异相类Fenton氧化处理T酸废母液的催化剂
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摘要
为了比较黄铁矿、钛铁矿、磁铁矿、钒钛磁铁矿、零价铁以及亚铁催化双氧水氧化处理T酸废母液的效能,研究了不同体系的催化氧化反应动力学以及p H值变化情况,考察了H2O2投加量、催化剂投加量及循环利用次数的影响。研究结果表明,黄铁矿、钛铁矿催化活性较亚铁离子更好,且受废水p H值变化影响小,T酸废母液TOC去除率高达75%左右,是十分有效的类Fenton反应催化剂。钛铁矿催化活性较黄铁矿好,重复利用5次,TOC去除率依然保持在72%以上,表明钛铁矿有着很好的重复利用性。
In order to compare the catalytic efficacy of pyrite,ilmenite,magnetite,vanadium titano-magnetite,zero-valent iron and ferrous ions,catalytic oxidation kinetics and p H variations were investigated using H2O2 as an oxidant to treat spent liquor of T-acid crystallization. The effects of H2O2 dosage and catalyst dosage as well its reuse on TOC removal were also examined. The experimental results demonstrated that pyrite and ilmenite showed a higher catalytic activity than ferrous iron in a wide range of p H. TOC removal was around 75% for the spent liquor of T-acid crystallization catalyzed by pyrite or ilmenite,which proved to be highly efficient catalysts of Fenton-like reaction. The TOC removal exceeded 72% even at 5 cycles of oxidation with ilmenite,indicating that ilmenite performed a good reusability.
In order to compare the catalytic efficacy of pyrite,ilmenite,magnetite,vanadium titano-magnetite,zero-valent iron and ferrous ions,catalytic oxidation kinetics and p H variations were investigated using H2O2 as an oxidant to treat spent liquor of T-acid crystallization. The effects of H2O2 dosage and catalyst dosage as well its reuse on TOC removal were also examined. The experimental results demonstrated that pyrite and ilmenite showed a higher catalytic activity than ferrous iron in a wide range of p H. TOC removal was around 75% for the spent liquor of T-acid crystallization catalyzed by pyrite or ilmenite,which proved to be highly efficient catalysts of Fenton-like reaction. The TOC removal exceeded 72% even at 5 cycles of oxidation with ilmenite,indicating that ilmenite performed a good reusability.
引文
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[15]Lin H.S.,Gurol M.D.Catalytic decomposition of hydrogen peroxide on iron oxide:Kinetics,mechanism,and implications.Environmental Science&Technology,1998,32(10):1417-1423
[16]吴忠标.环境催化原理及应用.北京:化学工业出版社,2006:462-472
[17]Quintanilla A.,Casas J.A.,Zazo J.A.,et al.Wet air oxidation of phenol at mild conditions with a Fe/activated carbon catalyst.Applied Catalysis B:Environmental,2006,62(1-2):115-120
[18]Bossmann S.H.,Oliveros E.,Gb S.,et al.New evidence against hydroxyl radicals as reactive intermediates in the thermal and photochemically enhanced Fenton reactions.The Journal of Physical Chemistry A,1998,102(28):5542-5550
[2]祝万鹏,杨志华,王利.亚铁-过氧化氢氧化法处理染料中间体H酸生产废液的研究.中国环境科学,1995,15(5):368-372Zhu Wanpeng,Yang Zhihua,Wang Li.Application of ferrous-hydrogen peroxide for treatment of H-acid manufacturing process wastewater.China Environmental Science,1995,15(5):368-372(in Chinese)
[3]陈胜兵,何少华,娄金生,等.Fenton试剂的氧化作用机理及其应用.环境科学与技术,2004,27(3):105-107Chen Shengbing,He Shaohua,Lou Jinsheng,et al.Oxidation mechanism and application of Fenton reagent.Environmental Science&Technology,2004,27(3):105-107(in Chinese)
