电解法生成自由基规律及处理有机废水的研究
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摘要
有机废水由于其产生量大,尤其是一些制药及化工废水,浓度高,并常含高浓度的有毒有害物质,对生物体产生毒性,不易自然降解以及易在生物体内积累等特性,而成为水环境中一类重要的污染物,对环境和人体健康产生严重的危害作用。本文研究了电解法产生自由基的一些规律,并以含酚废水为例,讨论了用电解法产生自由基处理含酚废水的一些影响因素。
羟自由基是许多自由基氧化反应的反应主体,利用它极强的氧化能力处理有机废水,可使废水的化学需氧量(COD)值大大降低,达到水处理的目的。水杨酸(2-HBA)的羟基化产物2,5-二羟基苯甲酸(2,5-DHBA)可以作为羟自由基产生的指示剂。在利用2-HBA及其羟基化产物2,5-DHBA研究羟自由基在电极电解过程中的形成规律中,用以钛网为基体,锡、锑为中间层的二氧化铅电极在高频交流电源下电解2-HBA的水溶液,然后利用高效液相色谱(HPLC)检测分析2-HBA和2,5-DHBA的浓度变化。结果表明:pH值和频率对羟自由基的产率影响明显,溶液碱性条件要优于酸性条件,电源高频情况要优于低频情况,即碱性和高频条件更有利于羟自由基的生成。同时利用该电解装置进行苯酚降解实验表明,利用电解法产生的自由基处理有机废水效果明显。
在本文讨论的因素中,高pH值,高温有利于苯酚的降解,而低pH值,低温以及CO_3~(2-)、PO_4~(3-)的存在不利于苯酚的降解,Cl~-的存在虽有利于酚的去除,但却影响溶液中有机物总的去除量。
Wastewater with organic pollutants is one of the most harmfulsubstances, because its characteristics of big volume, highconcentration, noxious to living beings, hard degradable by naturalprocesses and easy accumulated in bodies. Forming law of hydroxylradical during electrolysis process was discussed in this paper. Thentook wastewater with phenol for example, we described some factorsthat affected forming of hydroxyl radical, which further affectedphenol degradable effect.
Hydroxyl radical is the main specie of many free radical oxidationreactions. The strong oxidation ability of hydroxyl radical can be usedto oxidize organic substances and other impurities in water, decreasesthe Chemical Oxygen Demand (COD) value and achieves the goal ofwater treatment. Aromatic hydroxylation from the reaction betweenhydroxyl radical and salicylate or its related compounds has been oftenutilized as a marker for the generation of hydroxyl radicals. We hadinvestigated several technical aspects of applying this method to studyhydroxyl radical production during electrolysis using the salicylicacid(2-HBA) to form 2,5-dihydroxybenzoic acid(2,5-DHBA).Aqueous solution of 2-HBA was electrolyzed by Ti-base Lead DioxideElectrode regard Sn, Sb as the intermediate level, then the solutioncontaining 2-HBA and 2,5-DHBA was analyzed by High PerformanceLiquid Chromatography(HPLC) with fluorescence detection .It was
concluded that the oxidation of 2-HBA to 2,5-DHBA could be areliable and accurate indicator for the formation of hydroxyl radical ifthe experiments are well designed to avoid potential pitfalls associatedwith technical difficulties of the method. The results show that the pHvalue and frequency play important roles in the producing rate ofhydroxyl radical. High pH value is better than low pH value, also ishigh frequency than low frequency. The experiment of phenoldegradation was done at the same time;it indicated that using thehydroxyl radical produced by electrolysis to treat organic wastewatershave good effect.Because the degradation of phenol was achieved by hydroxylradical which formed by electrolysis, factors which affect hydroxylradical forming affect phenol degradation, too. Within the factorsdiscussed in this paper, high pH, high temperature was propitious tophenol degradation. On opposite, low pH, low temperature, theexisting of CO32-and PO43-went against phenol degradation. Theexisting of Cl-was propitious to phenol degradation, but went againstCOD removal.Through comparison of different initial phenol concentrations, wefound electrolysis efficiency was increased along with increasing ofinitial phenol concentrations. So this method was appropriate aspretreatment to other methods. Take it as advanced treatment wassuitable, too. Subsequently, the degradation of true wastewaterindicated that using this method to treat organic wastewaters has greatrealistic meanings and wide application prospects.
