掺硼金刚石膜电极电化学氧化双酚A的影响因素及机理研究
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摘要
采用响应曲面法系统研究了掺硼金刚石(Boron-doped Diamond,BDD)膜电极电化学氧化双酚A (BisphenolA,BPA)的影响因素及含氯副产物的生成。结果表明,电流密度是影响降解速率常数(k)和氯离子消耗量(Δc(Cl-))的最主要因素。以BPA有效降解的同时生成较少量的含氯副产物为标准,通过响应曲面法计算得到的最优反应条件为:对0. 06 mmol/L BPA、40 mmol/L NaCl(pH=8)的溶液,当电流密度为15 mA/cm2时,k为0. 318 min-1,Δc(Cl-)仅为3. 55 mmol/L。BDD电极电解不仅生成了高浓度的高氯酸盐,还生成了1,1,2,2-四氯乙烷、2,3,4,6-四氯苯酚和五氯苯酚等仅在BDD体系中被检测到的含氯有机副产物。综上,经BDD电极电化学氧化处理后尽管整个BPA溶液的毒性明显降低,但还需特别关注反应过程中生成的含氯副产物。
The present paper is engaged in a systematic investigation and determination of the influential factors and reasons for the presence of the chlorinated byproducts in the electrochemical oxidation process of bisphenol A( BPA) with the boron-doped diamond( BDD) by using the response surface methodology( RSM) for the first time. For the said purpose,we have chosen the initial BPA concentration,the chloride concentration,the chosen p H value,and the current density as the independent variables with the degradation rate of BPA( k) and the amount of Cl-consumed( Δc( Cl-)) for the targeted response. The results of our experiment prove that the current density serves as the most influential factor both on the k and Δc( Cl-),through which strong interactions have been taking place among the influential factors on these responses. It is attributed to their effects on the active chlorine,the hydroxyl radicals and the status of BPA in the electrolysis system. Based on the criteria of the effective degradation of estrogenic BPA with the relatively less generation of chlorinated byproducts,it has made us optimize the final solution with 0. 06 mmol/L BPA and 40 mmol/L Na Cl( p H = 8)and the current density of 15 m A/cm2 through RSM so as to get the BPA degradation rate of 0. 318 min-1 and Δc( Cl-) of 3. 55 mmol/L. The above results demonstrate the great advantages with BDD anodes compared with Pt anodes under the optimized conditions. The analysis of the specific orientation of the different forms of chlorine has been also analyzed under the differentoperation conditions. The active chlorine,chloroform,and perchlorate indicate the similar variation trends with the operating factors. It is indicated that the amount of chlorine consumed during the 240 min electrolysis is equal to 5. 03 mmol/L for BDD anode( but only 0. 30 mmol/L for Pt under the similar conditions). As a result, it emphasized that more varieties and amounts of the chlorinated byproducts in the BDD system have generated compared to the Pt system due to its stronger oxidizing capability. Besides,more chlorinated intermediates are discovered in the BDD cell,such as 1,1,2,2-tetrachloro-ethane,2,2-bis( chloromethyl)-1-propanol,1,1,1-tris( chloromethyl)-ethane,2,3,4,6-tetrachloro-phenol,and the pentachloro-phenol.Though the entire toxicity of the whole BPA solution obviously decreaseed,the formation of the organic and inorganic byproducts during the electrolysis should be cautiously paid attention to. Therefore,it is necessary to conduct the electrochemical oxidation experiment under the lower current density in the weakly alkaline electrolyte for the actual polluted water treatment with the organics and inevitable chloride ions.
