硫酸根自由基高级氧化技术处理有机废水研究
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摘要
硫酸根自由基高级氧化技术基于具有极高氧化还原电位的硫酸根自由基,可以氧化降解多种有机污染物,是近年来化学法水处理技术的研究热点。本项目通过Fe2+活化过硫酸钾产生的硫酸根自由基降解邻苯二甲酸氢钾,来模拟处理工业废水中的有机物。结果表明,初始pH值和Fe2+浓度对邻苯二甲酸氢钾去除效果影响不大,K_2S_2O_8投加量与邻苯二甲酸氢钾去除率呈现明显的正相关关系。当初始pH值为3,n(FeSO4·7H2O)︰n(K_2S_2O_8)=0.5︰1,m(K_2S_2O_8)︰m(COD)=30︰1时,COD去除率达到72.41%。在实际生产中,可将初始pH值控制在5左右,选用溶解度更大的过硫酸钠替代过硫酸钾。
The advanced oxidation process of sulfate radicals is a research hotspot on chemical treatment method of wastewater in recent years which able to degrade various organic pollutants based on its high ORP(Oxidation-Reduction Potential). This study simulatively treats the organic pollutants in industrial wastewater on degrading the KHP(potassium acid phthalate) by sulfate radicals produced by the KPS(potassium persulfate) activated by ferrous. The results show that the degradation of KHP is not greatly affected by the initial pH and ferrous concentration, but positively correlated with the dosage of KPS. The COD(Chemical Oxygen Demands) removal rate could reach to 72.41 % when the intial pH=3, n(FeSO_4·7H_2O)︰n(K_2S_2O_8)=0.5︰1, m(K_2S_2O_8)︰m(COD)=30︰1. In practice, the initial pH could be set around 5, and use the sodium persulfate(NaPS) which is better solubility instead of the KPS.
The advanced oxidation process of sulfate radicals is a research hotspot on chemical treatment method of wastewater in recent years which able to degrade various organic pollutants based on its high ORP(Oxidation-Reduction Potential). This study simulatively treats the organic pollutants in industrial wastewater on degrading the KHP(potassium acid phthalate) by sulfate radicals produced by the KPS(potassium persulfate) activated by ferrous. The results show that the degradation of KHP is not greatly affected by the initial pH and ferrous concentration, but positively correlated with the dosage of KPS. The COD(Chemical Oxygen Demands) removal rate could reach to 72.41 % when the intial pH=3, n(FeSO_4·7H_2O)︰n(K_2S_2O_8)=0.5︰1, m(K_2S_2O_8)︰m(COD)=30︰1. In practice, the initial pH could be set around 5, and use the sodium persulfate(NaPS) which is better solubility instead of the KPS.
引文
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[16]Liang C J,Bruell C J,Marley MC,et al.Persulfate oxidation for in situ remediation of TCE:I.Activated by ferrous ion with and without apersulfate-thiosulfate redox couple[J].Chemosphere,2004,55(9):1213-1223.
[17]ANIPSITAKIS G P,CRUZ A A,DIONYSIOU D D.Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt[J].Environrnental Science&Technology.2003,37(20):4790-4797.
[18]Xu X R,Li X.Degradation of azo dye Orange G in aqueous solutions by persulfate with ferrous ion[J].Separation and Purification Technology,2010,72:105-111.
[19]Yu-Chi Lee,Shang-Lien Lo,Pei-Te Chiueh,et al.Microwave-hydrothermal decomposition of perfluorooctanoic acid in water by iron-activated persulfate oxidation[J].Water research,2010,44:886-892.
[20]Justine Criquet,Nathalie Karpel Vel Leitner.Degradation of acetic acid with sulfate radical generated by persulfate ions photolysis[J].Chemosphere,2009,77,194-200.
[21]HJ 828-2017水质化学需氧量的测定重铬酸盐法[S].2017.
[22]兰氏化学手册[M].第十三版,科学出版社,1991.
