填充床电催化氧化工艺处理甲基橙废水实验研究
|
摘要
以甲基橙模拟废水为降解对象,研究了填充床电化学反应器对偶氮燃料废水的电催化降解特性;结果表明初始浓度450mg/L,电解质含量为2%的甲基橙废水在30A/m2电流密度下经180min降解出水甲基橙浓度为2.93mg/L,去除率达99.3%,UV分析表明降解过程以键裂解为主,无其他大分子组分生成,其浓度变化符合一级动力学降解模型;在此基础上,采用单因素变量实验方法研究了初始甲基橙浓度、电流密度、电解质含量及进水流速对甲基橙电催化过程中动力学常数k的影响,得到各因素控制下动力学常数的数学表达式。依据一级动力学模型给出填充床电化学反应器处理甲基橙废水的浓度预测方程,以其通过电化学反应操作条件的优化实现甲基橙废水的彻底降解或对出水甲基橙浓度的准确预测。
A bench scale experiment was described,in which a packed-bed electrode reactor filled with granular activated carbon was employed to the purification of wastewater containing methyl orange(MO),a kind of azo dyes. The experimental results showed that removal rate of MO could reach 99.3% and its degradation in terms of concentration was from 450mg/L down to 2.93mg/L in 180min when electrolyte content and current density were adequately adjusted. UV analysis indicated that bond breakage may take place but no macromolecular organic matters were formed during the electro-catalysis process,also the change of methyl orange concentration followed the first order kinetics model. Accordingly,further study were conducted using a single-factor experimental method to investigate the parameters of initial methyl orange concentration,electrolyte content,current density and flow rate on the effect of kinetic constant(k) during the methyl orange electric-catalytic process. By doing this,expressions that could explain the relationship between the factors above with k was given.Finally,an empirical model for methyl orange degradation by packed-bed electrode reactor was proposed for the purpose of complete breakdown of MO or predicting the MO concentration in the effluent under the optimum operating condition.
A bench scale experiment was described,in which a packed-bed electrode reactor filled with granular activated carbon was employed to the purification of wastewater containing methyl orange(MO),a kind of azo dyes. The experimental results showed that removal rate of MO could reach 99.3% and its degradation in terms of concentration was from 450mg/L down to 2.93mg/L in 180min when electrolyte content and current density were adequately adjusted. UV analysis indicated that bond breakage may take place but no macromolecular organic matters were formed during the electro-catalysis process,also the change of methyl orange concentration followed the first order kinetics model. Accordingly,further study were conducted using a single-factor experimental method to investigate the parameters of initial methyl orange concentration,electrolyte content,current density and flow rate on the effect of kinetic constant(k) during the methyl orange electric-catalytic process. By doing this,expressions that could explain the relationship between the factors above with k was given.Finally,an empirical model for methyl orange degradation by packed-bed electrode reactor was proposed for the purpose of complete breakdown of MO or predicting the MO concentration in the effluent under the optimum operating condition.
引文
[1]Neti Nageswara Rao,Misra Rohit,Gedam Nitin,et al.Kinetics of electeooxidation of landfill landfill leachate in a three-dimensional carbon bed electrochemical reactor[J].Chemosphere,2009,76:1206-1212.
[2]王婧,孟庆函,曹兵.三维电极电催化氧化处理邻氯苯胺废水的研究[J].环境科学与技术,2012,35(7):86-89.
[3]徐海青,刘秀宁,王育乔,等.复合金属氧化物Sn-Sb-Mn/陶瓷粒子电极体系的电催化性能[J].物理化学学报,2009,25(5):840-846.
[4]Li Fan,Fenglin Yang,Weishen Yang.Performance of the decolorization of an azo dye with bipolar packed bed cell[J].Separation and Purification Technology,2004,34(1/2/3):89-96.
[5]M Panizza,Agnieszka Kapalka,Ch Comninellis.Oxidation of organic pollutants on BDD anodes using modulated current eletrolysis[J].Eletrochimica Acta,2008,53:2289-2295.
[6]Huiling Liu,Yuan Liu,Cheng Zhang,et al.Electrocatalytic oxidation of nitrophenols in aqueous solution using modified Pb O2electrodes[J].Journal of Applied Electrochemistry,2008,38:101-108.
