第4期 史艳华等:贵金属氧化物涂层电极催化降解苯胺 .363. 80.5%,电解5h后水杯电解槽的电流效率达到 conditions on the properties of Ti based Ir02+Ta20s anodes.Ac- 8%,比不过滤时提高了近2倍。因此认为:采用贵 ta Metall Sin.2002.38(1):69 (胡吉明,孟惠民,张鉴清,等.制备条件对钛基1r02十Ta205涂 金属氧化物涂层电极,设计合理的电解装置,运用电 层阳极性能的影响.金属学报,2002,38(1):69) 解与过滤或沉降等物理手段相结合的工艺,可以有 [5]Hu J M.Zhang J Q.Cao C N.Thermolytic formation and mi- 效降解苯胺且节能降耗,为今后降解含苯胺有机废 crostructure of Ir02+Ta20s mixed oxide anodes from chloride 水的研究提供有力的参考 precursors.Thermochim Acta.2003.403:257 [6]Zhao G H.Chen R.Gao YY.The ways of oxidative degradation 3结论 of organic pollutant aniline on catalytic electrodes-Res Environ Sci,2003,16(3):51 (1)中性与碱性体系的苯胺降解过程类似,按 (赵国华,陈蕊,高廷耀.有机污染物苯胺在催化电极上氧化降 苯胺一苯醒一马来酸的过程氧化降解,碱性体系易 解途径.环境科学研究,2003,16(3):51) 于析氧而降低了降解效率;酸性体系生成聚苯胺物 [7]Liu Y.WeiS Q.Ba S H.Effect of surfactant SDS on the electro- 质增加了降解难度,降解效率最低, chemical synthesis of polyaniline and its degradation.Shenyang (2)苯胺在电化学催化氧化时最易形成对位和 1 nst Technol,2000,19(3):27 (刘瑛,魏守强,霸书红.表面活性剂SDS对聚苯胺电化学合成 间位的中间产物,而其对位和间位中间产物又难于 及其降解的影响.沈阳工业学院学报,2000,19(3):27) 降解,这是苯胺难于降解的根本原因 [8]Niu Z J.Ni Y H.LiZ L.Influence of zine ion on electrochemi- (③)提出在电解苯胺过程中增加物理过滤步骤 cally synthesis of polyaniline.IZhejiang Normal Univ Nat Sci. 的新工艺,该工艺不仅能够有效地降解苯胺,苯胺 2005,28(1)47 去除率由原来的55%提高到80.5%,电流效率比不 (牛振江,倪亚红,李则林.Z2十对电化学合成聚苯胺膜的影 响.浙江大学师范学报(自然科学版),2005,28(1):47) 过滤时提高了近2倍,达到了8%. [9]Song W F,Ma Q,Li Y J.Study on degradation aniline with dif- ferent DSA anode catalytic systems.Environ Prot Sci.2001.27: 参考文献 4 [1]Tao Y C.Tao JZ.Environmental Electrochemistry.Beijing: (宋卫锋,马前,李义久,不同DSA类阳极催化降解苯胺的试验 Chemical Industry Press.2003 研究.环境保护科学,2001,27.4) (陶映初,陶举洲.环境电化学.北京:化学工业出版社,2003) [10]Meguru T.Masakazu L.Plasma induced degradation of aniline [2]Meng H M.Li J H.Yu H Y.Electrolysis of organic pollutants in in aqueous solution.Thin Solid Films,2001,386 (2):204 wastewater using an IrO2 Ta2Os/Ti electrode.J Unin Sci Tech- [11]Sun DZ,Yu X J.Feng Y J.et al.High-level Oxidation for nol Beijing,2003,25(5):405 Environmental Project.Beijing:Chemical Industry Press,2002 (孙德智,于秀娟,冯玉杰,等.环境工程中的高级氧化技术.北 (孟惠民,李金鸿,俞宏英贵金属氧化物电极电解处理有机废 水.北京科技大学学报,2003,25(5):405) 京:化学工业出版社,2002) [3]Xu G Q.Yu HY.Li HQ.Study on treatment of alcohol simula- [12]Brillas E,CasadoJ.Aniline degradation by Electro-Fenton and tive wastewater by anodic electrolysis by noble metallic oxide. peroxi coagulation processes using a flow reactor for wastew ater Jiangsu Environ Sci Technol,2004,17(1):6 treatment.Chemosphere.2002.47(3):241 (许广勤,俞宏英,李辉勤贵金属氧化物阳极电解处理乙醇模 [13]WuZ C.Zhou M H.Wang D H.Synergetic effects of anodic 拟废水的研究.江苏环境科技,2004,17(1):6) cathodic electrocatalysis for phenol degradation in the presence of iron (I).Chemasphere,2002,48(10):1089 [4]Hu J M,Meng H M.Zhang J Q.et al.Effect of preparation80∙5%电解5h 后水杯电解槽的电流效率达到 8%比不过滤时提高了近2倍.