[4]郑怀礼,谢礼国,胡鹏,等.非均相类Fenton反应催化氧化脱色降解直接桃红12B.光谱学与光谱分析,2010,30(6):1647-1651Zheng Huili,Xie Liguo,Hu Peng,et al.Decoloration and degradation of direct pink 12B by microwave-promoted heterogeneous Fenton-like reaction.Spectroscopy and Spectral Analysis,2010,30(6):1647-1651(in Chinese)
[5]王彦彬,赵红颖,赵国华,等.基于铁化合物的异相Fenton催化氧化技术.化学进展,2013,25(8):1246-1259Wang Yanbin,Zhao Hongying,Zhao Guohua,et al.Iron compound-based heterogenous Fenton catalytic oxidation technology.Progress in Chemistry,2013,25(8):1246-1259(in Chinese)
[6]吴德礼,段冬,马鲁铭.黄铁矿烧渣催化H2O2氧化废水中难降解污染物.化工学报,2010,61(4):1001-1008Wu Deli,Duan Dong,Ma Luming.Fenton-like oxidation of refractory organic contaminants in wastewater using pyrite cinder at neutral p H.CIESC Journal,2010,61(4):1001-1008(in Chinese)
[7]陶长元,丁小红,刘作华,等.Fenton类氧化技术处理有机废水的研究进展.化学研究与应用,2007,19(11):1177-1180Tao Changyuan,Ding Xiaohong,Liu Zuohua,et al.Fenton reagents-based AOPs for purification of organic wastewater.Chemical Research and Application,2007,19(11):1177-1180(in Chinese)
[8]吴大清,刁桂仪,袁鹏.氧化铁矿物催化分解苯酚的动力学速率及其产物特征.矿物岩石地球化学通报,2006,25(4):293-298Wu Daqing,Diao Guiyi,Yuan Peng.A study on kinetic rates of catalytic decomposition of phenol by hydrogen peroxide with iron oxides and the characteristics of the decomposing products.Bulletin of Mineralogy,Petrology and Geochemistry,2006,25(4):293-298(in Chinese)
[9]Baldrian P.,MerhautováV.,Gabriel J.,et al.Decolorization of synthetic dyes by hydrogen peroxide with heterogeneous catalysis by mixed iron oxides.Applied Catalysis B:Environmental,2006,66(3-4):258-264
[10]胥焕岩,彭明生,刘羽,等.矿物类Fenton反应降解有机污染物的研究发展.矿物岩石地球化学通报,2009,28(4):394-400Xu Huanyan,Peng Mingsheng,Liu Yu,et al.Research progress on the decomposition of organic pollutants by mineral-catalyzed Fenton-like system:An overview.Bulletin of Mineralogy,Petrology and Geochemistry,2009,28(4):394-400(in Chinese)
[11]冯勇,吴德礼,马鲁铭.铁氧化物催化类Fenton反应.化学进展,2013,25(7):1219-1228Feng Yong,Wu Deli,Ma Luming.Iron oxide catalyzed Fenton-like reaction.Progress in Chemistry,2013,25(7):1219-1228(in Chinese)
[12]张钰,何燕,邹彩琼,等.铁锰矿类Fenton异相光催化降解有毒有机染料.环境化学,2010,29(6):1032-1037Zhang Yu,He Yan,Zou Caiqiong,et al.Photo-degradation of organic dye by iron-manganese ore as heterogeneous Fenton-like catalyst.Environmental Chemistry,2010,29(6):1032-1037(in Chinese)
[13]张国卿,王罗春,徐高田,等.Fenton试剂在处理难降解有机废水中的应用.工业安全与环保,2004,30(3):17-19Zhang Guoqing,Wang Luochun,Xu Gaotian,et al.The application of Fenton reagent in the treatment for degrading organic wastewater.Industrial Safety and Environmental Protection,2004,30(3):17-19(in Chinese)
[14]相欣奕,郑怀礼.Fenton反应处理染料废水研究进展.重庆建筑大学学报,2004,26(4):126-130Xiang Xinyi,Zheng Huaili.A review of Fenton oxidation used in degradation of dyes.Journal of Chongqing Jianzhu University,2004,26(4):126-130(in Chinese)
[15]Lin H.S.,Gurol M.D.Catalytic decomposition of hydrogen peroxide on iron oxide:Kinetics,mechanism,and implications.Environmental Science&Technology,1998,32(10):1417-1423
[16]吴忠标.环境催化原理及应用.北京:化学工业出版社,2006:462-472
[17]Quintanilla A.,Casas J.A.,Zazo J.A.,et al.Wet air oxidation of phenol at mild conditions with a Fe/activated carbon catalyst.Applied Catalysis B:Environmental,2006,62(1-2):115-120
[18]Bossmann S.H.,Oliveros E.,Gb S.,et al.New evidence against hydroxyl radicals as reactive intermediates in the thermal and photochemically enhanced Fenton reactions.The Journal of Physical Chemistry A,1998,102(28):5542-5550