废弃印刷线路板中金属回收工艺的研究
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摘要
随着我国废旧电器数量的增加,废弃的印刷线路板(废PCB)也在急剧增加。废弃PCB中含有大量的贵金属,可以被回收利用;同时,又含有多种重金属和有毒有害物质,处理不当会严重污染环境。目前,废弃印刷线路板回收处理技术主要包括三类:热处理法、化学处理法和机械物理处理法,但都存在回收效率偏低的问题。
本文研究了印刷线路板中贵重金属回收工艺的主要部分:印刷线路板的解离,破碎物料的气流分选、分选产品有机组分的去除。通过实验对贵重金属的回收条件做了优化,提高了回收效率,为今后走向工业化提供了重要理论基础。
解离实验结果表明:破碎后的物料主要集中在0.074～0.125mm,0.125～0.25mm,0.25～0.42mm,0.42～0.84mm的4个粒径范围;粒径小于0.84mm的废弃印刷线路板破碎料中金属和非金属基本解离;不同破碎时间下,随着时间增加,金属解离度也随之增加,但到了一定时间(130s),解离度变化不大;在最低转速下,金属解离度不够理想,在大于2000r/min的转速下就能达到较理想的分离效果。
气流分选技术对废弃印刷线路板破碎料有较好的分选富集作用,通过计算确定出不同粒径下的最佳操作气速:0.074～0.125mm,0.125～0.25mm,0.25～0.42mm,0.42～0.84mm 4个粒径对应的最佳分选气速分别是0.24m/s,0.28m/s,0.57m/s和0.71m/s,铜的回收率分别为90.56%,85.34%,86.28%,80.33%。
火法实验结果表明:火法焚烧可以有效去除物料中有机组分,即在冶炼中产生有毒有害气体的组分;在相同的加热时间下(60min),得出在600℃时为最优加热温度;在相同的温度(600℃)下进行试验,得出物料在加热40min的时间内能够充分燃烧。
With the rapid growth of waste electrical and electronic equipment(WEEE) in our country, the quantity of waste printed circuit board(PCB) is increasing sharply in recent years.Lots of precious metals were contained in the PCB and can be recycled as resources,at the same time, large amounts heavy metal and other toxic substances were contained in the PCB and may pollute environmental severely without appropriate treatment.There are three kinds of recycling techniques in recent:heat treatment,chemistry processing and mechanical treatment. Lower recycling efficiency was feature in these techniques.
This paper studies three main parts of the metal recovery process in the PCB:the PCB dissociation,flow separation of broken materials,remove the organic components of separated products.For each part of the experiment,all of the experimental conditions for recycling metals have been optimized,and the recycling efficiency was heightened significantly,the experimental results provide theoretic foundation for industrialization in the future.
Liberation experimental results show that:the crushed materials mainly concentrated in the size of 0.074 to 0.125 mm,0.125～0.25mm,0.42mm to 0.25,0.42 to 0.84mm;The metal and non-metallic in the material smaller than 0.84 mm are basically separated;At different broken time.as the time increases,metal liberation degree also will be increased gradually,but at a certain period of time(130 s),the liberation degree change little;In the minimum speed, metal liberation is not in expectation,when the rotate speed is over 2000r/min,can reach an ideal separation results.
Dealing with the printed circuit board scrap by using air separation technology have achieved separation enrichment effectively,different size can be identified by calculating the optimum operation of gas velocity:in the size of 0.074 to 0.125mm,0.125～0.25mm,0.42mm～0.25,0.42 to 0.84mm,the better separation gas velocity is 0.24 m/s,0.28m/s,0.57m/s and 0.71 m/s,copper recovery rates were 90.56%,85.34%,86.28%,80.33%respectively.
The fire experimental results show that:burning can effectively remove organic compounds in the separated material,which produced poisonous gas component in smelting technology:the copper concentrated at the size of 0.42～0.84mm,0.25-0.42mm.In the same heating time(60 min),600℃is the ideal heating temperature;under the same temperature(600℃),materials were fully burned over the time of 40 min.
