高锑铋废渣中回收有价金属的研究
摘要
本文对铜阳极泥的处理工艺、现状,以及废料中铜铅等有价金属的性质应用进行了全面的综述。提出了以氢氧化钠-甘油为浸出剂,从高锑铋废渣中浸取回收铜、铅、铋和锑有价金属的新工艺,为二次资源再利用和环境保护开辟了新的途径,具有重要的现实意义。
本文针对浸出工艺过程,考察了氢氧化钠浓度、甘油浓度、浸出温度、浸出时间以及液固比单因素实验条件对浸出过程的影响,得到浸出最优化工艺条件为:氢氧化钠浓度150g·L~(-1)、甘油浓度250g·L~(-1)、反应时间2h、反应温度50℃、液固比5:1。锑、铋、铜和铅浸出率分别为85.8%、95.9%、96.6%、92.8%。
同时,本文还讨论了在浸出液中加入硫化钠沉铜、铅、铋,回收铜、铅、铋,然后水解沉锑生成三氧化二锑回收锑的工艺条件。得到其最优化条件是:硫化钠用量为其理论量的1.2倍、反应温度为25℃、反应时间为30min,该过程中铜的回收率为98.2%;铅的回收率为98.7%;铋的回收率为92.9%。在硫化沉淀后,加硫酸调整pH值至6.0,锑化合物水解生成三氧化二锑,过滤,滤液蒸发至浸出液原体积,得到可利用的甘油,其甘油再生率可达85%以上。
本研究通过以氢氧化钠-甘油作浸出剂,经硫化沉铜、铅、铋,水解沉锑等工艺,综合回收利用了高锑铋废渣,其中铜、铅、铋、锑总的回收率分别达到94.9%、91.6%、90%、83.1%。
The treatment process and status of the copper anode mud,as well as the properties and application of valued metals such as copper and lead in the scrap,were comprehensively introduced in this article.A new technology which utilized hydroxide-glycerol as leach reagent to recycle valued metals of Cu,Pb and Bi and antimony from the residue of antimony-bismuth was advanced in this paper.The paper applied a new methodology for the recovery of secondary resources and environmental protection with great significance.
Aiming at the leaching process,the single-factor experiments were carried out to examine the influence of concentration of sodium hydroxide,concentration of glycerol,reaction temperature,reaction time and the ratio of liquid and solid.The optimum technique conditions were as follows:sodium hydroxide 150 g·L~(-1),glycerol 50g·L~(-1),reaction temperature as 50℃,reation time as 2h,ratio of liquid and solid as 5:1.The leaching rates of Sb,Bi,Cu and Pb are 85.8%、95.9%、96.6% and 92.8%,respectively.
The processing conditions of recovering Sb from Sb_2O_3 by hydrolysis,after the recovery of Cu,Pb and Bi by precipitation with the addition of sodium sulfide,were discussed in this paper.The optimum technique conditions were concluded as follows:the practical dosage of sodium sulfide as 1.2 times of its theoretical dosage,reaction temperature as 25℃,and reaction time as 30mins.At this conditions the recovery rates of Cu,Pb and Bi are 98.2%,98.7%and 92.9%,respectively.After the sulfides precipitation,Sb_2O_3 was produced by adjusting of pH value to 6.0 using sulfuric acid.Then filtration.When the filtrated solution was concentrated by evaporation,glycerol was produced with the recovery rate of glycerol over 85%.
Using sodium hydroxide-glycerin as leaching agent,this study comprehensively recycled and reused the waste residue of antimony- bismuth by the techniques of sulfides precipitation for Cu,Pb,Bi and the hydrolysis for Sb.The total recovery rates of Cu,Pb,Bi and Sb are 94.9%, 91.6%,90%and 83.1%,respectively.
本文针对浸出工艺过程,考察了氢氧化钠浓度、甘油浓度、浸出温度、浸出时间以及液固比单因素实验条件对浸出过程的影响,得到浸出最优化工艺条件为:氢氧化钠浓度150g·L~(-1)、甘油浓度250g·L~(-1)、反应时间2h、反应温度50℃、液固比5:1。锑、铋、铜和铅浸出率分别为85.8%、95.9%、96.6%、92.8%。
同时,本文还讨论了在浸出液中加入硫化钠沉铜、铅、铋,回收铜、铅、铋,然后水解沉锑生成三氧化二锑回收锑的工艺条件。得到其最优化条件是:硫化钠用量为其理论量的1.2倍、反应温度为25℃、反应时间为30min,该过程中铜的回收率为98.2%;铅的回收率为98.7%;铋的回收率为92.9%。在硫化沉淀后,加硫酸调整pH值至6.0,锑化合物水解生成三氧化二锑,过滤,滤液蒸发至浸出液原体积,得到可利用的甘油,其甘油再生率可达85%以上。
本研究通过以氢氧化钠-甘油作浸出剂,经硫化沉铜、铅、铋,水解沉锑等工艺,综合回收利用了高锑铋废渣,其中铜、铅、铋、锑总的回收率分别达到94.9%、91.6%、90%、83.1%。
The treatment process and status of the copper anode mud,as well as the properties and application of valued metals such as copper and lead in the scrap,were comprehensively introduced in this article.A new technology which utilized hydroxide-glycerol as leach reagent to recycle valued metals of Cu,Pb and Bi and antimony from the residue of antimony-bismuth was advanced in this paper.The paper applied a new methodology for the recovery of secondary resources and environmental protection with great significance.