羟自由基是许多自由基氧化反应的反应主体,利用它极强的氧化能力处理有机废水,可使废水的化学需氧量(COD)值大大降低,达到水处理的目的。水杨酸(2-HBA)的羟基化产物2,5-二羟基苯甲酸(2,5-DHBA)可以作为羟自由基产生的指示剂。在利用2-HBA及其羟基化产物2,5-DHBA研究羟自由基在电极电解过程中的形成规律中,用以钛网为基体,锡、锑为中间层的二氧化铅电极在高频交流电源下电解2-HBA的水溶液,然后利用高效液相色谱(HPLC)检测分析2-HBA和2,5-DHBA的浓度变化。结果表明:pH值和频率对羟自由基的产率影响明显,溶液碱性条件要优于酸性条件,电源高频情况要优于低频情况,即碱性和高频条件更有利于羟自由基的生成。同时利用该电解装置进行苯酚降解实验表明,利用电解法产生的自由基处理有机废水效果明显。
在本文讨论的因素中,高pH值,高温有利于苯酚的降解,而低pH值,低温以及CO_3~(2-)、PO_4~(3-)的存在不利于苯酚的降解,Cl~-的存在虽有利于酚的去除,但却影响溶液中有机物总的去除量。
Wastewater with organic pollutants is one of the most harmfulsubstances, because its characteristics of big volume, highconcentration, noxious to living beings, hard degradable by naturalprocesses and easy accumulated in bodies. Forming law of hydroxylradical during electrolysis process was discussed in this paper. Thentook wastewater with phenol for example, we described some factorsthat affected forming of hydroxyl radical, which further affectedphenol degradable effect.
Hydroxyl radical is the main specie of many free radical oxidationreactions. The strong oxidation ability of hydroxyl radical can be usedto oxidize organic substances and other impurities in water, decreasesthe Chemical Oxygen Demand (COD) value and achieves the goal ofwater treatment. Aromatic hydroxylation from the reaction betweenhydroxyl radical and salicylate or its related compounds has been oftenutilized as a marker for the generation of hydroxyl radicals. We hadinvestigated several technical aspects of applying this method to studyhydroxyl radical production during electrolysis using the salicylicacid(2-HBA) to form 2,5-dihydroxybenzoic acid(2,5-DHBA).Aqueous solution of 2-HBA was electrolyzed by Ti-base Lead DioxideElectrode regard Sn, Sb as the intermediate level, then the solutioncontaining 2-HBA and 2,5-DHBA was analyzed by High PerformanceLiquid Chromatography(HPLC) with fluorescence detection .It was
concluded that the oxidation of 2-HBA to 2,5-DHBA could be areliable and accurate indicator for the formation of hydroxyl radical ifthe experiments are well designed to avoid potential pitfalls associatedwith technical difficulties of the method. The results show that the pHvalue and frequency play important roles in the producing rate ofhydroxyl radical. High pH value is better than low pH value, also ishigh frequency than low frequency. The experiment of phenoldegradation was done at the same time;it indicated that using thehydroxyl radical produced by electrolysis to treat organic wastewatershave good effect.Because the degradation of phenol was achieved by hydroxylradical which formed by electrolysis, factors which affect hydroxylradical forming affect phenol degradation, too. Within the factorsdiscussed in this paper, high pH, high temperature was propitious tophenol degradation. On opposite, low pH, low temperature, theexisting of CO32-and PO43-went against phenol degradation. Theexisting of Cl-was propitious to phenol degradation, but went againstCOD removal.Through comparison of different initial phenol concentrations, wefound electrolysis efficiency was increased along with increasing ofinitial phenol concentrations. So this method was appropriate aspretreatment to other methods. Take it as advanced treatment wassuitable, too. Subsequently, the degradation of true wastewaterindicated that using this method to treat organic wastewaters has greatrealistic meanings and wide application prospects.
