Journal of Zhoukou Normal University,2007(5):85-86(in Chinese).
[20]张素.COD(Cr)测定中氯离子干扰消除方法的比较[J].山东工业技术,2016(5):13.ZHANG S.Comparison of elimination methods of chloride ion interference in determination of COD(Cr)[J].Shandong Industrial Technology,2016(5):13(in Chinese).
[21]亓丽丽.非均相臭氧催化氧化对氯苯酚机理研究及其工艺应用[D].哈尔滨:哈尔滨工业大学,2013.QI L L.Mechanism research and application process of catalytic ozonation for degradation of 4-chlorophenol[D].Harbin:Harbin Institute of Technology,2013(in Chinese).
[22]CHEN C,LI Y,MA W,et al.Mn-Fe-Mg-Ce loaded Al2O3,catalyzed ozonation for mineralization of refractory organic chemicals in petroleum refinery wastewater[J].Separation&Purification Technology,2017,183:1-10.
[23]莫丽焕,谈金强,王聪聪,等.γ-Al2O3催化臭氧深度处理蔗渣制浆废水[J].华南理工大学学报:自然科学版,2017,45(2):144-152.MO L H,TAN J Q,WANG C C,et al.Advanced treatment of bagasse pulping effluent viaγ-Al2O3-catalyzed ozonation[J].Journal of South China University of Technology:Natural Science Edition,2017,45(2):144-152(in Chinese).
[24]IKHLAQ A,BROWN D R,KASPRZYK-HORDERN B.Mechanisms of catalytic ozonation:An investigation into superoxide ion radical and hydrogen peroxide formation during catalytic ozonation on alumina and zeolites in water[J].Applied Catalysis B:Environmental,2013,129:437-449.
[25]QI F,XU B,CHEN Z,et al.Catalytic ozonation of 2-isopropyl-3-methoxypyrazine in water byγ-Al OOH andγ-Al2O3:Comparison of removal efficiency and mechanism[J].Chemical Engineering Journal,2013,219:527-536.
[26]LI C,JIANG F,SUN D,et al.Catalytic ozonation for advanced treatment of incineration leachate using(Mn O2-Co3O4)/AC as a catalyst[J].Chemical Engineering Journal,2017,325:624-631.
[27]孙志忠.臭氧/多相催化氧化去除水中有机污染物效能与机理[D].哈尔滨:哈尔滨工业大学,2006.SUN Z Z.Efficiency and mechanism of ozone/heterogeneous catalytic oxidation for the degradation of organic pollutants in water[D].Harbin:Harbin Institute of Technology,2006(in Chinese).
[28]王树涛.O3/BAF联合工艺深度处理生活污水二级出水的研究[D].哈尔滨:哈尔滨工业大学,2008.WANG S T.Advanced treatment of secondary effluent by combined pre-ozonation and biofiltration[D].Harbin:Harbin Institute of Technology,2008(in Chinese).
[2]WANG J B,ZHOU Y R,ZHU W P,et al.Catalytic ozonation of dimethyl phthalate and chlorination disinfection by-product precursors over Ru/AC[J].Journal of Hazardous Materials,2009,166:502-507.
[3]JUDITH S,SUSANA C,PENA O,et al.Studyof the aromatic by-products formed from ozonation of ani-lines in aqueous solution[J].Water Research,2002,36(12):3035-3044.
[4]NAYDENOV A,KONOVA P,NIKOLOV P,et al.Decomposition of ozone on Ag/Si O2catalyst for abatement of wastegases emissions[J].Catalysis Today,2007,137(2/3/4):471-474.
[5]ESPLUGA S S,BILA D M,KRAUSE L G,et al,Ozonation and advanced oxidation technologies to remove endocrine disrupting chemical(EDCs)and pharmaceuticals and personal care products(PPCPs)in water effluents[J].Journal of Hazardous Materials,2007,149(3):631-642.
[6]KREETACHAT T,DAMRONGSRI D,PUNSUWON V,et al,Effects of ozonation process on lignin-derived compounds in pulp and paper mill effluents[J].Journal of Hazardous Materials,2007,142(1/2):250-257.
[7]BALCIOGLUA L A,TARLANB E,KIVICIMDANC C,et al.Merits of ozonation and catalytic ozonation pretreatment in the algal treatment of pulp and paper mill effluents[J].Journal of Environmental Management,2007,85(4):918-926.
[8]马宁,刘操,黄涛,等.多相催化臭氧氧化-纳滤工艺污水深度净化研究[J].环境科学与技术,2014(12):182-186,198.MA N,LIU C,HUANG T,et al.Wastewater advanced purification by integrating heterogeneous catalytic ozonation and nanofiltration process[J].Environment Science&Technology,2014(12):182-186,198(in Chinese).
[9]朱秋实,陈进富,姜海涛,等.臭氧催化氧化机理及其技术研究进展[J].化工进展,2014,33(4):1010-1014,1034.ZHU Q S,CHEN J F,JIANG H T,et al.A view of catalytic ozonation:Mechanisms and efficiency[J].Chemical In dustry and Engineering Progress,2014,33(4):1010-1014,1034(in Chinese).
[10]尤特,唐运平.Photo-Fenton技术处理难降解有机废水的研究进展[J].天津工业大学学报,2010,29(4):68-73.YOU T,TANG Y P.Progress of research with Photo-Fenton technology in treatment of non-degradable organic wastewater[J].Journal of Tianjin Polytechnic University,2010,29(4):68-73(in Chinese).
