含锗物料的氧化浸出及除砷研究
|
摘要
实验所用原料为含锗的锌冶炼真空炉渣,该物料主要含有锌和铅,此外还含有砷、锗、铟、银等元素,主要以金属或金属间化合物的形式存在。采用氧化浸出工艺浸出物料中的有价元素,回收有价元素后的废液通过化学沉淀法进行除砷,达到排放标准后排放。实验结果表明,氧化浸出的最优工艺条件为:游离酸浓度5 mol·L-1;双氧水过剩系数αH2O2=1.5;浸出时间1 h;液固比5∶1。在此条件下,Ge和As的平均浸出率分别为99.64%和99.43%。含砷废液除砷未达标严禁排放,以石灰为沉淀剂,废液经过化学沉淀法除砷处理,得到的砷酸钙废渣用水泥固化技术进行稳定化处理,避免造成二次砷污染;除砷后的废液运用氢化物发生-原子荧光光谱法(HG-AFS)测定残留的砷含量,检测得到溶液中的砷含量(0.008 mol·L-1)低于饮用水排放标准(0.01 mol·L-1),并进一步用石灰中和使废液pH达到9左右,达到排放标准。
The vacuum slag used in the experiment was germanium-containing material,which was mainly composed of a large amount of zinc,lead,arsenic and other valuable elements such as indium,germanium,and silver. The elements in the material were mainly in the form of metal or intermetallic compound( IMC). In this paper,oxidation leaching process was used for the leaching of valuable elements in the material,and chemical precipitation method was applied to remove arsenic in the effluent in order to meet the emission standards before discharge. The optimum condition of the oxidation leaching process was obtained: free acid concentration of5 mol·L- 1,αH2O2of 1. 5,leaching time of 1 h and L∶ S( liguid-solid ratio) of 5∶ 1. The leaching ratio of germanium and arsenic under the optimum condition were 99. 64% and 99. 43%,respectively. Arsenic-containing effluent was forbidden to discharge before the arsenic content met the emission standard. Lime was used as the precipitant in the removal of arsenic by chemical precipitation method,and calcium arsenate obtained in the process was treated by the cement solidification technology to avoid secondary arsenic contamination. The concentration of the arsenic remaining in the wastewater was detected by means of hydride generation-atomic fluorescence spectrometry( HG-AFS),the result showed that the arsenic concentration was 0. 008 mol·L- 1,below the drinking water discharge standard( 0. 01 mol·L- 1),and the pH of the effluent was further neutralized to about 9. The effluent could completely meet the discharge standard.
The vacuum slag used in the experiment was germanium-containing material,which was mainly composed of a large amount of zinc,lead,arsenic and other valuable elements such as indium,germanium,and silver. The elements in the material were mainly in the form of metal or intermetallic compound( IMC). In this paper,oxidation leaching process was used for the leaching of valuable elements in the material,and chemical precipitation method was applied to remove arsenic in the effluent in order to meet the emission standards before discharge. The optimum condition of the oxidation leaching process was obtained: free acid concentration of5 mol·L- 1,αH2O2of 1. 5,leaching time of 1 h and L∶ S( liguid-solid ratio) of 5∶ 1. The leaching ratio of germanium and arsenic under the optimum condition were 99. 64% and 99. 43%,respectively. Arsenic-containing effluent was forbidden to discharge before the arsenic content met the emission standard. Lime was used as the precipitant in the removal of arsenic by chemical precipitation method,and calcium arsenate obtained in the process was treated by the cement solidification technology to avoid secondary arsenic contamination. The concentration of the arsenic remaining in the wastewater was detected by means of hydride generation-atomic fluorescence spectrometry( HG-AFS),the result showed that the arsenic concentration was 0. 008 mol·L- 1,below the drinking water discharge standard( 0. 01 mol·L- 1),and the pH of the effluent was further neutralized to about 9. The effluent could completely meet the discharge standard.
引文
[1]Moskalyk R R.Review of germanium processing worldwide[J].Minerals Engineering,2004,17(3):393.
[2]Marco-Lozar J P,Cazorla-Amorós D,Linares-Solano A.A new strategy for germanium adsorption on activated carbon by complex formation[J].Carbon,2007,45(13):2519.
[3]Pu S K,Lan Y Z,Jin L,Xiao C H.Improving germanium distillation recovery rate from coal dust[J].Chinese Journal of Rare Metals,2012,36(5):817.(普世坤,兰尧中,靳林,肖春宏.提高含锗煤烟尘氯化蒸馏回收率的工艺研究[J].稀有金属,2012,36(5):817.)
[4]Gao H W,Liu W G.Spectrophotometric investigation of germanium complex solution with o-chlorophenylfluorone and determination of trace amounts of germanium[J].Bull.Korean Chem.Soc.,2000,21(11):1090.
[5]Sami Virolainen,Jari Heinonen,Erkki Paatero.Selective recovery of germanium with N-methylglucamine functional resin from sulfate solutions[J].Separation and Purification Technology,2013,104:193.
[6]Meawad Amr S,Bojinova Darinka Y,Pelovski Yoncho G.An overview of metals recovery from thermal power plant solid wastes[J].Waste Management,2010,30(12):2548.
[7]Torralvo F Arroyo,Fernández-Pereira C.Recovery of germanium from real fly ash leachates by ion-exchange extraction[J].Minerals Engineering,2011,24(1):35.
[8]Fátima Arroyo,Constantino Fernández-Pereira.Hydrometallurgical recovery of germanium from coal gasification fly ash.Solvent Extraction Method[J].Ind.Eng.Chem.Res.,2008,47(9):3186.