[2]POYATOS J M,ALMECIJA M C,TORRES J C,et al.Advanced oxidation processes for wastewater treatment:state of the art[J].Water Air Soil Pollute.2010,205(1-4):187-204.
[3]常文贵,张胜义.高级氧化技术中羟基自由基产生的机理[J].安庆师范学院学报.2004,4(10):24-26.
[4]张旋,王启山.高级氧化技术在废水处理中的应用[J].水处理技术.2009,35(3):18-22.
[5]陈晓旸.基于硫酸自由基的高级氧化技术降解水中典型有机污染物研究[D].大连:大连理工大学.2007.
[6]杨世迎,陈友媛,胥慧真,等.过硫酸盐活化高级氧化新技术[J].化学展,2008,20(9):1433-1437.
[7]RENGANATHAN R,MARUTHAMUTHU P.Kineties and mechanism of oxidation of aliphatic aldehydes by peroxomonosulphate[J].International Journal of Chemical Kinetics.1986,18(1):49-58.
[8]Liang C J,Bruell C J,Marley M C,et al.Persulfate oxidation for in situ remediation of TCE:II.Activated by chelated ferrous ion[J].Chemo-sphere,2004,55(9):1225-1233.
[9]郑伟,张金凤,王联红,等.柠檬酸-Fe(II)/K2S2O8对敌草隆降解的研究[J].环境化学,2008,27(1):19-22.
[10]Hisao Hori,Ari Yamamoto,Kazuhide Koike.Persulfate-induced photochemical decomposition of a fluorotelomer unsaturated carboxylic acid in water[J].Water Research,2007,41:2962-2968.
[11]Hitoshi Kubota,Yayoi Hariya,Shin-ichi Kuroda,et al.Effect of photoirradiation on potassium persulfate-surface oxidation of low-density polyethylene[J].Polymer Degradation and Stability,2001,72:223-227.
[12]Yang S Y,Wang P,Yang X,et al.Degradation efficiencies of azo dye Acid Orange 7 by the interaction of heat,UV and anions with common oxidants:Persulfate,peroxymonosulfate and hydrogen peroxide[J].Journal of Hazardous Materials,2010,179:552-558.
[13]Hori H,YamamotoA,Hayakawa E,et al.Efficient decomposition of environmentally persistent perfluorocarboxylic acids by use of persulfate as a photochemical oxidant[J].Environ Sci Technol,2005,39:2383-2388.
[14]左传梅,李宏.Fe(II)活化过硫酸盐高级氧化技术处理燃料废水研究[D].重庆:重庆大学.2012.
[15]Kislenko V N,Berlin A A,Litocvhenko N V.Kinetics of glucose oxidation with persulfateions,catalyzed by iron salts[J].Russian Journal of General Chemistry,1995,65:1092-1096.
[16]Liang C J,Bruell C J,Marley MC,et al.Persulfate oxidation for in situ remediation of TCE:I.Activated by ferrous ion with and without apersulfate-thiosulfate redox couple[J].Chemosphere,2004,55(9):1213-1223.
[17]ANIPSITAKIS G P,CRUZ A A,DIONYSIOU D D.Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt[J].Environrnental Science&Technology.2003,37(20):4790-4797.
[18]Xu X R,Li X.Degradation of azo dye Orange G in aqueous solutions by persulfate with ferrous ion[J].Separation and Purification Technology,2010,72:105-111.
[19]Yu-Chi Lee,Shang-Lien Lo,Pei-Te Chiueh,et al.Microwave-hydrothermal decomposition of perfluorooctanoic acid in water by iron-activated persulfate oxidation[J].Water research,2010,44:886-892.
[20]Justine Criquet,Nathalie Karpel Vel Leitner.Degradation of acetic acid with sulfate radical generated by persulfate ions photolysis[J].Chemosphere,2009,77,194-200.
[21]HJ 828-2017水质化学需氧量的测定重铬酸盐法[S].2017.
[22]兰氏化学手册[M].第十三版,科学出版社,1991.