电化学氧化法处理含盐苯醌模拟废水
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摘要
利用钛基二氧化铅电极(Ti/PbO_2)作为电催化活性阳极,通过电化学氧化技术对苯醌进行降解矿化,考察常见共存无机盐对苯醌废水降解效率的影响。结果表明,NaCl存在下苯醌废水溶液的COD去除率相比硝酸盐提高了62%,相比硫酸盐提高了45%,NaCl能够显著增强电氧化去除苯醌的电流效率。苯醌的降解对氯离子非常敏感,存在少量的氯离子即可以引起氧化效率明显增加。氯离子浓度越高,苯醌模拟废水的COD去除率越高;但当氯离子浓度高于0.3mol·L~(-1)时,COD去除率反而有所下降。pH为8的弱碱性环境更有利于含氯离子苯醌废水的电氧化降解反应。提高电流密度可增大COD去除率;但升高温度会降低COD去除率。在pH为8、NaCl浓度为0.3 mol·L~(-1)、电流密度为10mA·cm~(-2)、温度为20℃的条件下,初始浓度为100 mg·L~(-1)的苯醌经3 h电化学氧化降解后COD去除率可达80.9%。通过高效液相色谱对电氧化降解苯醌的中间产物进行分析,发现氯离子存在下苯醌的降解速度显著提高,中间产物顺丁烯二酸的生成速度更快,这说明由氯离子生成的强氧化剂对苯醌具有极强的开环能力。
In this study, an electrochemical oxidation technique with titanium-based lead dioxide(Ti/PbO_2) as an active anode was used to degrade and mineralize benzoquinone. The effect of common inorganic salts on the degradation efficiency of benzoquinone wastewater was investigated. The results showed that in the presence of NaCl, the removal rate of COD in benzoquinone wastewater was 62% higher than that of nitrate and 45% higher than that of sulfate. NaCl could significantly enhance the current efficiency of benzoquinone mineralization by this electrochemical oxidation technique. The electro-degradation of benzoquinone was very sensitive to chloride ions, and a small amount of chloride ions could lead to a significant increase in degradation efficiency. The higher the chloride concentration, the higher the COD removal rate for the simulated wastewater with benzoquinone. However, the COD removal rate decreased when the chloride concentration was higher than 0.3 mol·L~(-1). The weak alkaline environment with pH = 8 was more favorable to the electrochemical oxidation and degradation in benzoquinone wastewater containing chloride ions. COD removal rate increased with the increase of the current density, while it decreased with increase of temperature. At pH=8, 0.3 mol· L~(-1) NaCl, current density of 10 mA·cm~(-2) and 20 ℃, the COD removal rate for benzoquinone wastewater with initial concentration of100 mg·L~(-1) could reach 80.9% after 3 h electro-oxidation degradation. High performance liquid chromatography(HPLC) was used to analyze the intermediate products of electro-oxidation degradation of benzoquinone. It was found that the benzoquinone degradation rate increased significantly in the presence of chloride ion, and the intermediate product of maleic acid was fast produced, which implied that the strong oxidant produced by chlorine ions has strong ability to open the aromatic ring of benzoquinone.
In this study, an electrochemical oxidation technique with titanium-based lead dioxide(Ti/PbO_2) as an active anode was used to degrade and mineralize benzoquinone. The effect of common inorganic salts on the degradation efficiency of benzoquinone wastewater was investigated. The results showed that in the presence of NaCl, the removal rate of COD in benzoquinone wastewater was 62% higher than that of nitrate and 45% higher than that of sulfate. NaCl could significantly enhance the current efficiency of benzoquinone mineralization by this electrochemical oxidation technique. The electro-degradation of benzoquinone was very sensitive to chloride ions, and a small amount of chloride ions could lead to a significant increase in degradation efficiency. The higher the chloride concentration, the higher the COD removal rate for the simulated wastewater with benzoquinone. However, the COD removal rate decreased when the chloride concentration was higher than 0.3 mol·L~(-1). The weak alkaline environment with pH = 8 was more favorable to the electrochemical oxidation and degradation in benzoquinone wastewater containing chloride ions. COD removal rate increased with the increase of the current density, while it decreased with increase of temperature. At pH=8, 0.3 mol· L~(-1) NaCl, current density of 10 mA·cm~(-2) and 20 ℃, the COD removal rate for benzoquinone wastewater with initial concentration of100 mg·L~(-1) could reach 80.9% after 3 h electro-oxidation degradation. High performance liquid chromatography(HPLC) was used to analyze the intermediate products of electro-oxidation degradation of benzoquinone. It was found that the benzoquinone degradation rate increased significantly in the presence of chloride ion, and the intermediate product of maleic acid was fast produced, which implied that the strong oxidant produced by chlorine ions has strong ability to open the aromatic ring of benzoquinone.
引文
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[16]王宇,王栋,殷先雄,等.恒电流下电生成活性氯降解活性艳红K-2BP[J].环境科学与技术,2009,32(1):55-58.
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[18]ALAN H,DEGAKI G F,PEREIRA R C,et al.Effect of specific active chlorine species and temperature on the electrochemical degradation of the reactive blue 19 dye using a boron-doped diamond or DSA anode in a flow reactor[J].Electrocatalysis,2014,5:8-15.