本文研究了印刷线路板中贵重金属回收工艺的主要部分:印刷线路板的解离,破碎物料的气流分选、分选产品有机组分的去除。通过实验对贵重金属的回收条件做了优化,提高了回收效率,为今后走向工业化提供了重要理论基础。
解离实验结果表明:破碎后的物料主要集中在0.074～0.125mm,0.125～0.25mm,0.25～0.42mm,0.42～0.84mm的4个粒径范围;粒径小于0.84mm的废弃印刷线路板破碎料中金属和非金属基本解离;不同破碎时间下,随着时间增加,金属解离度也随之增加,但到了一定时间(130s),解离度变化不大;在最低转速下,金属解离度不够理想,在大于2000r/min的转速下就能达到较理想的分离效果。
气流分选技术对废弃印刷线路板破碎料有较好的分选富集作用,通过计算确定出不同粒径下的最佳操作气速:0.074～0.125mm,0.125～0.25mm,0.25～0.42mm,0.42～0.84mm 4个粒径对应的最佳分选气速分别是0.24m/s,0.28m/s,0.57m/s和0.71m/s,铜的回收率分别为90.56%,85.34%,86.28%,80.33%。
火法实验结果表明:火法焚烧可以有效去除物料中有机组分,即在冶炼中产生有毒有害气体的组分;在相同的加热时间下(60min),得出在600℃时为最优加热温度;在相同的温度(600℃)下进行试验,得出物料在加热40min的时间内能够充分燃烧。
With the rapid growth of waste electrical and electronic equipment(WEEE) in our country, the quantity of waste printed circuit board(PCB) is increasing sharply in recent years.Lots of precious metals were contained in the PCB and can be recycled as resources,at the same time, large amounts heavy metal and other toxic substances were contained in the PCB and may pollute environmental severely without appropriate treatment.There are three kinds of recycling techniques in recent:heat treatment,chemistry processing and mechanical treatment. Lower recycling efficiency was feature in these techniques.
This paper studies three main parts of the metal recovery process in the PCB:the PCB dissociation,flow separation of broken materials,remove the organic components of separated products.For each part of the experiment,all of the experimental conditions for recycling metals have been optimized,and the recycling efficiency was heightened significantly,the experimental results provide theoretic foundation for industrialization in the future.
Liberation experimental results show that:the crushed materials mainly concentrated in the size of 0.074 to 0.125 mm,0.125～0.25mm,0.42mm to 0.25,0.42 to 0.84mm;The metal and non-metallic in the material smaller than 0.84 mm are basically separated;At different broken time.as the time increases,metal liberation degree also will be increased gradually,but at a certain period of time(130 s),the liberation degree change little;In the minimum speed, metal liberation is not in expectation,when the rotate speed is over 2000r/min,can reach an ideal separation results.
Dealing with the printed circuit board scrap by using air separation technology have achieved separation enrichment effectively,different size can be identified by calculating the optimum operation of gas velocity:in the size of 0.074 to 0.125mm,0.125～0.25mm,0.42mm～0.25,0.42 to 0.84mm,the better separation gas velocity is 0.24 m/s,0.28m/s,0.57m/s and 0.71 m/s,copper recovery rates were 90.56%,85.34%,86.28%,80.33%respectively.
The fire experimental results show that:burning can effectively remove organic compounds in the separated material,which produced poisonous gas component in smelting technology:the copper concentrated at the size of 0.42～0.84mm,0.25-0.42mm.In the same heating time(60 min),600℃is the ideal heating temperature;under the same temperature(600℃),materials were fully burned over the time of 40 min.