Aiming at the leaching process,the single-factor experiments were carried out to examine the influence of concentration of sodium hydroxide,concentration of glycerol,reaction temperature,reaction time and the ratio of liquid and solid.The optimum technique conditions were as follows:sodium hydroxide 150 g·L~(-1),glycerol 50g·L~(-1),reaction temperature as 50℃,reation time as 2h,ratio of liquid and solid as 5:1.The leaching rates of Sb,Bi,Cu and Pb are 85.8%、95.9%、96.6% and 92.8%,respectively.
The processing conditions of recovering Sb from Sb_2O_3 by hydrolysis,after the recovery of Cu,Pb and Bi by precipitation with the addition of sodium sulfide,were discussed in this paper.The optimum technique conditions were concluded as follows:the practical dosage of sodium sulfide as 1.2 times of its theoretical dosage,reaction temperature as 25℃,and reaction time as 30mins.At this conditions the recovery rates of Cu,Pb and Bi are 98.2%,98.7%and 92.9%,respectively.After the sulfides precipitation,Sb_2O_3 was produced by adjusting of pH value to 6.0 using sulfuric acid.Then filtration.When the filtrated solution was concentrated by evaporation,glycerol was produced with the recovery rate of glycerol over 85%.
Using sodium hydroxide-glycerin as leaching agent,this study comprehensively recycled and reused the waste residue of antimony- bismuth by the techniques of sulfides precipitation for Cu,Pb,Bi and the hydrolysis for Sb.The total recovery rates of Cu,Pb,Bi and Sb are 94.9%, 91.6%,90%and 83.1%,respectively.
引文
[1]彭容秋.重金属冶金工厂原料的综合利用.长沙:中南大学出版社,2006.7-19
[2]彭容秋.铜冶金.长沙:中南大学出版社,2004.7-19
[3]兰兴华.铜的生产和应用.世界有色金属,2005,(3):60-62
[4]黄坚.高纯铜加工方法综述.湖南有色金属,1996,12(6):36-39
[5]乐颂光,鲁君乐.再生有色金属生产.长沙:中南工业出版社,1994.198-201
[6]彭容秋.铅冶金.长沙:中南大学出版社,2004.1-7
[7]谭治河,郭春雨.减低高纯铅中的Cu、Bi、Sn等杂质含量.四川有色金属,2004,(2):37-39
[8]赵天从.有色金属提取冶炼手册-锌镉铅铋.北京:冶金工业出版社,1992.193-198
[9]赵天从.有的金属提取冶炼手册-锡锑汞.北京:冶金工业出版社,1992.155-160
[10]黎鼎鑫.贵金属提取与精炼.长沙:中南工业大学出版社,1991.14-18
[11]孙戬.金银冶金.北京:冶金工业出版社,1998.11-15
[12]胡建辉,张传福.铜阳极泥预处理脱铜工艺优化.贵金属,2002,23(04):1-5
[13]王日.铜阳极泥预处理工艺优化.矿冶,2004,13(04):46-49
[14]王日.铜阳极泥处理工艺优化.南昌工程学院学报,2004,23(04):75-78
[15]Yang Tianzu,Zhao Tianeong,Lu Yiyuan.The preparation of arsenie trioxide from the liquid and residue eontainingarsenie.J.Cent 一South Inst Min Metall,1993,24(4):483-489
[16]余贵林.阳极泥预处理工艺探讨.江西铜业工程,1995,(4):49-52
[17]侯慧芬.从铜阳极泥中综合回收重有色金属和稀、贵金属.上海有色金属,2000,21(02):88-93
[18]从阳极泥中回收金、银并综合回收铜、铅、锑.黄金科学技术,2002,(02):39
[19]尹湘华.高杂质铜阳极泥的处理.有色金属(冶炼部分),2005,(05):16-18
[20]P.Hannialaetal.Proeeeding of Copper 99 International Conferenee,Vol.v,Edited by D.B.George,e tal.Apublieation of The Minerals Metals and Materials Soeiety,USA,1999,221-237.