[7]莫德清,郭亚栋.H2O2协同三维电极法处理罗丹明B废水的研究[J].环境科学与技术,2011,34(6):167-172.
[8]A M Polcaro,S Palmas,F Renolodi,et al.Three-dimensional electrodes for the electrochemical combustion of organic pollutants[J].Electrochimica Acta,2000,46(2/3):389-394.
[9]Jari Aromaa,Olof Forsén.Evalyation of the electrochemical activity of a Ti-Ru O2-Ti O2permanent anode[J].Electrochimica Acta,2006,51:6104-6010.
[10]张芳,李光明,盛怡,等.电催化氧化法处理苯酚废水的MnSn-Sb/γ-Al2O3粒子电极研制[J].化学学报,2006,64(3):235-239.
[11]张乃东,李宁,彭永臻.涂膏热解法制备钛基Sn、Sb氧化物电极[J].物理化学学报,2003,19(12):1154-1158.Zhang Naidong,Li Ning,Peng Yongzhen.Preparation and properties of Ti/Sn,Sb oxide electrode by the paste-coating method[J].Acta Physico-Chimica Sinica,2003,19(12):1154-1158.(in Chinese)
[12]Slokar Y M,Marechal A M L.Methods of decoloration of textile wastewater[J].Dyes Pigments,1998,37:335-356.
[13]Lin S H,Chen M L.Treatment of textile wastewater by chemical methods for reuse[J].Water Research,1997,31:868-876.
[14]程爱华,王林红,叶向德,等.三维电极电解法处理偶氮燃料废水的试验研究[J].西安建筑科技大学学报,2009,41(1):117-120.Cheng Aihua,Wang Linhong,Ye Xiangde,et al.Treatment of azo dye wastewater by electrolysis of three 3D electrode[J].Journal of Xi'an University of Architecture and Technology,2009,41(1):117-120.(in Chinese)
[15]杨润昌,周书天,谢磊.高浓度甲基橙低压湿式催化氧化及动力学研究[J].湘潭大学自然科学学报,2000,22(3):59-62.Yang Runchang,Zhou Shutian,Xie Lei.Low pressure wet catalytic oxidation of high concentrated methyl orange and its kinetic studies[J].Natural Science Journal of Xiangtan University,2000,22(3):59-62.(in Chinese)
[16]夏良树,王孟,李来丙,等.US/Fe3+/H2O2体系超声催化降解甲基橙的研究[J].化学工程,2007,35(7):58-62Xia Liangshu,Wang Meng,Li Laibing,et al.Study on ultrasonic and catalytic degradation of methyl orange by US/Fe3+/H2O2system[J].Chemical Engineering,2007,35(7):58-62.(in Chinese)
[17]徐夫元,宋天顺,陈英文,等.Cu(Ⅱ)-Fe(Ⅱ)-H2O2协同催化氧化降解甲基橙[J].中南大学学报,2007,38(3):480-485Xu Fuyuan,Song Tianshun,Chen Yingwen,et al.Synergetic degradation of Cu(Ⅱ)-Fe(Ⅱ)-H2O2for methyl orange[J].Journal of Central South University:Science and Technology,2007,38(3):480-485.(in Chinese)
[18]Wang Lizhang,Hu Yunlong,Zhang Yanle,et al.A novel cost-saving strategy for electrochemical oxidation of organic matters by multi-current controlled operation[J].Separation and Purification Technology,2013,19:18-22.
[19]王雅琼,顾彬,许文林,等.钛基Pb O2电极上苯酚的电化学氧化[J].稀有金属材料与工程,2007,36(5):874-878.Wang Yaqiong,Gu Bin,Xu Wenlin,et al.Electrochemical oxidation of phenol on Ti-based Pb O2electrodes[J].Rare Metal Materials and Engineering,2007,36(5):874-878.(in Chinese)
[20]李爱昌,胡晓红,王瑞燕,等.复合电沉积制备Sn O2/Ti O2薄膜及其光电催化性能[J].材料科学与工艺,2008,16(1):62-65.Li Aichang,Hu Xiaohong,Wang Ruiyan,et al.Preparation of Sn O2/Ti O2film photoelectrodes by composite electroplating and its photocatalytic activity[J].Materials Science and Technology,2008,16(1):62-65.(in Chinese)
[21]Ya Xiong,Hans T Karlsson.An experimental investigation of chemical oxygen demand removal from the wastewater containing oxalic acid using three-phase three-dimensional electrode reactor[J].Advances in Environmental Research,2002,7(1):139-145.