[11]金星龙,马俊华,刘勇,等.Fe-Ni/ZSM-5分子筛催化H2O2降解硝基苯[J].天津工业大学学报,2016,35(6):45-49.JIN X L,MA J H,LIU Y,et al.Fe-Ni/ZSM-5 catalyzing degradation of nitrobenzene by H2O2[J].Journal of Tianjin Polytechnic University,2016,35(6):45-49(in Chinese).
[12]KIM H C,CHOI W J,MAENG S K,et al.Ozonation of piggery wastewater for enhanced removal of contaminants by S.quadricauda and the impact on organic characteristics[J].Bioresource Technology,2014,159:128-135.
[13]苏金钰.活性炭负载Ti O2催化臭氧氧化去除水中的酚[D].湘潭:湘潭大学,2005:9-15.SU J Y.Catalytic ozonation of phenol by Ti O2nano-immobilized on activated carbon[D].Xiangtan:Xiangtan University,2005:9-15(in Chinese).
[14]WANG M,ZHANG P,LI J,et al.The effects of Mn loading on the structure and ozone decomposition activity of Mn Ox supported on activated carbon[J].Chinese Journal of Catalysis,2014,35(3):335-341.
[15]向罗京.非均相Fenton反应催化剂的制备及其在难降解有机物处理中的应用[D].武汉:武汉大学,2009:11-13.XIANG L J.Preparation of heterogeneous Fenton-type catalysts and their application in the treatment of refractory organic pollutants[D].Wuhan:Wuhan University,2009:11-13(in Chinese).
[16]沈悦欣.负载型钯基催化剂的制备及对CO低温氧化的催化性能研究[D].上海:华东理工大学,2011:16-29.SHEN Y X.Praparation and catalytic performance of supported Pd-based catalysts for low-temperature CO oxidation[D].Shanghai:East China University of Science and Technology,2011:16-29(in Chinese).
[17]逯瑶.臭氧催化氧化垃圾渗滤技术研究[D].长春:吉林建筑大学,2014.LU Y.Study on the technology of landfill leachate by catalytic ozonation[D].Changchun:Jilin Jianzhu University,2014(in Chinese).
[18]李绍英,任风兰,于令第.高氯废水中COD的测定[J].哈尔滨师范大学自然科学学报,1991(4):51-55.LI S Y,REN F L,YU L D.The determination of COD in wastewater containing high density of chloride[J].Natural Sciences Journal of Harbin Normal University,1991(4):51-55(in Chinese).
[19]李生,张晓霞,褚彬.高氯废水中COD测定方法探讨[J].周口师范学院学报,2007(5):85-86.LI S,ZHANG X X,CHU B.Discussion on the methods for COD measurement in high-chlorine wastewater[J].Journal of Zhoukou Normal University,2007(5):85-86(in Chinese).
[20]张素.COD(Cr)测定中氯离子干扰消除方法的比较[J].山东工业技术,2016(5):13.ZHANG S.Comparison of elimination methods of chloride ion interference in determination of COD(Cr)[J].Shandong Industrial Technology,2016(5):13(in Chinese).
[21]亓丽丽.非均相臭氧催化氧化对氯苯酚机理研究及其工艺应用[D].哈尔滨:哈尔滨工业大学,2013.QI L L.Mechanism research and application process of catalytic ozonation for degradation of 4-chlorophenol[D].Harbin:Harbin Institute of Technology,2013(in Chinese).
[22]CHEN C,LI Y,MA W,et al.Mn-Fe-Mg-Ce loaded Al2O3,catalyzed ozonation for mineralization of refractory organic chemicals in petroleum refinery wastewater[J].Separation&Purification Technology,2017,183:1-10.
[23]莫丽焕,谈金强,王聪聪,等.γ-Al2O3催化臭氧深度处理蔗渣制浆废水[J].华南理工大学学报:自然科学版,2017,45(2):144-152.MO L H,TAN J Q,WANG C C,et al.Advanced treatment of bagasse pulping effluent viaγ-Al2O3-catalyzed ozonation[J].Journal of South China University of Technology:Natural Science Edition,2017,45(2):144-152(in Chinese).
[24]IKHLAQ A,BROWN D R,KASPRZYK-HORDERN B.Mechanisms of catalytic ozonation:An investigation into superoxide ion radical and hydrogen peroxide formation during catalytic ozonation on alumina and zeolites in water[J].Applied Catalysis B:Environmental,2013,129:437-449.
[25]QI F,XU B,CHEN Z,et al.Catalytic ozonation of 2-isopropyl-3-methoxypyrazine in water byγ-Al OOH andγ-Al2O3:Comparison of removal efficiency and mechanism[J].Chemical Engineering Journal,2013,219:527-536.
[26]LI C,JIANG F,SUN D,et al.Catalytic ozonation for advanced treatment of incineration leachate using(Mn O2-Co3O4)/AC as a catalyst[J].Chemical Engineering Journal,2017,325:624-631.
[27]孙志忠.臭氧/多相催化氧化去除水中有机污染物效能与机理[D].哈尔滨:哈尔滨工业大学,2006.SUN Z Z.Efficiency and mechanism of ozone/heterogeneous catalytic oxidation for the degradation of organic pollutants in water[D].Harbin:Harbin Institute of Technology,2006(in Chinese).
[28]王树涛.O3/BAF联合工艺深度处理生活污水二级出水的研究[D].哈尔滨:哈尔滨工业大学,2008.WANG S T.Advanced treatment of secondary effluent by combined pre-ozonation and biofiltration[D].Harbin:Harbin Institute of Technology,2008(in Chinese).
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