[21]杜三保.国内外铜阳极泥处理方法综述.中国物资再生,1997,(2):16-19
[22]张金成.白银公司几种冶炼渣综合回收现状及其建议.中国有色冶金,2004,(04):34-38
[23]杨勇,陈鹤群.铜阳极泥选冶联合流程的特点与展望.昆明理工大学学报,2002,27(1):31-35
[24]余真荣.铜阳极泥湿法处理工艺的技术改造.黄金,1999,20(4):34-38
[25]陈昌禄.铜阳极泥处理新工艺.昆明贵金属研究所(内部资料),1983
[26]吕高平.铜阳极泥湿法处理工艺的改进与优化.有色冶炼,2003,8(4):28-30
[27]农大桂.铜阳极泥处理工艺的改进.中国有色冶金,2004,(06):44-49
[28]夏光祥,石伟,方兆珩.铜阳极泥全湿法处理工艺研究.有色金属(冶炼部分),2002,(01):29-33
[29]周彝,赵忱.阳极泥处理工艺优化实践.有色金属(冶炼部分),2003,(01):26-28
[30]余真荣.铜阳极泥湿法处理工艺的技术改造.黄金,1999,(04):34-37
[31]杨茂才.从铜阳极泥中提取金银.贵金属,1999,18(4):24-26
[32]王小龙,张昕红.铜阳极泥处理工艺的探讨.矿冶工程,2005,14(4):46-48
[33]陈庆邦.铜阳极泥湿法回收贵金属工艺研究.黄金,1999,20(5):38-40
[34]夏光祥.全湿法处理铜阳极泥新工艺.有色金属(冶炼部分),2002,(1):29-34
[35]宣善伦.铜阳极泥处理工艺的改进实践.黄金,2007,28(02):39-41
[36]胡少华.铜阳极泥中金银及有价金属的回收.江西有色金属,1999,13(03):37-39
[37]王秋风,黄开国.综述银的回收.国外金属矿选矿,1996,(3):34-36
[38]陈昌禄,冯学.铜阳极泥处理新工艺研究.昆明冶金工业部贵金属研究所(内部资料),1980
[39]S.L.Fletcher.Recent developments in contact conductance heat transfer.Journal of Heat Transfer,1988,(110):1059-1070.
[40]M.Van der Voort,M.Dougherty,S.Watson.Combining KOHONEN maps with ARIMA time series model to forecast traffic flow.Transportation Research,1996,4C(5):307-318.
[41]潘朝群,邓先和,宾万达,等.冶炼副产物中金银的富集新工艺.贵金属,2001,22(4):17-22
[42]彭光复,张学发.铝冶炼副产物白灰中金银的富集方法:甘油,碱液浸取除 锑铅的研究.有色金属(冶炼部分),1990,(2):33-35
[43]翟昕,朱启忠.有色金属废弃物资源化是可持续经济发展的重要选择.中国人口资源与环境,1999,9(4):42-46
[44]彭容秋.重金属冶金学.长沙:中南大学出版社,2004.59-60
[45]潘朝群,邓先和,宾万达,等.NaOH、甘油的水溶液浸出三氧化二锑的机理研究.矿冶,2001,(2):31-36
[46]T.Oda.An algorithm for prediction of travel time using vehicle sensor data.In Third International Conference OnRoad Traffic Control.1990,40-44.
[47]钟云波,梅光贵,钟竹前.硫化法脱除铜电解废液中As、Sb、Bi的试验.中南大学学报,1997,28(4):336-339
[48]梅光贵,钟云波,钟竹前.硫化沉淀法净化铜废电解液的热力学分析.中南大学学报,1996,27(1):31-35
[2]彭容秋.铜冶金.长沙:中南大学出版社,2004.7-19
[3]兰兴华.铜的生产和应用.世界有色金属,2005,(3):60-62
[4]黄坚.高纯铜加工方法综述.湖南有色金属,1996,12(6):36-39
[5]乐颂光,鲁君乐.再生有色金属生产.长沙:中南工业出版社,1994.198-201
[6]彭容秋.铅冶金.长沙:中南大学出版社,2004.1-7
[7]谭治河,郭春雨.减低高纯铅中的Cu、Bi、Sn等杂质含量.四川有色金属,2004,(2):37-39
[8]赵天从.有色金属提取冶炼手册-锌镉铅铋.北京:冶金工业出版社,1992.193-198
[9]赵天从.有的金属提取冶炼手册-锡锑汞.北京:冶金工业出版社,1992.155-160
[10]黎鼎鑫.贵金属提取与精炼.长沙:中南工业大学出版社,1991.14-18
[11]孙戬.金银冶金.北京:冶金工业出版社,1998.11-15
[12]胡建辉,张传福.铜阳极泥预处理脱铜工艺优化.贵金属,2002,23(04):1-5
[13]王日.铜阳极泥预处理工艺优化.矿冶,2004,13(04):46-49
[14]王日.铜阳极泥处理工艺优化.南昌工程学院学报,2004,23(04):75-78
[15]Yang Tianzu,Zhao Tianeong,Lu Yiyuan.The preparation of arsenie trioxide from the liquid and residue eontainingarsenie.J.Cent 一South Inst Min Metall,1993,24(4):483-489
[16]余贵林.阳极泥预处理工艺探讨.江西铜业工程,1995,(4):49-52
[17]侯慧芬.从铜阳极泥中综合回收重有色金属和稀、贵金属.上海有色金属,2000,21(02):88-93
[18]从阳极泥中回收金、银并综合回收铜、铅、锑.黄金科学技术,2002,(02):39
[19]尹湘华.高杂质铜阳极泥的处理.有色金属(冶炼部分),2005,(05):16-18
[20]P.Hannialaetal.Proeeeding of Copper 99 International Conferenee,Vol.v,Edited by D.B.George,e tal.Apublieation of The Minerals Metals and Materials Soeiety,USA,1999,221-237.
