铅鼓风炉烟尘的综合回收
摘要
本文主要研究了一种从鼓风炉高砷含铟烟尘中分离砷及提取铟、锌的对环境友好的新工艺。
通过对云锡铅鼓风炉烟尘浸出过程中锌、铟、砷等主要元素的分布走向进行分析,重点开展了循环浸出富集铟、锌、砷的工艺实验研究,提出了“中酸循环浸出-保温过滤-冷却过滤分离砷-改变酸度过滤分离锌-萃取提铟”工艺,回收其中的锌、砷、铟。通过系统的实验研究,开发出了适宜于处理云锡铅鼓风炉烟尘的工艺方法,得到了可以指导实际工业生产的数据和经验。
本研究实验包括条件实验和循环浸出实验。由于硫酸锌和三氧化二砷在不同酸度和不同温度下的溶解度不同;因此,通过改变浸出液温度和调节其酸度的方法脱锌和砷。研究内容包括浸出酸度、温度、液固比、时间对各元素浸出率的影响。
条件实验表明:浸出酸度在7mol/L,温度85℃,时间1.5小时,液固比为4:1时,各元素的浸出率达到最大。
小型实验表明:浸出酸度控制在7mol/L,温度85℃,时间设定1.5小时,液固比为4:1,每轮浸出后浸出液冷却过滤得到74.90%的粗三氧化二砷晶体,七轮浸出后提高浸出液酸度至13mol/L后,过滤得到84.73%的粗制品七水硫酸锌;浸出液萃取提铟,萃取率达82.46%。
试验所提出的流程,实现了溶液闭路循环,无废渣排放,成功分离了砷、铟、锌,为今后该物料的处理提供了一条新的思路。
In this paper, a new process was studied to separate arsenic and extract Indium and zinc from lead blast furnace dust contaning Indium, zinc and arsenic.
The distributiones of Zinc and Indium and Arsenic in the leaching process of the lead blast furnace dust from YunnanTin Co.were studied. A new process, which consist of middle acid circle leching, heat preservation filtering, arsenic oxide crystalizing were introduced. In the experiments, separating Zinc and Arsenic and extracting Indium according to the process were studied mainly. The suitable process and technological parameters were determined for the practical application.
The experiments include two parts: condition experiments and circle leaching. Base on the solubility of ZnSO_4 and As_2O_3 was different on the conditions of different acidity and temperature, separating Zinc and Arsenic were achieved by the way of changing the temperature and leaching acidity. Some influence factors: temperature, acidity, liquid/solid and leaching time, etc were studied.
The results from the laboratory experiment showed that when the acidity was 7mol/l, the temperature was 85℃, the liquid/solid was 4:1 and the leaching time was 1.5h, a rough As_2O_3 amount to 74.90% was gained in the crystal step, a rough ZnSO_4·7H_2O amount to 84.73% was gained when the acidity get to 13mol/l after seventh leching rounds, and a 82.46% extraction rate of Indium was achieved.
The process has the advantages of simplicity, low cost, high recovery rate for valuable metals, high production and a little pollution, etc. A new idea is provided to deal with containing arsenic materials.
通过对云锡铅鼓风炉烟尘浸出过程中锌、铟、砷等主要元素的分布走向进行分析,重点开展了循环浸出富集铟、锌、砷的工艺实验研究,提出了“中酸循环浸出-保温过滤-冷却过滤分离砷-改变酸度过滤分离锌-萃取提铟”工艺,回收其中的锌、砷、铟。通过系统的实验研究,开发出了适宜于处理云锡铅鼓风炉烟尘的工艺方法,得到了可以指导实际工业生产的数据和经验。
本研究实验包括条件实验和循环浸出实验。由于硫酸锌和三氧化二砷在不同酸度和不同温度下的溶解度不同;因此,通过改变浸出液温度和调节其酸度的方法脱锌和砷。研究内容包括浸出酸度、温度、液固比、时间对各元素浸出率的影响。
条件实验表明:浸出酸度在7mol/L,温度85℃,时间1.5小时,液固比为4:1时,各元素的浸出率达到最大。
小型实验表明:浸出酸度控制在7mol/L,温度85℃,时间设定1.5小时,液固比为4:1,每轮浸出后浸出液冷却过滤得到74.90%的粗三氧化二砷晶体,七轮浸出后提高浸出液酸度至13mol/L后,过滤得到84.73%的粗制品七水硫酸锌;浸出液萃取提铟,萃取率达82.46%。
试验所提出的流程,实现了溶液闭路循环,无废渣排放,成功分离了砷、铟、锌,为今后该物料的处理提供了一条新的思路。
In this paper, a new process was studied to separate arsenic and extract Indium and zinc from lead blast furnace dust contaning Indium, zinc and arsenic.