[19]于丽花,薛娟琴,蒋朦,等.离子液体对PbO2电极电化学性能的影响[J].稀有金属材料与工程,2015,44(8):1932-1936.
[20]胡俊生,谢添,任雪冬,等.电生成活性氯的影响因素及其在有机废水处理中的应用[J].辽宁化工,2008,37(9):598-600.
[21]高文宇,李刚,张跃,等.电解质类型对电化学降解苯酚的影响[J].绿色科技,2007(4):78-82.
[22]王鹏,刘伟藻,方汉平.电化学氧化与厌氧技术联用处理垃圾渗沥水[J].环境科学,2001,22(5):70-73.
[23]李晓萍,林海波,吴岩,等.Ti/PbO2阳极在氯化钠溶液中电解生成活性氯的研究[J].吉林大学学报,2005,43(3):358-362.
[24]HOUK L L,JOHNSON S K,FENG J,et al.Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte[J].Journal of Applied Electrochemistry,1998,28:1167-1177.
[2]WU Z C,ZHOU M H.Partial degradation of phenol by advanced electrochemical oxidation process[J].Environmental Science Technology,2001,35(13):2698-2703.
[3]阎建中,曲久辉,李梅,等.SnO2/Ti电极催化降解1,4-苯醌的研究[J].中国给水排水,2003,19(12):58-60.
[4]李明玉,赵倩,曾小龙,等.TiO2光电催化中光生电子降解对苯醌的行为研究[J].中国环境科学,2015,35(5):1397-1402.
[5]李国亭,王海荣,李东颖,等.紫外光协助下DSA电极对1,4苯醌的强化开环作用研究[J].环境科学,2009,30(7):1955-1961.
[6]李国亭,冯艳敏,柴晓琪,等.镧改性活性炭纤维高效吸附去除对苯醌[J].环境工程学报,2016,10(4):1638-1644.
[7]朱灵峰,何怡雪,张昊,等.锰改性玉米秸秆生物炭吸附去除1,4-苯醌[J].江苏农业学报,2016,32(3):570-574.
[8]LI N,GREEN J R,WANG J C.The concurrence of photoreduction and bromination of 1,4-benzoquinone in aqueous solution[J].Chemical Physics Letters,2007,447:241-246.
[9]MOHAMMED A A,MOHMED K A,WAN M A W D.p-benzoquinone anodic degradation by carbon black diamond composite electrodes[J].Electrochimica Acta,2015,169:46-51.
[10]RIVAS F J,BELTRAN F J,GIMENO O,et al.Optimisation of Fenton.s reagent usage as a pre-treatment for fermentation brines[J].Journal of Hazardous Materials,2003,96(2/3):277-290.
[11]LEFEBVRE O,MOLETTA R.Treatment of organic pollution in industrial saline wastewater:A literature review[J].Water Research,2006,40(20):3671-3682.
[12]PANIZZA M,BARBUCCI A,RICOTTI R,et al.Electrochemical degradation of methylene blue[J].Separation and Purification Technology,2007,54(3):382-387.
[13]LOPEZ-GRIMAU V,GUTIERREZ M C.Decolourisation of simulated reactive dyebath effluents by electrochemical oxidation assisted by UV light[J].Chemosphere,2006,62(1):106-112.
[14]VLYSSIDESl A,ARAPOGLOU D,MAI S,et al.Electrochemical detoxification of four phosphorothioate obsolete pesticides stocks[J].Chemosphere,2005,58(4):439-447.
[15]王璇,黄卫民,刘小波,等.氯离子对苯酚电化学氧化降解过程的影响[J].高等学校化学学报,2011,32(2):363-365.
[16]王宇,王栋,殷先雄,等.恒电流下电生成活性氯降解活性艳红K-2BP[J].环境科学与技术,2009,32(1):55-58.
[17]ZOU J X,PENG X L,LI M,et al.Electrochemical oxidation of COD from real textile wastewaters:Kinetic study and energy consumption[J].Chemosphere,2017,171:332-338.
[18]ALAN H,DEGAKI G F,PEREIRA R C,et al.Effect of specific active chlorine species and temperature on the electrochemical degradation of the reactive blue 19 dye using a boron-doped diamond or DSA anode in a flow reactor[J].Electrocatalysis,2014,5:8-15.
[19]于丽花,薛娟琴,蒋朦,等.离子液体对PbO2电极电化学性能的影响[J].稀有金属材料与工程,2015,44(8):1932-1936.
[20]胡俊生,谢添,任雪冬,等.电生成活性氯的影响因素及其在有机废水处理中的应用[J].辽宁化工,2008,37(9):598-600.
[21]高文宇,李刚,张跃,等.电解质类型对电化学降解苯酚的影响[J].绿色科技,2007(4):78-82.
[22]王鹏,刘伟藻,方汉平.电化学氧化与厌氧技术联用处理垃圾渗沥水[J].环境科学,2001,22(5):70-73.
[23]李晓萍,林海波,吴岩,等.Ti/PbO2阳极在氯化钠溶液中电解生成活性氯的研究[J].吉林大学学报,2005,43(3):358-362.
[24]HOUK L L,JOHNSON S K,FENG J,et al.Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte[J].Journal of Applied Electrochemistry,1998,28:1167-1177.