[22]Zhang Naidong,Li Ning,Peng Yongzhen.Preparation and properties of Ti/Sn,Sb oxide electrode by the paste-coating method[J].Acta Physico-Chimica Sinica,2003,19(12):1154-1158.
[23]Stéphane Fierro,Tina Nagel,Helmut Baltruschat,et al.Investigation of oxygen evolution reaction on Ti/Ir O2electrodes using isotope labelling and on-line mass spectrometry[J].Electrochemistry Communications,2007,9(8):1969-1974.
[24]O Simond,V Schaller,Ch Comninellis.Theoretical model for the anodic oxidation of organics on metal oxide electrodes[J].Electrochimica Acta,1997,42(13/14):2009-2012.
[25]柴立元,尤翔宇,舒余德,等.三维电极电化学反应器降解有机废水中的EDTA[J].中南大学学报:自然科学版,2010,4(4):1240-1245.Chai Liyuan,You Xiangyu,Shu Yude,et al.Electrochemical degradation of organic wastewater containing EDTA with three-dimensional electrode reactor[J].Journal of Central South University:Science and Technology Edition,2010,4(4):1240-1245.(in Chinese)
[26]Lizhang Wang,Peng Li,Qian Yan.Modeling approach to phenol oxidation by a sand-based packed-bed electrode systems(SPBEs)[J].Water Science and Technology,2012,66(2):422-428.
[2]王婧,孟庆函,曹兵.三维电极电催化氧化处理邻氯苯胺废水的研究[J].环境科学与技术,2012,35(7):86-89.
[3]徐海青,刘秀宁,王育乔,等.复合金属氧化物Sn-Sb-Mn/陶瓷粒子电极体系的电催化性能[J].物理化学学报,2009,25(5):840-846.
[4]Li Fan,Fenglin Yang,Weishen Yang.Performance of the decolorization of an azo dye with bipolar packed bed cell[J].Separation and Purification Technology,2004,34(1/2/3):89-96.
[5]M Panizza,Agnieszka Kapalka,Ch Comninellis.Oxidation of organic pollutants on BDD anodes using modulated current eletrolysis[J].Eletrochimica Acta,2008,53:2289-2295.
[6]Huiling Liu,Yuan Liu,Cheng Zhang,et al.Electrocatalytic oxidation of nitrophenols in aqueous solution using modified Pb O2electrodes[J].Journal of Applied Electrochemistry,2008,38:101-108.
[7]莫德清,郭亚栋.H2O2协同三维电极法处理罗丹明B废水的研究[J].环境科学与技术,2011,34(6):167-172.
[8]A M Polcaro,S Palmas,F Renolodi,et al.Three-dimensional electrodes for the electrochemical combustion of organic pollutants[J].Electrochimica Acta,2000,46(2/3):389-394.
[9]Jari Aromaa,Olof Forsén.Evalyation of the electrochemical activity of a Ti-Ru O2-Ti O2permanent anode[J].Electrochimica Acta,2006,51:6104-6010.
[10]张芳,李光明,盛怡,等.电催化氧化法处理苯酚废水的MnSn-Sb/γ-Al2O3粒子电极研制[J].化学学报,2006,64(3):235-239.
[11]张乃东,李宁,彭永臻.涂膏热解法制备钛基Sn、Sb氧化物电极[J].物理化学学报,2003,19(12):1154-1158.Zhang Naidong,Li Ning,Peng Yongzhen.Preparation and properties of Ti/Sn,Sb oxide electrode by the paste-coating method[J].Acta Physico-Chimica Sinica,2003,19(12):1154-1158.(in Chinese)
[12]Slokar Y M,Marechal A M L.Methods of decoloration of textile wastewater[J].Dyes Pigments,1998,37:335-356.
[13]Lin S H,Chen M L.Treatment of textile wastewater by chemical methods for reuse[J].Water Research,1997,31:868-876.
