铈铁复合类Fenton反应去除邻苯二酚的性能及机制探究
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摘要
研究了Fe~(2+)/Ce~(3+)/H_2O_2类Fenton反应体系去除邻苯二酚的性能.结果表明,在c(邻苯二酚)=10 mmol/L,pH=7及n(Fe~(2+))∶n(Ce~(3+))∶n(H_2O_2)=1∶2∶30的条件下,邻苯二酚的去除率可以达到85%以上,明显高于经典Fenton的去除率,且铈的加入改善了经典Fenton反应最适pH值在酸性范围内的缺点.通过对反应后生成沉淀物的FTIR和XPS表征,推测将Ce~(3+)引入经典Fenton体系后,其提高了HO_2·/O_2~-·的生成速率,进而促进了类Fenton反应中Fe~(3+)向Fe~(2+)的转化,进一步催化了羟基自由基的产生,从而有效提高了邻苯二酚的降解转化.此外,部分铁和铈在反应过程中形成的沉淀化合物也有助于邻苯二酚及其降解中间产物的吸附去除.
The removal performance of catechol by Fe~(2+)/Ce~(3+)/H_2O_2 Fenton-like reaction system was studied.The results showed that the optimum reaction conditions for the treatment of 10 mmol/L catechol were as follows:pH=7,n(Fe~(2+))∶n(Ce~(3+))∶n(H_2O_2) was 1∶2∶30,the removal rate of catechol could reach more than 85 %,which was obviously higher than that of classical fenton.The addition of cerium overcome the disadvantage of narrow application range of pH value in a classical Fenton reaction.The composition of the precipitates was characterized by FTIR and XPS.The influence of the addition of cerium on the classical Fenton reaction and the possible removal mechanism were investigated.In addition,the precipitated compounds formed from the reaction of some iron and cerium ions also contribute to the adsorption and removal of catechol and its degradation intermediates.
The removal performance of catechol by Fe~(2+)/Ce~(3+)/H_2O_2 Fenton-like reaction system was studied.The results showed that the optimum reaction conditions for the treatment of 10 mmol/L catechol were as follows:pH=7,n(Fe~(2+))∶n(Ce~(3+))∶n(H_2O_2) was 1∶2∶30,the removal rate of catechol could reach more than 85 %,which was obviously higher than that of classical fenton.The addition of cerium overcome the disadvantage of narrow application range of pH value in a classical Fenton reaction.The composition of the precipitates was characterized by FTIR and XPS.The influence of the addition of cerium on the classical Fenton reaction and the possible removal mechanism were investigated.In addition,the precipitated compounds formed from the reaction of some iron and cerium ions also contribute to the adsorption and removal of catechol and its degradation intermediates.
引文
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[14] 姜成春,庞素艳,马军,等.钛盐光度法测定Fenton氧化中的过氧化氢[J].中国给水排水,2006,22:88-91.doi:10.3321/j.issn.1000-4602.2006.04.025JIANG Chengchun,PANG Suyan,MA Jun.Spectrophotometric Determination of Hydrogen Peroxide in Fenton Reaction with Titanium Oxalate[J].China Water & Wastewater,2006,22:88-91.
[15] 赵建军,李炳伟,付连永.铈催化双氧水去除废水中的COD研究[C]//第十七届全国稀土催化学术会议论文集.上海:中国稀土催化专业委员会,2010:156-159.ZHAO Jianjun,LI Bingwei,FU Lianyong.Cerium Catalyze Hydrogen Peroxide to Remove the COD of Wastewater[C]//Papers Collection of the Seventeenth National Academic Conference on Rare Earth Catalysis.Shanghai:Rare Earth Society of China,2010:156-159.
[16] HARGRAVE K R.Reactions of Ferrous and Ferric Ions with Hydrogen Peroxide[J].Trans Faraday Soc,1951,47:591-616.doi:10.1039/TF9514700462
[17] 赵吉.双金属芬顿体系氧化水中有机物的效能与机理研究[D].哈尔滨:哈尔滨工业大学,2014.ZHAO Ji.Performance and Mechanism of the Oxidation of Organic Pollutants by Bimetallic Fenton Reactions[D].Harbin:Harbin Institute of Technology,2014.
