含砷酸性废水中砷的氧化过程研究
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摘要
研究了含砷酸性废水中As(Ⅲ)的氧化过程,分析了As-H2O系E-p H图,采用电解产生的H2SO5对As(Ⅲ)进行氧化和电解,对硫酸-砷混合体系中的砷进行氧化。试验结果表明,三价砷的氧化电位高于0. 3 V,且低于氧气析出电位,随着pH值的增大,砷的氧化电位逐渐降低。电解电压选取6 V,在此条件下会产生过一硫酸,加入0. 5 g/L硫氰酸铵抑制析氧副反应的发生,提高电流效率。对比了相同条件下单纯利用电解产生的过一硫酸氧化As(Ⅲ)和电解氧化As(Ⅲ)的效果,发现电解氧化As(Ⅲ)的氧化率要高于单纯过一硫酸的氧化率,说明在利用较高电压电解氧化三价砷时,其实质是电化学氧化和电解产生的过一硫酸氧化共同作用的结果。
The oxidation process of As( Ⅲ) in acidic wastewater containing arsenic was studied.The E-p H diagram of As-H2 O system was analyzed.The oxidation effects of As( Ⅲ) oxidized by H2 SO5 produced by electrolysis and electrolytic oxidation of arsenic in sulfuric acid-arsenic mixed system were compared.The experimental results show that the oxidation potential of trivalent arsenic is higher than 0.3 V,and it is lower than the oxygen deposition potential.As p H value increases,the oxidation potential of arsenic gradually decreases.The experimental electrolysis voltage was selected as 6 V.Under this condition,Caro 's acid is generated.The addition of 0.5 g/L ammonium thiocyanate is added to suppress the occurrence of oxygen evolution side reactions and the current efficiency is improved.Comparing the effects of oxidizing As( Ⅲ) Caro 's acid produced by electrolysis and under the same conditions,the effect of electrolytically oxidizing As( Ⅲ) at this voltage,it 's found that the oxidation rate of electrolytic oxidation As( Ⅲ) is higher than the oxidation rate of Caro's acid,indicating that in the case of electrolytic oxidation of trivalent arsenic using a higher voltage,the nature of the oxidation is the combined effect of electrode oxidation and Caro's acid oxidation produced by electrolysis.
The oxidation process of As( Ⅲ) in acidic wastewater containing arsenic was studied.The E-p H diagram of As-H2 O system was analyzed.The oxidation effects of As( Ⅲ) oxidized by H2 SO5 produced by electrolysis and electrolytic oxidation of arsenic in sulfuric acid-arsenic mixed system were compared.The experimental results show that the oxidation potential of trivalent arsenic is higher than 0.3 V,and it is lower than the oxygen deposition potential.As p H value increases,the oxidation potential of arsenic gradually decreases.The experimental electrolysis voltage was selected as 6 V.Under this condition,Caro 's acid is generated.The addition of 0.5 g/L ammonium thiocyanate is added to suppress the occurrence of oxygen evolution side reactions and the current efficiency is improved.Comparing the effects of oxidizing As( Ⅲ) Caro 's acid produced by electrolysis and under the same conditions,the effect of electrolytically oxidizing As( Ⅲ) at this voltage,it 's found that the oxidation rate of electrolytic oxidation As( Ⅲ) is higher than the oxidation rate of Caro's acid,indicating that in the case of electrolytic oxidation of trivalent arsenic using a higher voltage,the nature of the oxidation is the combined effect of electrode oxidation and Caro's acid oxidation produced by electrolysis.
引文
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[19]赵建宏,孙培永,王留成,等.电解法生产过硫酸铵的研究[J].郑州大学学报(工学版),2006,27(1):109-112.ZHAO Jianhong,SUN Peiyong,WANG Liucheng,et al.Study on the process for electrosynthesis of ammonium persulfate[J]. Journal of Zhengzhou University(Engineering Edition),2006,27(1):109-112.
[2]赵素莲,王玲芬,梁京辉.饮用水中砷的危害及除砷措施[J].现代预防医学,2002,29(05):651-652.ZHAO Sulian,WANG Lingfen,LIANG Jinghui. Hazard of arsenic in drinking water and removal measures[J].Modern Preventive Medicine,2002,29(5):651-652.
[3] BGS D. Groundwater studies for arsenic contamination in Bangladesh[R]. Department of Public Health,Government of Bangladesh,Mott MacDonald and British Geological Survey:Final report, rapid investigation phase,1999.
