铜质量比对Fe/Cu还原2,4-二氯酚影响及还原途径
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摘要
针对Fe/Ni、Fe/Pd双金属成本高,疏水性较差的问题,采用改性纳米Fe/Cu双金属还原水中2,4-二氯酚(2,4-DCP),考察了铜质量比(ω(Cu))对Fe/Cu还原降解2,4-DCP效果的影响,结果表明:反应进行到80 h时,ω(Cu)=10%的Fe/Cu还原效果最佳,对2,4-DCP的去除率接近100%,中间产物4-氯酚(4-CP)也基本转化为终产物苯酚(CA),CA产率达91.8%。还原通过2种途径进行:(1)2,4-DCP先被还原脱去一个氯生成中间产物4-CP,随着反应进行再被脱去一个氯生成CA;(2)2,4-DCP被直接脱去2个氯生成终产物CA。XRD分析表明:反应后Fe/Cu中的Fe~0被氧化为Fe_3O_4和Fe_2O_3,Cu~0被氧化为CuO。
Aim at the problems that Fe/Ni and Fe/Pd bimetal are high cost and weak hydrophobicity,nanoscale Fe/Cu bimetal was modified and used to dechlorinate 2,4-dichlorophenol(2,4-DCP). The effects of mass ratio of copper(ω(Cu))on the reduction of 2,4-dichlorophenol by Fe/Cu were investigated. The results showed that when the reaction time was 80 h,the removal rate of 2,4-DCP by Fe/Cu(ω(Cu)=10%) was nearly 100% and the intermediate,4-chlorophenol(4-CP),was converted into end product,phenol(CA). The yield of CA was found to reach to 91.8%. The dechlorination pathways of 2,4-DCP were confirmed,that is,2,4-DCP was dechlorinated a chlorine atom to produce 4-CP at first,and then the dechlorination was performed sequentially to form CA. 2,4-DCP was dechlorinated two chlorine atoms simultaneously to generate CA. XRD analysis indicated that Fe~0 was oxidized to Fe_3O_4 and Fe_2O_3 and Cu~0 was oxidized to Cu O after the reaction.
Aim at the problems that Fe/Ni and Fe/Pd bimetal are high cost and weak hydrophobicity,nanoscale Fe/Cu bimetal was modified and used to dechlorinate 2,4-dichlorophenol(2,4-DCP). The effects of mass ratio of copper(ω(Cu))on the reduction of 2,4-dichlorophenol by Fe/Cu were investigated. The results showed that when the reaction time was 80 h,the removal rate of 2,4-DCP by Fe/Cu(ω(Cu)=10%) was nearly 100% and the intermediate,4-chlorophenol(4-CP),was converted into end product,phenol(CA). The yield of CA was found to reach to 91.8%. The dechlorination pathways of 2,4-DCP were confirmed,that is,2,4-DCP was dechlorinated a chlorine atom to produce 4-CP at first,and then the dechlorination was performed sequentially to form CA. 2,4-DCP was dechlorinated two chlorine atoms simultaneously to generate CA. XRD analysis indicated that Fe~0 was oxidized to Fe_3O_4 and Fe_2O_3 and Cu~0 was oxidized to Cu O after the reaction.
引文
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[16]Chen Wenfang,Pan Ling,Chen Lifang,et al.Dechlorination of hexachlorobenzene by nano zero-valent iron/activated carbon composite:iron loading,kinetics and pathway[J].RSC Advances,2014(4):46689-46696.
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[18]Wu Pingxiao,Liu Chongmin,Huang Zhujian,et al.Enhanced dechlorination performance of 2,4-dichlorophenol by vermiculite supported iron nanoparticles doped with palladium[J].RSC Advances,2014(4):25580-25587.
[19]Macarena M,Zahara M D,Jose A,et al.Chlorophenols breakdown by a sequential hydrodechlorination-oxidation treatment with a magnetic Pde Fe/g-Al2O3catalyst[J].Water Research,2013,47(9):3070-3080.
[20]Zhen Z,Qiao H S,Naman C,et al.Catalytic dechlorination of 2,4-dichlorophenol by Pd/Fe bimetallic nanoparticles in the presence of humic acid[J].Journal of Hazardous Materials,2010,182(1):252-258.
[21]Han Y,Li W,Zhang M H,et al.Catalytic dechlorination of monochlorobenzene with a new type of nanoscale Ni(B)/Fe(B)bimetallic catalytic reductant[J].Chemosphere,2008,72(1):53-58.
[22]Cheng Rong,Zhou Wei,Wang Jianlong,et al.Dechlorination of pentachlorophenol using nanoscale Fe/Ni particles:role of nano-Ni and its size effect[J].Journal of Hazardous Materials,2010,180(1):79-85.
[23]彭秀达,刘红,秦雄,等.十六烷基三甲基溴化铵对膨润土负载纳米铁去除水中铬(Ⅵ)的增强作用[J].硅酸盐学报,2014,42(4):514-521.Peng Xiuda,Liu Hong,Qin Xiong,et al.Removal of chromium(Ⅵ)using zero-valent nanoscale iron spported on bentonite trimethyl ammonium bromide[J].Journal of the Chinese Ceramic Society,2014,42(4):514-521.(in Chinese)
[2]Ruiz N,Seal S,Reinhart D.Surface chemical reactivity in selected zero-valent iron samples used in groundwater remediation[J].J ournal of Hazardous Materials,2000,80(1):107-117.