The present paper is engaged in a systematic investigation and determination of the influential factors and reasons for the presence of the chlorinated byproducts in the electrochemical oxidation process of bisphenol A( BPA) with the boron-doped diamond( BDD) by using the response surface methodology( RSM) for the first time. For the said purpose,we have chosen the initial BPA concentration,the chloride concentration,the chosen p H value,and the current density as the independent variables with the degradation rate of BPA( k) and the amount of Cl-consumed( Δc( Cl-)) for the targeted response. The results of our experiment prove that the current density serves as the most influential factor both on the k and Δc( Cl-),through which strong interactions have been taking place among the influential factors on these responses. It is attributed to their effects on the active chlorine,the hydroxyl radicals and the status of BPA in the electrolysis system. Based on the criteria of the effective degradation of estrogenic BPA with the relatively less generation of chlorinated byproducts,it has made us optimize the final solution with 0. 06 mmol/L BPA and 40 mmol/L Na Cl( p H = 8)and the current density of 15 m A/cm2 through RSM so as to get the BPA degradation rate of 0. 318 min-1 and Δc( Cl-) of 3. 55 mmol/L. The above results demonstrate the great advantages with BDD anodes compared with Pt anodes under the optimized conditions. The analysis of the specific orientation of the different forms of chlorine has been also analyzed under the differentoperation conditions. The active chlorine,chloroform,and perchlorate indicate the similar variation trends with the operating factors. It is indicated that the amount of chlorine consumed during the 240 min electrolysis is equal to 5. 03 mmol/L for BDD anode( but only 0. 30 mmol/L for Pt under the similar conditions). As a result, it emphasized that more varieties and amounts of the chlorinated byproducts in the BDD system have generated compared to the Pt system due to its stronger oxidizing capability. Besides,more chlorinated intermediates are discovered in the BDD cell,such as 1,1,2,2-tetrachloro-ethane,2,2-bis( chloromethyl)-1-propanol,1,1,1-tris( chloromethyl)-ethane,2,3,4,6-tetrachloro-phenol,and the pentachloro-phenol.Though the entire toxicity of the whole BPA solution obviously decreaseed,the formation of the organic and inorganic byproducts during the electrolysis should be cautiously paid attention to. Therefore,it is necessary to conduct the electrochemical oxidation experiment under the lower current density in the weakly alkaline electrolyte for the actual polluted water treatment with the organics and inevitable chloride ions.
引文
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[14] WANG Bing(王兵),LI Jie(李洁),REN Hongyang(任宏洋),et al. On the treatment of polymer floodingsewage left-over from the oil drilling by the electrochemi-cal process[J]. Journal of Safety and Environment(安全与环境学报),2015,15(6):245-249.
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[16] COSTA C R,MONTILLA F,MORALLON E,et al. Elec-trochemical oxidation of acid black 210 dye on the boron-doped diamond electrode in the presence of phosphate ions:effect of current density,p H,and chloride ions[J]. Elec-trochimica Acta,2009,54(27):7048-7055.
[17] RAJAB M,HEIM C,LETZEL T. Helmreich,Electro-chemical disinfection using boron-doped diamond elec-trode-the synergetic effects of in situ ozone and free chlo-rine generation[J]. Chemosphere,2015,121:47-53.
[18] ZHU X,NI J,WEI J,et al. Scale-up of BDD anodesystem for electrochemical oxidation of phenol simulatedwastewater in continuous mode[J]. Journal of Hazard-ous Materials,2010,184(1/2/3):493-498.
[19] PINKOWSKA H,WOLAKA P,OLIVEEROS E. Pro-duction of xylose and glucose from rapeseed straw in sub-critical water-use of Doehlert design for optimizing the re-action conditions[J]. Biomass and Bioenergy,2013,58:188-197.
[20] DEBORDE M,VON-GUNTEN U. Reactions of chlorinewith inorganic and organic compounds during water treat-ment-kinetics and mechanisms:a critical review[J].Water Research,2008,42(1/2):13-51.
[21] MOHAN N,BALASUBRAMANIAN N,BASHA N A.Electrochemical oxidation of textile wastewater and its re-use[J]. Journal of Hazardous Materials,2007,147:644-651.
[22] VACCA A,MASCIA M,PALMAS S. Electrochemi-cal treatment of water containing chlorides under non-ideal flow conditions with BDD anodes[J]. Journal ofApplied Electrochemistry,2011,41:1087-1097.
[23] AZIZI O,HUBLER D,SCHRADER G. Mechanism ofperchlorate formation on boron-doped diamond anodes[J]. Environmental Science&Technology,2011,45:10582-10590.
[24] GALLARD H,LECLERCQ A,CROUE J. Chlorinationof bisphenol A:kinetics and by-products formation[J].Chemosphere,2004,56:465-473.