The distributiones of Zinc and Indium and Arsenic in the leaching process of the lead blast furnace dust from YunnanTin Co.were studied. A new process, which consist of middle acid circle leching, heat preservation filtering, arsenic oxide crystalizing were introduced. In the experiments, separating Zinc and Arsenic and extracting Indium according to the process were studied mainly. The suitable process and technological parameters were determined for the practical application.
The experiments include two parts: condition experiments and circle leaching. Base on the solubility of ZnSO_4 and As_2O_3 was different on the conditions of different acidity and temperature, separating Zinc and Arsenic were achieved by the way of changing the temperature and leaching acidity. Some influence factors: temperature, acidity, liquid/solid and leaching time, etc were studied.
The results from the laboratory experiment showed that when the acidity was 7mol/l, the temperature was 85℃, the liquid/solid was 4:1 and the leaching time was 1.5h, a rough As_2O_3 amount to 74.90% was gained in the crystal step, a rough ZnSO_4·7H_2O amount to 84.73% was gained when the acidity get to 13mol/l after seventh leching rounds, and a 82.46% extraction rate of Indium was achieved.
The process has the advantages of simplicity, low cost, high recovery rate for valuable metals, high production and a little pollution, etc. A new idea is provided to deal with containing arsenic materials.
引文
[1]周令治,邹家炎.稀散金属手册.中南工业大学出版社,1993,13-37
[2]费多洛夫,阿克楚林.铟化学手册.北京大学出版社,2005,183-248
[3]A.H泽里克曼.稀有金属冶金.北京:冶金工业出版社,1959,419
[4]稀有金属应用编写组.稀有金属应用.北京:冶金工业出版社,1974,127-134
[5]伍锡军.国内外锗和铟回收工艺的发展.1995(3)218-223
[6]屠海令,赵国全,郭青蔚.有色金属冶金、材料、再生与环保.北京:化学工业出版社,2003,303
[7]刘世友.铟的生产、应用和开发.稀有金属和硬质合金,1994(12):49-53
[8]王顺昌等.铟的资源、应用和市场.世界有色金属,2000(12):22-24
[9]Barakat,M A Recovery of lead,tin and indium from alloy wire scrap.Hydrometallurgy,1998(49)1-2:63-73
[10]Meng,Li-Jian,Crossan,etal."Indium-tin-oxide thin film prepared by microwave-enhanced reactive magnetron sputtering for telecommunication wavelengths"Thin Solid Films 2002 pp.80-86
[11]刘大春,杨斌,戴永年等.云南铟资源及其产业发展.广东有色金属学报,2005,15(1):1-3
[12]Pla J,Tamasi M,Rizzoli R,Losurdo M,Centurioni E,Summonte C,Rubinelli F."Optimization of ITO layers for applications in a-Si/c-Si heterojunction solar cells" Thin Solid Films 2003 pp.185-192
[13]Eberl K,Lipinski M,Manz YM,Jin-Phillipp NY,Winter W,Lange C,Schmidt OG."Self-assembling InAs and InP quantum dots for Optoelectronic devices" Thin Solid Films 2000 pp.183-188
[14]曾东铭,刘又年,舒万良等.低酸浸出-溶剂萃取法从含铟溶液中回收铟.稀有金属,2002(8):42-44
[15]王树楷.铟冶金.冶金工业出版社,2006,30-73
[16]Heng C L,Liu Y J,Wee A T S,Finstad T G."Thef ormation of Ge nanocrystals in a metal-insulator-semiconductor structure and its memory effect" Journal of Crystal Growth 2004 pp.95-104
[17]Wu XC,Hong JM,Han Z J,TaoYR."Fabrication and photoluminescence characteristics of single crystalline In203 nanowires" Chemical Physics Letters 2003 pp.28-32
[18]Zudans I,Seliskar C J,Heineman W R."In situ measurements of sensor film dynamics by spectroscopic ellipsometry.Demonstration of back-side measurements and the etching of indium tin oxide" Thin Solid Films 2003 pp.238-245
[19]Hultaker,Annette,Jarrendahl,Kenneth,Lu Jun,Granqvist,Claes-Goran,Niklasson,Gunnar A."Electrical and optical properties of oxide thin films with silver additive" Thin Solid Films 2001 pp.305-310
[20]戴永年主编.金属及矿产品深加工.北京:冶金工业出版社,2007
[21]冯树屏.砷分析化学,北京:中国环境科学出版社,1986:1-101
[22]肖若珀.砷的提取、环保和应用方向,南宁:广西金属学会出版社,1992:12-296
[23]Norbert L Pirt,Albert E Melin.Descussion about Arsenic Subjects in the Nonferrous Metallurgy.Koch M,Tayor J C.Productivity and Technology in the Metallurgical Industries,New York:The Minerals and Matels Materials Society,1989:735-824
[24]株洲冶炼厂情报室.“国内砷资源及生产和应用调查报告”,1981.