[14]程爱华,王林红,叶向德,等.三维电极电解法处理偶氮燃料废水的试验研究[J].西安建筑科技大学学报,2009,41(1):117-120.Cheng Aihua,Wang Linhong,Ye Xiangde,et al.Treatment of azo dye wastewater by electrolysis of three 3D electrode[J].Journal of Xi'an University of Architecture and Technology,2009,41(1):117-120.(in Chinese)
[15]杨润昌,周书天,谢磊.高浓度甲基橙低压湿式催化氧化及动力学研究[J].湘潭大学自然科学学报,2000,22(3):59-62.Yang Runchang,Zhou Shutian,Xie Lei.Low pressure wet catalytic oxidation of high concentrated methyl orange and its kinetic studies[J].Natural Science Journal of Xiangtan University,2000,22(3):59-62.(in Chinese)
[16]夏良树,王孟,李来丙,等.US/Fe3+/H2O2体系超声催化降解甲基橙的研究[J].化学工程,2007,35(7):58-62Xia Liangshu,Wang Meng,Li Laibing,et al.Study on ultrasonic and catalytic degradation of methyl orange by US/Fe3+/H2O2system[J].Chemical Engineering,2007,35(7):58-62.(in Chinese)
[17]徐夫元,宋天顺,陈英文,等.Cu(Ⅱ)-Fe(Ⅱ)-H2O2协同催化氧化降解甲基橙[J].中南大学学报,2007,38(3):480-485Xu Fuyuan,Song Tianshun,Chen Yingwen,et al.Synergetic degradation of Cu(Ⅱ)-Fe(Ⅱ)-H2O2for methyl orange[J].Journal of Central South University:Science and Technology,2007,38(3):480-485.(in Chinese)
[18]Wang Lizhang,Hu Yunlong,Zhang Yanle,et al.A novel cost-saving strategy for electrochemical oxidation of organic matters by multi-current controlled operation[J].Separation and Purification Technology,2013,19:18-22.
[19]王雅琼,顾彬,许文林,等.钛基Pb O2电极上苯酚的电化学氧化[J].稀有金属材料与工程,2007,36(5):874-878.Wang Yaqiong,Gu Bin,Xu Wenlin,et al.Electrochemical oxidation of phenol on Ti-based Pb O2electrodes[J].Rare Metal Materials and Engineering,2007,36(5):874-878.(in Chinese)
[20]李爱昌,胡晓红,王瑞燕,等.复合电沉积制备Sn O2/Ti O2薄膜及其光电催化性能[J].材料科学与工艺,2008,16(1):62-65.Li Aichang,Hu Xiaohong,Wang Ruiyan,et al.Preparation of Sn O2/Ti O2film photoelectrodes by composite electroplating and its photocatalytic activity[J].Materials Science and Technology,2008,16(1):62-65.(in Chinese)
[21]Ya Xiong,Hans T Karlsson.An experimental investigation of chemical oxygen demand removal from the wastewater containing oxalic acid using three-phase three-dimensional electrode reactor[J].Advances in Environmental Research,2002,7(1):139-145.
[22]Zhang Naidong,Li Ning,Peng Yongzhen.Preparation and properties of Ti/Sn,Sb oxide electrode by the paste-coating method[J].Acta Physico-Chimica Sinica,2003,19(12):1154-1158.
[23]Stéphane Fierro,Tina Nagel,Helmut Baltruschat,et al.Investigation of oxygen evolution reaction on Ti/Ir O2electrodes using isotope labelling and on-line mass spectrometry[J].Electrochemistry Communications,2007,9(8):1969-1974.
[24]O Simond,V Schaller,Ch Comninellis.Theoretical model for the anodic oxidation of organics on metal oxide electrodes[J].Electrochimica Acta,1997,42(13/14):2009-2012.
[25]柴立元,尤翔宇,舒余德,等.三维电极电化学反应器降解有机废水中的EDTA[J].中南大学学报:自然科学版,2010,4(4):1240-1245.Chai Liyuan,You Xiangyu,Shu Yude,et al.Electrochemical degradation of organic wastewater containing EDTA with three-dimensional electrode reactor[J].Journal of Central South University:Science and Technology Edition,2010,4(4):1240-1245.(in Chinese)
[26]Lizhang Wang,Peng Li,Qian Yan.Modeling approach to phenol oxidation by a sand-based packed-bed electrode systems(SPBEs)[J].Water Science and Technology,2012,66(2):422-428.