[4] XU Y,NAKAJIMA T,OHKI A. Adsorption and removal of arsenic(V)from drinking water by aluminum-loaded Shirasu-zeolite[J]. Journal of Hazardous Materials,2002,92(3):275-287.
[5]黄自力,刘缘缘,陶青英,等.石灰沉淀法除砷的影响因素[J].环境工程学报,2012,6(3):734-738.HUANG Zili, LIU Yuanyuan, TAO Qingying,et al.Influencing factors of arsenic removal by lime precipitation[J]. Chinese Journal of Environmental Engineering,2012,6(3):734-738.
[6] SUZUKI T M,BOMANI J O,MATSUNAGA H,et al.Removal of As(III)and As(V)by a porous spherical resin loaded with monoclinic hydrous zirconium oxide[J].Chemistry Letters,1997,26(11):1119-1120.
[7]BRANDHUBER P,AMY G. Arsenic removal by a charged ultrafiltration membrane—influences of membrane operating conditions and water quality on arsenic rejection[J].Desalination,2001,140(1):1-14.
[8]韩光辉.高砷酸性浸出液中回收铜、锌及除砷的研究[D].乌鲁木齐:新疆大学,2015.HAN Guanghui. Study on recovery of copper,zinc and arsenic removal from high acidic leaching liquor[D].Urumqi:Xinjiang University,2015.
[9]GOMES J A G,DAIDA P,KESMEZ M,et al. Arsenic removal by electrocoagulation using combined Al-Fe electrode system and characterization of products[J].Journal of Hazardous Materials,2007,139(2):220-231.
[10] ASADULLAH M,JAHAN I,AHMED M B,et al.Preparation of microporous activated carbon and its modification for arsenic removal from water[J]. Journal of Industrial and Engineering Chemistry, 2014, 20(3):887-896.
[11] AHORANTA S H,KOKKO M E,PAPIRIO S,et al.Arsenic removal from acidic solutions with biogenic ferric precipitates[J]. Journal of hazardous materials,2016,306:124-132.
[12]王薇.生物氧化与吸附相结合处理高浓度含砷废水[D].南京:南京工业大学,2006.WANG Wei. To treat high concentration arseniccontaining wastewater with bio-oxidation and adsorption[D]. Nanjing:Nanjing University of Technology,2006.
[13]李慧婷.电化学氧化法在工业废水处理中的应用研究[D].长春:吉林大学,2011.Li Huiting. The study on electrochemical oxidation processes applied in industrial wastewater treatment[D].Changchun:Jilin University,2011.
[14]蒋慧明.砷钼蓝法测定硫酸生产废水中的砷含量[J].硫酸工业,2008(6):37-39.JIANG Huiming. Determination of arsenic in wastewater from sulphuric acid production arsenic by arsenomolybdenum blue method[J]. Sulphuric Acid Industry,2008(6):37-39.
[15]王军学.氢化物发生-原子荧光光谱法测定精碲中微量砷[J].冶金分析,2010,30(2):55-57.WANG Junxue. Hydride generation-atomic fluorescence spectrometry for determination of micro arsenic in refined tellurium[J]. Metallurgical Analysis,2010,30(2):55-57.
[16]马戈,谢文兵,刘晶,等.氢化物发生原子荧光光谱法直接测定水样中砷(III)和砷(V)[J].光谱学与光谱分析,2007,27(4):807-809.MA Ge,XIE Wenbing,LIU Jing,et al. Speciation of arsenic(iii)and arsenic(v)in water by hydride generation atomic fluorescence spectrometry[J].Spectroscopy and Spectral Analysis, 2007, 27(4):807-809.
[17]YANG J Q,CHAI L Y,LI Q Z,et al. Redox behavior and chemical species of arsenic in acidic aqueous system[J]. Transactions of Nonferrous Metals Society of China,2017,27(9):2063-2072.
[18]张毅,洪涛,雒俊,等.湿法冶金浸出用强氧化剂过一硫酸的合成研究[J].湿法冶金,2011,30(1):20-23.ZHANG Yi,HONG Tao,LUO Jun,et al. Synthesis research of strong oxidant caro's acid used hydrometallurgical leaching[J]. Hydrometallurgy,2011,30(1):20-23.
[19]赵建宏,孙培永,王留成,等.电解法生产过硫酸铵的研究[J].郑州大学学报(工学版),2006,27(1):109-112.ZHAO Jianhong,SUN Peiyong,WANG Liucheng,et al.Study on the process for electrosynthesis of ammonium persulfate[J]. Journal of Zhengzhou University(Engineering Edition),2006,27(1):109-112.