[18] BUXTON G V,GREENSTOCK C L,HELMAN W P,et al.Critical Review of Rate Constants for Reactions of Hydrated Electrons,Hydrogen Atoms and Hydroxyl Radicals(·OH/·O-) in Aqueous Solution[J].Journal of Physical & Chemical Reference Data,1998,17:583-586.doi:10.1063/1.555805
[19] BIELSKI B H J,CABELLI D E,ARUDI R L,et al.Reactivity of HO2/O2- Radicals in Aqueous Solution[J].Journal of Physical & Chemical Reference Data,1985,14:1041-1100.doi:10.1063/1.555739
[20] GUBLER L,KOPPENOL W H.Kinetic Simulation of the Chemical Stabilization Mechanism in Fuel Cell Membranes Using Cerium and Manganese Redox Couples[J].Journal of the Electrochemical Society,2011,159:B211-B217.doi:10.1149/2.075202jes
[21] DANILCZUK M,SCHLICK S,COMS F D.Cerium(Ⅲ) as a Stabilizer of Perfluorinated Membranes Used in Fuel Cells:In Situ Detection of Early Events in the ESR Resonator[J].Macromolecules,2009,42:89-113.doi:10.1021/ma9017108
[2] HUANG C P,DONG C,TANG Z.Advanced Chemical Oxidation:Its Present Role and Potential Future in Hazardous Waste Treatment[J].Waste Management,1993,13:361-377.doi:10.1016/0956-053X(93)90070-D
[3] 汤鸿霄.无机高分子絮凝剂的基础研究[J].环境化学,1990,9(3):1-12.TANG Hongxiao.Basic Research on Inorganic Polymer Flocculant[J].Environmental Chemistry,1990,9(3):1-12.
[4] GALLARD H,LAAT J D,LEGUBE B.Spectrophotometric Study of the Formation of Iron(Ⅲ)-hydroperoxy Complexes in Homogeneous Aqueous Solutions[J].Water Research,1999,33:2929-2936.doi:10.1016/S0043-1354(99)00007-X
[5] 高迎新,张昱,杨敏.Fenton反应中氧化还原电势的变化规律[J].环境化学,2004,23(2):135-139.doi:10.3321/j.issn.0254-6108.2004.02.003GAO Yingxin,ZHANG Yu,YANG Min.Characteristics of Orp in Fenton′s Reaction[J].Environmental Chemistry,2004,23(2):135-139.
[6] 周曼.非铁基芬顿(Fenton)体系高级氧化技术的发展和现状[J].化学工程与装备,2014(9):173-176.ZHOU Man.Development and Present Situation of Advanced Oxidation Technology in Non-ferrofenton(Fenton) System[J].Chemical Engineering & Equipment,2014(9):173-176.
[7] ISSA H H,FINQUENEISEL G,AZAMBRE B.Removal of Binary Dyes Mixtures with Opposite and Similar Charges by Adsorption,Coagulation/Flocculation and Catalytic Oxidation in the Presence of CeO2/H2O2 Fenton-like System[J].Journal of Environmental Management,2017,195:195-207.doi:10.1016/J.Jenvman.2016.07.067
[8] RUI C M,AMARALl-SILVA N,QUINTA-FERREIRA R M.Ceria Based Solid Catalysts for Fenton′s Depuration of Phenolic Wastewaters,Biodegradability Enhancement and Toxicity Removal[J].Applied Catalysis B Environmental,2010,99:135-144.doi:10.1016/j.apcatb.2010.06.010
[9] ROSSI A F,AMARAL-SILVA N,RUI C M,et al.Heterogeneous Fenton Using Ceria Based Catalysts:Effects of the Calcination Temperature in the Process Efficiency[J].Applied Catalysis B Environmental,2012,111:254-263.doi:10.1016/j.apcatb.2011.10.006
[10] ZHANG Yaping,JIA Chengguang,PENG Ran,et al.Heterogeneous Photo-assisted Fenton Catalytic Removal of Tetracycline Using Fe-Ce Pillared Bentonite[J].Journal of Central South University(English Edition),2014,21:310-316.doi:10.1007/S11771-014-1942-3
[11] SCHWEIGERT N,ZEHNDER A J B,EGGEN R I L.Chemical Properties of Catechols and Their Molecular Modes of Toxic Action in Cells,From Microorganisms to Mammals[J].Environmental Microbiology,2010,3:81-91.doi:10.1046/j.1462-2920.2001.00176.x
[12] 王景明.邻苯二酚的应用及合成方法探析[J].煤炭与化工,1997(4):46-48.WANG Jingming.Analysis of the Application and Synthesis of Catechol[J].Coal and Chemical Industry,1997(4):46-48.