因此认为:采用贵 金属氧化物涂层电极设计合理的电解装置运用电 解与过滤或沉降等物理手段相结合的工艺可以有 效降解苯胺且节能降耗为今后降解含苯胺有机废 水的研究提供有力的参考. 3 结论 (1) 中性与碱性体系的苯胺降解过程类似按 苯胺—苯醌—马来酸的过程氧化降解.碱性体系易 于析氧而降低了降解效率;酸性体系生成聚苯胺物 质增加了降解难度降解效率最低. (2) 苯胺在电化学催化氧化时最易形成对位和 间位的中间产物而其对位和间位中间产物又难于 降解这是苯胺难于降解的根本原因. (3) 提出在电解苯胺过程中增加物理过滤步骤 的新工艺.该工艺不仅能够有效地降解苯胺苯胺 去除率由原来的55%提高到80∙5%电流效率比不 过滤时提高了近2倍达到了8%. 参 考 文 献 [1] Tao Y CTao J Z.Environmental Electrochemistry.Beijing: Chemical Industry Press2003 (陶映初陶举洲.环境电化学.北京:化学工业出版社2003) [2] Meng H MLi J HYu H Y.Electrolysis of organic pollutants in wastewater using an IrO2-Ta2O5/Ti electrode.J Univ Sci Technol Beijing200325(5):405 (孟惠民李金鸿俞宏英.贵金属氧化物电极电解处理有机废 水.北京科技大学学报200325(5):405) [3] Xu G QYu H YLi H Q.Study on treatment of alcohol simulative wastewater by anodic electrolysis by noble metallic oxide. Jiangsu Environ Sci Technol200417(1):6 (许广勤俞宏英李辉勤.贵金属氧化物阳极电解处理乙醇模 拟废水的研究.江苏环境科技200417(1):6) [4] Hu J MMeng H MZhang J Qet al.Effect of preparation conditions on the properties of Ti based IrO2+Ta2O5anodes.Acta Metall Sin200238(1):69 (胡吉明孟惠民张鉴清等.制备条件对钛基 IrO2+Ta2O5 涂 层阳极性能的影响.金属学报200238(1):69) [5] Hu J MZhang J QCao C N.Thermolytic formation and microstructure of IrO2+ Ta2O5 mixed oxide anodes from chloride precursors.Thermochim Acta2003403:257 [6] Zhao G HChen RGao Y Y.The ways of oxidative degradation of organic pollutant aniline on catalytic electrodes.Res Environ Sci200316(3):51 (赵国华陈蕊高廷耀.有机污染物苯胺在催化电极上氧化降 解途径.环境科学研究200316(3):51) [7] Liu YWei S QBa S H.Effect of surfactant SDS on the electrochemical synthesis of polyaniline and its degradation.J Shenyang Inst Technol200019(3):27 (刘瑛魏守强霸书红.表面活性剂 SDS 对聚苯胺电化学合成 及其降解的影响.沈阳工业学院学报200019(3):27) [8] Niu Z JNi Y HLi Z L.Influence of zinc ion on electrochemically synthesis of polyaniline.J Zhejiang Normal Univ Nat Sci 200528(1):47 (牛振江倪亚红李则林.Zn2+对电化学合成聚苯胺膜的影 响.浙江大学师范学报(自然科学版)200528(1):47) [9] Song W FMa QLi Y J.Study on degradation aniline with different DSA anode catalytic systems.Environ Prot Sci200127: 4 (宋卫锋马前李义久.不同 DSA 类阳极催化降解苯胺的试验 研究.环境保护科学200127:4) [10] Meguru TMasakazu L.Plasma-induced degradation of aniline in aqueous solution.Thin Solid Films2001386(2):204 [11] Sun D ZYu X JFeng Y Jet al.High-level Oxidation for Environmental Project.Beijing:Chemical Industry Press2002 (孙德智于秀娟冯玉杰等.环境工程中的高级氧化技术.北 京:化学工业出版社2002) [12] Brillas ECasado J.Aniline degradation by Electro-Fenton○R and perox-i coagulation processes using a flow reactor for wastewater treatment.Chemosphere200247(3):241 [13] Wu Z CZhou M HWang D H.Synergetic effects of anodic cathodic electrocatalysis for phenol degradation in the presence of iron (Ⅱ).Chemosphere200248(10):1089 第4期 史艳华等: 贵金属氧化物涂层电极催化降解苯胺 ·363·