[3]李保华,孙治荣,杨冬梅.铁系金属对氯代有机物的还原脱氯研究进展[J].化工环保,2007,27(4):323-326.Li Baohua,Sun Zhirong,Yang Dongmei.Research progresses in removal of chlorinated organic compounds by iron based metal reduction[J].Environmental Protection of Chemical Industry,2007,27(4):323-326.(in Chinese)
[4]Gillham R W,O’Hannesin,Stephanie F.Enhanced degradation of halogenated aliphatics by zero-valent iron[J].Ground Water,1994,32(6):958-962.
[5]Dombek T,Dolan E,Schultz J,et al.Rapid reductive dechlorintion of atrazine by zero-valent iron under acidic conditions[J].Environmental Pollution,2001,11l(1):2l-27.
[6]Matheson L J,Tratnyek P G.Reductive dehalogenation of chlorinated methanes by iron metal[J].Environmental Science and Technology,1994,28(12):2045-2053.
[7]庞龙,周庆祥,苏现伐.纳米零价铁修饰技术研究进展[J].化工进展,2004,30(6):1361-1368.Pang Long,Zhou Qingxiang,Su Xianfa.Progress of in-situ modification techniques of nanoscale zero-valent iron[J].Chemical Industry and Engineering Progress,2004,30(6):1361-1368.(in Chinese)
[8]Mallat T,Bodnar Z S,Petro J.Reduction by dissolving bimetals[J].Tetrahedron,1991,47(3):441-446.
[9]徐新华,卫建军,汪大翚.Pd/Fe及纳米Pd/Fe对氯酚的脱氯研究[J].中国环境科学,2004,24(1):76-80.Xu Xinhua,Wei Jianjun,Wang Dahui.Studies on dechlorination of chlorophenols with Pd/Fe and nanoscale Pd/Fe[J].China Environmental Science,2004,24(1):76-80.(in Chinese)
[10]全燮,刘会娟,杨凤林,等.二元金属体系对水中多氯有机物的催化还原脱氯特性[J].中国环境科学,1998,18(4):333-336.Quan Xie,Liu Huijuan,Yang Fenglin,et al.Dechlorination of three polychlorinated hydreocarbons in water using bimetallic systems[J].China Environmental Science,1998,18(4):333-336.(in Chinese)
[11]Muftikian R,Fernaando Q,Korte N.A method of the rapid dechlorination of low molecular weight chlorinated hydrocarbons in water[J].Water Research,1995,29(10):2434-2439.
[12]Mallouk T E,Schrick B,Blough J L,et al.Hydrodechlorination of trichloroethylene to hydrocarbons using bimetallic nickel-iron nanoparticles[J].Chemistry of Materials,2002,14(12):5140-5147.
[13]Xu X H,Wo J J,Zhang J H,et al.Catalytic dechlorination of p-NCB in water by nanoscale Ni/Fe[J].Desalination,2009,242(1):346-354.
[14]Kim J,Tratnyek P G,Chang Y.Rapid dechlorination of polychlorinated dibenzo-p-dioxins by bimetallic and nanosized zerovalent iron[J].Environmental Science and Technology,2008,42(11):4106-4112.
[15]徐新华,金剑,卫建军,等.纳米Pd/Fe双金属对2,4-二氯酚的脱氯机理及动力学[J].环境科学学报,2004,24(4):561-567.Xu Xinhua,Jing Jian,Wei Jianjun,et al.Dechlorination mechanism and kinetic of 2,4-DCP by nanoscale Pd/Fe systems[J].Acta Scientiae Circumstantiae,2004,24(4):561-567.(in Chinese)
[16]Chen Wenfang,Pan Ling,Chen Lifang,et al.Dechlorination of hexachlorobenzene by nano zero-valent iron/activated carbon composite:iron loading,kinetics and pathway[J].RSC Advances,2014(4):46689-46696.
[17]Elsayed M Zahran,Dibakar Bhattacharyya,Leonidas G Bachas.Development of reactive Pd/Fe bimetallic nanotubes for dechlorination reactions[J].Journal of Materials Chemistry,2011(21):10454-10462.
[18]Wu Pingxiao,Liu Chongmin,Huang Zhujian,et al.Enhanced dechlorination performance of 2,4-dichlorophenol by vermiculite supported iron nanoparticles doped with palladium[J].RSC Advances,2014(4):25580-25587.
[19]Macarena M,Zahara M D,Jose A,et al.Chlorophenols breakdown by a sequential hydrodechlorination-oxidation treatment with a magnetic Pde Fe/g-Al2O3catalyst[J].Water Research,2013,47(9):3070-3080.
[20]Zhen Z,Qiao H S,Naman C,et al.Catalytic dechlorination of 2,4-dichlorophenol by Pd/Fe bimetallic nanoparticles in the presence of humic acid[J].Journal of Hazardous Materials,2010,182(1):252-258.
[21]Han Y,Li W,Zhang M H,et al.Catalytic dechlorination of monochlorobenzene with a new type of nanoscale Ni(B)/Fe(B)bimetallic catalytic reductant[J].Chemosphere,2008,72(1):53-58.
[22]Cheng Rong,Zhou Wei,Wang Jianlong,et al.Dechlorination of pentachlorophenol using nanoscale Fe/Ni particles:role of nano-Ni and its size effect[J].Journal of Hazardous Materials,2010,180(1):79-85.
[23]彭秀达,刘红,秦雄,等.十六烷基三甲基溴化铵对膨润土负载纳米铁去除水中铬(Ⅵ)的增强作用[J].硅酸盐学报,2014,42(4):514-521.Peng Xiuda,Liu Hong,Qin Xiong,et al.Removal of chromium(Ⅵ)using zero-valent nanoscale iron spported on bentonite trimethyl ammonium bromide[J].Journal of the Chinese Ceramic Society,2014,42(4):514-521.(in Chinese)