[25] GARCIA-SEGURA S,KELLER J,BRILLAS E,et al.Removal of organic contaminants from secondary effluentby anodic oxidation with a boron-doped diamond anodeas tertiary treatment[J]. Journal of Hazardous Materi-als,2015,283:551-557.
[26] National Institute for Occupational Safety and Health. Reg-istry of toxic effects of chemical substances[M],Washing-ton:World Heritage Encyclopedia,1985.
[27] TAI Chao,PENG Jinfeng,LIU Jingfu,et al. Determi-nation of hydroxyl radicals in advanced oxidation proces-ses with dimethyl sulfoxide trapping and liquid chroma-tography[J]. Analytical Chimica Acta,2004,527(1):73-80.
[28] ZAVISK F,DROGUI P. Electrochemical treatment ofbisphenol A using response surface methodology[J].Journal of Applied Electrochemistry,2012,42:95-109.
[29] ONODERA S,YAMADA K,YAMAJI Y. Chemical chan-ges of organic compounds in chlorinated water IX. Forma-tion of polychlorinated phenoxyphenols during the reactionof phenol with hypochlorite in dilute aqueous solution[J].Journal of Chromatogramphy,1984,288:91-100.
[30] BARRIOS J A,BECERRIL E,LEON C D,et al. Elec-trooxidation treatment for removal of emerging pollutantsin wastewater sludge[J]. Fuel,2015,149:26-33.
[2] PANIZZA M,CERISOLA G. Application of diamondelectrodes to electrochemical processes[J]. Electrochimi-ca Acta,2005,51:191-199.
[3] LI H,ZHU X,NI J. Inactivation of escherichia coli inNa2SO4electrolyte using boron-doped diamond anode[J].Electrochimic Acta,2010,56:448-453.
[4] ADAMS R N. Anodic oxidation pathways of aromatic hy-drocarbons and amines[J]. Accounts of Chemical Re-search,1968,2:175-180.
[5] ZHAO Guohua(赵国华),LI Mingli(李明利),WUWeiwei(吴薇薇),et al. Electrocatalytic behavior of dia-mond electrode for organic pollutant[J]. EnvironmentalScience(环境科学),2004,25(5):163-167.
[6] XIANG Ping(向平),ZHANG Yaqing(张亚晴),ZHANGRuohan(张若汉),et al. Study on the inactivation of highconcentration algae water by boron-doped diamond filmelectrode[J]. Environmental Science&Technology(环境科学与技术),2017,8:56-61.
[7] ZHANG Jiawei(张佳维),WANG Ting(王婷),ZHENGTong(郑彤),et al. Effect of current density on electro-chemical mineralization of indole at BDD electrode and itsmechanism[J]. Environmental Science(环境科学),2017,38(9):3755-3761.
[8] PANIZZA M,CERISOLA G. Direct and mediated anodicoxidation of organic pollutants[J]. Chemical Reviews,2009,109:6541-6569.
[9] ZOU Xu(邹徐),ZHOU Shiqing(周石庆),LU Xianlei(陆先镭),et al. Oxidative degradation of diolone byelectrode and its influencing factors with boron-doped dia-mond electrode[J]. Journal of Safety and Environment(安全与环境学报),2017,17(6):2322-2326.
[10] LI H,NI J. Electrogeneration of disinfection byproductsat a boron-doped diamond anode with resorcinol as amodel substance[J]. Electrochimica Acta,2012,69:268-274.
[11] BRILLAS E,MARTINEZ-HUITLE C A. Decontamina-tion of wastewaters containing synthetic organic dyes byelectrochemical methods. An updated review[J]. Ap-plied Catalysis B:Environment, 2015, 166/167:603-643.
[12] LI H,LONG Y,WANG Y,ZHU C,NI J. Electro-chemical degradation of bisphenol A in chloride electro-lyte—factor analysis and mechanisms study[J]. Electro-chimica Acta,2016,222:1144-1152.
[13] KORBAHTI B K,TASYUEK S. Electrochemical oxida-tion of sulfadiazine antibiotic using boron-doped diamondanode:application of response surface methodology forprocess optimization[J]. Desalination Water Treatment,2016,57:2522-2533.