[9]Erwin Rosenberg.Germanium:environmental occurrence,importance and speciation[J].Rev.Environ.Sci.Biotechnol.,2009,8(1):29.
[10]Peng C H,Tang M T.Prevention of arsenic pollution and development and application of wood antiseptic containing arsenic[J].Journal of Safety and Environment,2001,1(4):10.(彭长宏,唐谟堂.砷污染防治与含砷木材防腐剂的开发应用[J].安全与环境学报,2001,1(4):10.)
[11]Tang M T.The arsenic harm and protection measurement in nonferrous industry in China[J].Hunan Nonferrous Metals,1989,5(2):15.(唐谟堂.我国有色冶金中的砷害及其对策[J].湖南有色金属,1989,5(2):15.)
[12]Badal Kumar Mandal,Suzuki Kazuo T.Arsenic round the world:a review[J].Talanta,2002,58(1):201.
[13]Mohan D,C U Pittman Jr.Arsenic removal from water/wastewater using adsorbents—a critical review[J].J.Hazard.Mater,2007,142(1-2):1.
[14]Leist M,Casey R J,Caridi D.The management of arsenic wastes:problems and prospects[J].Journal of Hazardous Materials,2000,76(1):125.
[15]Han J T,William S F.Arsenic removal from water by iron-sulphide minerals[J].Chinese Science Bulletin,2000,45(15):1430.
[16]Zheng S D,Chen S M,Lin X M,Li Y H,Li J H.Test and research on comprehensive recovery if indium,germanium,lead and silver from residue of zinc dross leaching[J].Nonferrous Smelting,2001,30(2):34.(郑顺德,陈世民,林兴铭,李裕后,李俊红.从锌渣浸渣中综合回收铟锗铅银的试验研究[J].有色冶炼,2001,30(2):34.)
[17]Nie Y F,Jin Y Y,Liu F Q.Handbook on Solid Waste Management and Technology[M].Beijing:Chemical Industry Press,2012.625(聂永丰,金宜英,刘富强.固体废物处理工程技术手册[M].北京:化学工业出版社,2012.625.)
[2]Marco-Lozar J P,Cazorla-Amorós D,Linares-Solano A.A new strategy for germanium adsorption on activated carbon by complex formation[J].Carbon,2007,45(13):2519.
[3]Pu S K,Lan Y Z,Jin L,Xiao C H.Improving germanium distillation recovery rate from coal dust[J].Chinese Journal of Rare Metals,2012,36(5):817.(普世坤,兰尧中,靳林,肖春宏.提高含锗煤烟尘氯化蒸馏回收率的工艺研究[J].稀有金属,2012,36(5):817.)
[4]Gao H W,Liu W G.Spectrophotometric investigation of germanium complex solution with o-chlorophenylfluorone and determination of trace amounts of germanium[J].Bull.Korean Chem.Soc.,2000,21(11):1090.
[5]Sami Virolainen,Jari Heinonen,Erkki Paatero.Selective recovery of germanium with N-methylglucamine functional resin from sulfate solutions[J].Separation and Purification Technology,2013,104:193.
[6]Meawad Amr S,Bojinova Darinka Y,Pelovski Yoncho G.An overview of metals recovery from thermal power plant solid wastes[J].Waste Management,2010,30(12):2548.
[7]Torralvo F Arroyo,Fernández-Pereira C.Recovery of germanium from real fly ash leachates by ion-exchange extraction[J].Minerals Engineering,2011,24(1):35.
[8]Fátima Arroyo,Constantino Fernández-Pereira.Hydrometallurgical recovery of germanium from coal gasification fly ash.Solvent Extraction Method[J].Ind.Eng.Chem.Res.,2008,47(9):3186.
[9]Erwin Rosenberg.Germanium:environmental occurrence,importance and speciation[J].Rev.Environ.Sci.Biotechnol.,2009,8(1):29.
[10]Peng C H,Tang M T.Prevention of arsenic pollution and development and application of wood antiseptic containing arsenic[J].Journal of Safety and Environment,2001,1(4):10.(彭长宏,唐谟堂.砷污染防治与含砷木材防腐剂的开发应用[J].安全与环境学报,2001,1(4):10.)
[11]Tang M T.The arsenic harm and protection measurement in nonferrous industry in China[J].Hunan Nonferrous Metals,1989,5(2):15.(唐谟堂.我国有色冶金中的砷害及其对策[J].湖南有色金属,1989,5(2):15.)
[12]Badal Kumar Mandal,Suzuki Kazuo T.Arsenic round the world:a review[J].Talanta,2002,58(1):201.
[13]Mohan D,C U Pittman Jr.Arsenic removal from water/wastewater using adsorbents—a critical review[J].J.Hazard.Mater,2007,142(1-2):1.
[14]Leist M,Casey R J,Caridi D.The management of arsenic wastes:problems and prospects[J].Journal of Hazardous Materials,2000,76(1):125.
[15]Han J T,William S F.Arsenic removal from water by iron-sulphide minerals[J].Chinese Science Bulletin,2000,45(15):1430.
[16]Zheng S D,Chen S M,Lin X M,Li Y H,Li J H.Test and research on comprehensive recovery if indium,germanium,lead and silver from residue of zinc dross leaching[J].Nonferrous Smelting,2001,30(2):34.(郑顺德,陈世民,林兴铭,李裕后,李俊红.从锌渣浸渣中综合回收铟锗铅银的试验研究[J].有色冶炼,2001,30(2):34.)
[17]Nie Y F,Jin Y Y,Liu F Q.Handbook on Solid Waste Management and Technology[M].Beijing:Chemical Industry Press,2012.625(聂永丰,金宜英,刘富强.固体废物处理工程技术手册[M].北京:化学工业出版社,2012.625.)