引文
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[2] 魏杰,于秀娟,王东田,钛基氧化物电极的制备及其在水处理中的应用[J],环境保护科学,2002,18(112):10-12
[3] Ahamim A.,Astoshi K.,Kiyohisa O.,et al Waste Water Treatment by Natural and Waste Materials [J],Water Research,2001,35(15):3738-3742
[4] 王惠君,二氧化铅电极的制备及其应用[J],浙江海洋学院学报(自然科学版),1999,18(2):165-167
[5] Maurizio D.F.,Paola C.,On the Design of Electrochemical Reactors for the Treatment of Polluted Water [J],Journal of Cleaner Production,2004,(12):159-163
[6] 黄彦瑜,浅谈自由基[J],高等函授学报(自然科学版),2001,14(2):29-33
[7] J. A. Fraser. Hydrogen peroxide in municipal landfill and industrial effluent treatment[J],Effluent Water Treatment, 1984,24(5): 184-188
[8] 张乃东,郑威,羟自由基·OH在水处理中的应用[J],哈尔滨商业大学学报(自然科学版),2001,17(3):22-24,28
[9] Tryk D.A.,Fujishima. A.,and Honda K., Recent topics in photoelectrochemistry:achievements and future prospects[J], Electrochimica Acta,2000,45(15-16):2363-2376
[10]扈胜禄,李坚斌,黄伟等,水的高级氧化技术——自由基反应[J],矿产与地质,2003,17(1):82-86
[11]钟理,严益群,吕扬效,高级氧化过程的研究与进展[J],现代化工,1997(12):16-19
[12]薛向东,金奇庭,水处理中的高级氧化技术[J],环境保护,2001(6):13-15
[13]刘冬莲,黄艳斌,·OH的形成机理及在水处理中的应用[J],环境科学与技术,2003,26(2):44-46
[14]宋卫锋,吴斌,李义久等,形稳阳极电解处理有机废水的机理研究[J],重庆环境科学,2000,22(6):60-63
[15]Enrique Brillas et al,Electrochemical Destruction of Aniline and 4-chloroaniline for Wastewater Treatment Using a Carbon——PTFEO2——Fed Cathode,Jour Electrochem. Soc.,1995,(142)6:1733-1741
[16]R. Tomat et al. Electrochemical Oxidation of Tolence Promoted by OH Radicals,Journal of Applied Electrochemistry,1984,14:1-8
[17]宋卫锋,吴斌,马前等,电解法降解有机污染物机理及动力学的研究[J],化工环保,2001,21(3):131-135
[18]顾桂松,胡湖生,杨明德,含氰废水的处理技术最近进展[J],环境保护,2001,(2):16—19
[19]魏健美,池乃书,电解水制取臭氧 [J],南昌大学学报(理科版),1994,18(4):419—423
[20]冯玉杰,沈宏,崔玉虹等,钛基二氧化铅电催化电极的制备及电催化性能研究[J],分子催化,2002,16(3):181-186
[21]张招贤,钛基二氧化铅电极的改进和应用[J],氯碱工业,1996,(8):17-23
[22]冯玉杰等,电化学技术在环境工程中的应用[M],北京:化学工业出版社,2002
[23] Ho C.C.,Electrochemical treatment of effluents: a preliminary study of anodic oxidation of simple sugars using lead dioxide-coated titanium anodes [J],J Chemical Technology and Biotechnology,1986,36(1):7—14
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