[14] WANG Bing(王兵),LI Jie(李洁),REN Hongyang(任宏洋),et al. On the treatment of polymer floodingsewage left-over from the oil drilling by the electrochemi-cal process[J]. Journal of Safety and Environment(安全与环境学报),2015,15(6):245-249.
[15] MARTINEZ-HUITLE C A,FERRO S. Electrochemicaloxidation of organic pollutants for the wastewater treat-ment:direct and indirect processes[J]. Chemical Socie-ty Reviews,2006,35:1324-1340.
[16] COSTA C R,MONTILLA F,MORALLON E,et al. Elec-trochemical oxidation of acid black 210 dye on the boron-doped diamond electrode in the presence of phosphate ions:effect of current density,p H,and chloride ions[J]. Elec-trochimica Acta,2009,54(27):7048-7055.
[17] RAJAB M,HEIM C,LETZEL T. Helmreich,Electro-chemical disinfection using boron-doped diamond elec-trode-the synergetic effects of in situ ozone and free chlo-rine generation[J]. Chemosphere,2015,121:47-53.
[18] ZHU X,NI J,WEI J,et al. Scale-up of BDD anodesystem for electrochemical oxidation of phenol simulatedwastewater in continuous mode[J]. Journal of Hazard-ous Materials,2010,184(1/2/3):493-498.
[19] PINKOWSKA H,WOLAKA P,OLIVEEROS E. Pro-duction of xylose and glucose from rapeseed straw in sub-critical water-use of Doehlert design for optimizing the re-action conditions[J]. Biomass and Bioenergy,2013,58:188-197.
[20] DEBORDE M,VON-GUNTEN U. Reactions of chlorinewith inorganic and organic compounds during water treat-ment-kinetics and mechanisms:a critical review[J].Water Research,2008,42(1/2):13-51.
[21] MOHAN N,BALASUBRAMANIAN N,BASHA N A.Electrochemical oxidation of textile wastewater and its re-use[J]. Journal of Hazardous Materials,2007,147:644-651.
[22] VACCA A,MASCIA M,PALMAS S. Electrochemi-cal treatment of water containing chlorides under non-ideal flow conditions with BDD anodes[J]. Journal ofApplied Electrochemistry,2011,41:1087-1097.
[23] AZIZI O,HUBLER D,SCHRADER G. Mechanism ofperchlorate formation on boron-doped diamond anodes[J]. Environmental Science&Technology,2011,45:10582-10590.
[24] GALLARD H,LECLERCQ A,CROUE J. Chlorinationof bisphenol A:kinetics and by-products formation[J].Chemosphere,2004,56:465-473.
[25] GARCIA-SEGURA S,KELLER J,BRILLAS E,et al.Removal of organic contaminants from secondary effluentby anodic oxidation with a boron-doped diamond anodeas tertiary treatment[J]. Journal of Hazardous Materi-als,2015,283:551-557.
[26] National Institute for Occupational Safety and Health. Reg-istry of toxic effects of chemical substances[M],Washing-ton:World Heritage Encyclopedia,1985.
[27] TAI Chao,PENG Jinfeng,LIU Jingfu,et al. Determi-nation of hydroxyl radicals in advanced oxidation proces-ses with dimethyl sulfoxide trapping and liquid chroma-tography[J]. Analytical Chimica Acta,2004,527(1):73-80.
[28] ZAVISK F,DROGUI P. Electrochemical treatment ofbisphenol A using response surface methodology[J].Journal of Applied Electrochemistry,2012,42:95-109.
[29] ONODERA S,YAMADA K,YAMAJI Y. Chemical chan-ges of organic compounds in chlorinated water IX. Forma-tion of polychlorinated phenoxyphenols during the reactionof phenol with hypochlorite in dilute aqueous solution[J].Journal of Chromatogramphy,1984,288:91-100.
[30] BARRIOS J A,BECERRIL E,LEON C D,et al. Elec-trooxidation treatment for removal of emerging pollutantsin wastewater sludge[J]. Fuel,2015,149:26-33.