[25]R.G.Robins et al.Research and Developmentin Extractive Metallurgy,May 1987:29-36
[26]陈维平,李仲英,边可君等.中国环境科学,1999,19(4):310-312
[27]T.R.Harper,N.W.Kingham.Water Environment Research,1992,64(3):200-203
[28]杨天足.高砷金矿提取金、砷新工艺和基础理论研究,中南工业大学,1990
[29]杜清枝,杨继舜.物理化学.重庆:重庆大学出版社,1997
[30]宋世谟,李世丰等.物理化学.北京:冶金工业出版社,1992
[31]A.W.Adamson:Understanding Physical Chemistry,1978
[32]曾庆恒.物理化学.武汉:中南工业大学出版社,1992
[33]砷译文集,云南锡业公司,1985,6
[34]殷德洪,黄其兴,刘特明.有色金属(冶炼部分),1984,6,12
[35]有色金属冶炼设备委员会.有色金属冶炼设备第二卷湿法冶炼设备.北京:冶金工业出版社,1993
[36]Monhemius A J,Swash P M.Removing and StabilizingArsenic f rom Copper Refining Circuits by Hydrot hermalprocessing[J].Journal of Hazardous Materials.1999,51(9):30-33.
[37]Tony Jong,David L Parry.Evaluation of t he Stability of Arsenic Immobilized by Microbial Sulfate Reduction Using TCLP Extractions and Long-term Leaching Techniques[J].Chemosphere.2005,60:254-265.
[38]赵萌,宁平.含砷污泥的固化处理[J].昆明理工大学学报(理工版).2003,28(5):100.104
[39]Leist M,Casey R J,Caridi D.the Management of Arsenic Wastes:Problems and Prospects[J].Journal of Hazardous Material.2000(B76):125-138.
[40]张玉洋,盖赫莉,程卉.砷污染及其防治[J].黑龙江环境通报.2000,24(2):83-84
[41]梅光贵,王德润,周敬元,等.湿法冶锌学.长沙:中南工业大学出版社,2001
[42]彭荣秋主编.重金属冶金学(第二版).长沙:中南大学出版社,2004
[43]魏昶.湿法炼锌理论与应用.昆明:云南科技出版社,2003
[44]陈雪云.利用铟萃余液和烟化炉ZnO生产ZnS04.7H20的试验研究.湖南有色金属.2003.19(4)24-26
[45]梅光贵,钟竹前.湿法冶金新工艺,长沙:中南工业大学出版社,1994.
[46]魏昶,姜琪.等.重有色金属冶炼中砷的脱除与回收.有色冶金,2003,55(3):46-50
[47]文岳中,刘又年等.酸化焙烧.水浸提铟的研究.稀有金属,1999(23):227-231
[48]陈维平.清洁生产方法制备砷新工艺及其基础理论研究.湖南大学博士学位论文,2000.
[2]费多洛夫,阿克楚林.铟化学手册.北京大学出版社,2005,183-248
[3]A.H泽里克曼.稀有金属冶金.北京:冶金工业出版社,1959,419
[4]稀有金属应用编写组.稀有金属应用.北京:冶金工业出版社,1974,127-134
[5]伍锡军.国内外锗和铟回收工艺的发展.1995(3)218-223
[6]屠海令,赵国全,郭青蔚.有色金属冶金、材料、再生与环保.北京:化学工业出版社,2003,303
[7]刘世友.铟的生产、应用和开发.稀有金属和硬质合金,1994(12):49-53
[8]王顺昌等.铟的资源、应用和市场.世界有色金属,2000(12):22-24
[9]Barakat,M A Recovery of lead,tin and indium from alloy wire scrap.Hydrometallurgy,1998(49)1-2:63-73
[10]Meng,Li-Jian,Crossan,etal."Indium-tin-oxide thin film prepared by microwave-enhanced reactive magnetron sputtering for telecommunication wavelengths"Thin Solid Films 2002 pp.80-86
[11]刘大春,杨斌,戴永年等.云南铟资源及其产业发展.广东有色金属学报,2005,15(1):1-3
[12]Pla J,Tamasi M,Rizzoli R,Losurdo M,Centurioni E,Summonte C,Rubinelli F."Optimization of ITO layers for applications in a-Si/c-Si heterojunction solar cells" Thin Solid Films 2003 pp.185-192
[13]Eberl K,Lipinski M,Manz YM,Jin-Phillipp NY,Winter W,Lange C,Schmidt OG."Self-assembling InAs and InP quantum dots for Optoelectronic devices" Thin Solid Films 2000 pp.183-188
[14]曾东铭,刘又年,舒万良等.低酸浸出-溶剂萃取法从含铟溶液中回收铟.稀有金属,2002(8):42-44
[15]王树楷.铟冶金.冶金工业出版社,2006,30-73