[13] 庞振涛,焦凤茹,刘晓东.邻苯二酚技术进展与市场分析[J].当代化工研究,2008(3):30-33.doi:10.3969/j.issn.1672-8114.2008.01.009PANG Zhentao,JIAO Fengru,LIU Xiaodong.Market Analysis and Technological Progress of Pyroeatechol[J].Modern Chemical Research,2008(3):30-33.
[14] 姜成春,庞素艳,马军,等.钛盐光度法测定Fenton氧化中的过氧化氢[J].中国给水排水,2006,22:88-91.doi:10.3321/j.issn.1000-4602.2006.04.025JIANG Chengchun,PANG Suyan,MA Jun.Spectrophotometric Determination of Hydrogen Peroxide in Fenton Reaction with Titanium Oxalate[J].China Water & Wastewater,2006,22:88-91.
[15] 赵建军,李炳伟,付连永.铈催化双氧水去除废水中的COD研究[C]//第十七届全国稀土催化学术会议论文集.上海:中国稀土催化专业委员会,2010:156-159.ZHAO Jianjun,LI Bingwei,FU Lianyong.Cerium Catalyze Hydrogen Peroxide to Remove the COD of Wastewater[C]//Papers Collection of the Seventeenth National Academic Conference on Rare Earth Catalysis.Shanghai:Rare Earth Society of China,2010:156-159.
[16] HARGRAVE K R.Reactions of Ferrous and Ferric Ions with Hydrogen Peroxide[J].Trans Faraday Soc,1951,47:591-616.doi:10.1039/TF9514700462
[17] 赵吉.双金属芬顿体系氧化水中有机物的效能与机理研究[D].哈尔滨:哈尔滨工业大学,2014.ZHAO Ji.Performance and Mechanism of the Oxidation of Organic Pollutants by Bimetallic Fenton Reactions[D].Harbin:Harbin Institute of Technology,2014.
[18] BUXTON G V,GREENSTOCK C L,HELMAN W P,et al.Critical Review of Rate Constants for Reactions of Hydrated Electrons,Hydrogen Atoms and Hydroxyl Radicals(·OH/·O-) in Aqueous Solution[J].Journal of Physical & Chemical Reference Data,1998,17:583-586.doi:10.1063/1.555805
[19] BIELSKI B H J,CABELLI D E,ARUDI R L,et al.Reactivity of HO2/O2- Radicals in Aqueous Solution[J].Journal of Physical & Chemical Reference Data,1985,14:1041-1100.doi:10.1063/1.555739
[20] GUBLER L,KOPPENOL W H.Kinetic Simulation of the Chemical Stabilization Mechanism in Fuel Cell Membranes Using Cerium and Manganese Redox Couples[J].Journal of the Electrochemical Society,2011,159:B211-B217.doi:10.1149/2.075202jes
[21] DANILCZUK M,SCHLICK S,COMS F D.Cerium(Ⅲ) as a Stabilizer of Perfluorinated Membranes Used in Fuel Cells:In Situ Detection of Early Events in the ESR Resonator[J].Macromolecules,2009,42:89-113.doi:10.1021/ma9017108