[21]杜三保.国内外铜阳极泥处理方法综述.中国物资再生,1997,(2):16-19
[22]张金成.白银公司几种冶炼渣综合回收现状及其建议.中国有色冶金,2004,(04):34-38
[23]杨勇,陈鹤群.铜阳极泥选冶联合流程的特点与展望.昆明理工大学学报,2002,27(1):31-35
[24]余真荣.铜阳极泥湿法处理工艺的技术改造.黄金,1999,20(4):34-38
[25]陈昌禄.铜阳极泥处理新工艺.昆明贵金属研究所(内部资料),1983
[26]吕高平.铜阳极泥湿法处理工艺的改进与优化.有色冶炼,2003,8(4):28-30
[27]农大桂.铜阳极泥处理工艺的改进.中国有色冶金,2004,(06):44-49
[28]夏光祥,石伟,方兆珩.铜阳极泥全湿法处理工艺研究.有色金属(冶炼部分),2002,(01):29-33
[29]周彝,赵忱.阳极泥处理工艺优化实践.有色金属(冶炼部分),2003,(01):26-28
[30]余真荣.铜阳极泥湿法处理工艺的技术改造.黄金,1999,(04):34-37
[31]杨茂才.从铜阳极泥中提取金银.贵金属,1999,18(4):24-26
[32]王小龙,张昕红.铜阳极泥处理工艺的探讨.矿冶工程,2005,14(4):46-48
[33]陈庆邦.铜阳极泥湿法回收贵金属工艺研究.黄金,1999,20(5):38-40
[34]夏光祥.全湿法处理铜阳极泥新工艺.有色金属(冶炼部分),2002,(1):29-34
[35]宣善伦.铜阳极泥处理工艺的改进实践.黄金,2007,28(02):39-41
[36]胡少华.铜阳极泥中金银及有价金属的回收.江西有色金属,1999,13(03):37-39
[37]王秋风,黄开国.综述银的回收.国外金属矿选矿,1996,(3):34-36
[38]陈昌禄,冯学.铜阳极泥处理新工艺研究.昆明冶金工业部贵金属研究所(内部资料),1980
[39]S.L.Fletcher.Recent developments in contact conductance heat transfer.Journal of Heat Transfer,1988,(110):1059-1070.
[40]M.Van der Voort,M.Dougherty,S.Watson.Combining KOHONEN maps with ARIMA time series model to forecast traffic flow.Transportation Research,1996,4C(5):307-318.
[41]潘朝群,邓先和,宾万达,等.冶炼副产物中金银的富集新工艺.贵金属,2001,22(4):17-22
[42]彭光复,张学发.铝冶炼副产物白灰中金银的富集方法:甘油,碱液浸取除 锑铅的研究.有色金属(冶炼部分),1990,(2):33-35
[43]翟昕,朱启忠.有色金属废弃物资源化是可持续经济发展的重要选择.中国人口资源与环境,1999,9(4):42-46
[44]彭容秋.重金属冶金学.长沙:中南大学出版社,2004.59-60
[45]潘朝群,邓先和,宾万达,等.NaOH、甘油的水溶液浸出三氧化二锑的机理研究.矿冶,2001,(2):31-36
[46]T.Oda.An algorithm for prediction of travel time using vehicle sensor data.In Third International Conference OnRoad Traffic Control.1990,40-44.
[47]钟云波,梅光贵,钟竹前.硫化法脱除铜电解废液中As、Sb、Bi的试验.中南大学学报,1997,28(4):336-339
[48]梅光贵,钟云波,钟竹前.硫化沉淀法净化铜废电解液的热力学分析.中南大学学报,1996,27(1):31-35