[16]Heng C L,Liu Y J,Wee A T S,Finstad T G."Thef ormation of Ge nanocrystals in a metal-insulator-semiconductor structure and its memory effect" Journal of Crystal Growth 2004 pp.95-104
[17]Wu XC,Hong JM,Han Z J,TaoYR."Fabrication and photoluminescence characteristics of single crystalline In203 nanowires" Chemical Physics Letters 2003 pp.28-32
[18]Zudans I,Seliskar C J,Heineman W R."In situ measurements of sensor film dynamics by spectroscopic ellipsometry.Demonstration of back-side measurements and the etching of indium tin oxide" Thin Solid Films 2003 pp.238-245
[19]Hultaker,Annette,Jarrendahl,Kenneth,Lu Jun,Granqvist,Claes-Goran,Niklasson,Gunnar A."Electrical and optical properties of oxide thin films with silver additive" Thin Solid Films 2001 pp.305-310
[20]戴永年主编.金属及矿产品深加工.北京:冶金工业出版社,2007
[21]冯树屏.砷分析化学,北京:中国环境科学出版社,1986:1-101
[22]肖若珀.砷的提取、环保和应用方向,南宁:广西金属学会出版社,1992:12-296
[23]Norbert L Pirt,Albert E Melin.Descussion about Arsenic Subjects in the Nonferrous Metallurgy.Koch M,Tayor J C.Productivity and Technology in the Metallurgical Industries,New York:The Minerals and Matels Materials Society,1989:735-824
[24]株洲冶炼厂情报室.“国内砷资源及生产和应用调查报告”,1981.
[25]R.G.Robins et al.Research and Developmentin Extractive Metallurgy,May 1987:29-36
[26]陈维平,李仲英,边可君等.中国环境科学,1999,19(4):310-312
[27]T.R.Harper,N.W.Kingham.Water Environment Research,1992,64(3):200-203
[28]杨天足.高砷金矿提取金、砷新工艺和基础理论研究,中南工业大学,1990
[29]杜清枝,杨继舜.物理化学.重庆:重庆大学出版社,1997
[30]宋世谟,李世丰等.物理化学.北京:冶金工业出版社,1992
[31]A.W.Adamson:Understanding Physical Chemistry,1978
[32]曾庆恒.物理化学.武汉:中南工业大学出版社,1992
[33]砷译文集,云南锡业公司,1985,6
[34]殷德洪,黄其兴,刘特明.有色金属(冶炼部分),1984,6,12
[35]有色金属冶炼设备委员会.有色金属冶炼设备第二卷湿法冶炼设备.北京:冶金工业出版社,1993
[36]Monhemius A J,Swash P M.Removing and StabilizingArsenic f rom Copper Refining Circuits by Hydrot hermalprocessing[J].Journal of Hazardous Materials.1999,51(9):30-33.
[37]Tony Jong,David L Parry.Evaluation of t he Stability of Arsenic Immobilized by Microbial Sulfate Reduction Using TCLP Extractions and Long-term Leaching Techniques[J].Chemosphere.2005,60:254-265.
[38]赵萌,宁平.含砷污泥的固化处理[J].昆明理工大学学报(理工版).2003,28(5):100.104
[39]Leist M,Casey R J,Caridi D.the Management of Arsenic Wastes:Problems and Prospects[J].Journal of Hazardous Material.2000(B76):125-138.
[40]张玉洋,盖赫莉,程卉.砷污染及其防治[J].黑龙江环境通报.2000,24(2):83-84
[41]梅光贵,王德润,周敬元,等.湿法冶锌学.长沙:中南工业大学出版社,2001
[42]彭荣秋主编.重金属冶金学(第二版).长沙:中南大学出版社,2004
[43]魏昶.湿法炼锌理论与应用.昆明:云南科技出版社,2003
[44]陈雪云.利用铟萃余液和烟化炉ZnO生产ZnS04.7H20的试验研究.湖南有色金属.2003.19(4)24-26
[45]梅光贵,钟竹前.湿法冶金新工艺,长沙:中南工业大学出版社,1994.
[46]魏昶,姜琪.等.重有色金属冶炼中砷的脱除与回收.有色冶金,2003,55(3):46-50
[47]文岳中,刘又年等.酸化焙烧.水浸提铟的研究.稀有金属,1999(23):227-231
[48]陈维平.清洁生产方法制备砷新工艺及其基础理论研究.湖南大学博士学位论文,2000.