引文
[1]温雪峰.废弃线路板的资源化研究.中国矿业大学硕士学位论文[D],2001:12-22
[2]电阻的基础知识.http://jinfengab.51.net/dzyl-1.htm
[3]王晖,顾帼华.报废电子器件处理技术进展[J].环境污染与防治,2003,25(4):218-220
[4]Klaus Gockmann.Recycling of copper[M].CIM BULLETIN,VOLUME 85.1992.3
[5]Legarth J.B.Environmental decision making for recycling options[J].Resources Conservation and Recycling,1997,19:109-135
[6]刘子卫.印刷线路板制造业废弃物之回收与处理.工业污染防治报导[J].1995,8(85):1-3
[7]张洪建,赵跃民,王全,段晨龙.湿法破碎在废弃线路板资源化中的应用[J].环境工程.2006,24(5):60-63
[8]Shunli Zhang.Elic Forssberg.Resources,Conservation and Recycling[J].1997,21,247-269
[9]祝大同.亚洲印制电路板业的现状和发展[J].电子工艺技术,1997,9:175-178
[10]中国电了工业年鉴[M].第一版,北京:1998.12
[11]辜信实.印制电路用覆铜箔层压板[M].北京:化学工业出版社材料科学与工程出版中心北京,2002
[12]闻芹堂,刘梅生.我国印制电路板配套用化工材料的现状及发展趋势[J].江苏化工,1998 26(4):4-6
[13]温雪峰.物理法回收废弃电路板中金属富集体的研究[D].博士学位论文,江苏徐州:中国矿业大学.2004
[14]Wang JW,Xu JQ.Environmental Implications of PCB Manufacturing in China[C].IEEE International Symposium on Electronics and the Environment,2004,USA:156-158
[15]邱胜鹏.国内电子废弃物处理现状[J].能源环境与环境,2006 1:61-63
[16]沈志刚.废印刷线路板回收处理技术进展[J].新材料产业,2006;10:43-46
[17]郑智和.印刷线路板废板边料资源化技术及设备[M].台湾环保产业,2002
[18]Bemardes A.,Bohlinger I,Rodriguez D.,Milbrandt H.,Wuth W.Recycling of printed circuit boards by melting with oxidizing/reducing top blowing process[C].TMS Annual Meeting,9 a13 de fevereiro de 1997,Orlando,Florida,EU
[19]韩洁,聂永丰,王晖.废印刷线路板的回收利用[J].城市环境与城市生态,2001,14(6)6:11-14
[20]Chien Y.,Wang H.P.,Lin K.S.,Huang Y.J.,Yang Y.W.Fate of bromine in pyrolysis of printed circuit board wastes[J].Chemosphere,2000,40:383-387
[21]查建宁.电子废弃物的环境污染及防治对策[J].污染防治技术,2002,15(3):35-36
[22]丘波,彭琳.电子废弃物回收拆解业工人健康调查[J].环境与健康,2005,22(6):419-421
[23]彭琳,霍霞.电子废物回收拆解污染对儿童血铅的影响[J].汕头大学医学院学报,2005,18(1):48-50
[24]段晨龙,赵跃民,温雪峰,叶璀玲,王全.废弃电路板破碎中热解气体的研究[J].中国矿业大学学报.2005,34(6):730-734
[25]孙路石.废弃印刷线路板的热解机理及产物回收利用的试验研究[D].博士学位论文,湖北武汉:华中科技大学,2004
[26]罗志华.火法冶金工艺处理电子线路板并富集贵稀金属的试验研究[D].同济大学工学硕士学位论文.2007.3
[27]朱雯.废电脑及配件的材料回收南京理工大学硕士学位论文[D].2004.2
[28]杨玉芬,盖国胜,徐盛明,陈清如.废印刷线路板中稀贵金属的回收现状[J].稀有金属.2004,28(4):716-719
[29]Yokoyama S,IjiM.Recycling Of Printed Writing Board waste[J].Proceedings of 1993IEEE/Tsukuba.Intenaational Workshop on Advance-d Robotics.IEEE,1993.55-58
[30]Shunli Zhang,Eric Forssberg.Intelligent liberation and classification electronic scrap[J].Powder Technology,1999,(105):295-301
[31]Melchiorre M.Jakob R.Electronic scrap Recycling[J].Micro electronic Janoumal,IEEE,1996,28(8-10):ⅹⅹⅱ-ⅹⅹⅳ.
[32]Zhang Shunli,Forssberg Eric,Arvidson Bo,et al.Aluminum Recovery from Electronic Scrap by High-Force Eddy Current Separation[J].Resources,Conservation and Recycling,1998(23):225-241
[33]丁涛,夏志东,毛倩瑾,雷永平.废弃印刷线路板的气流分选研究.电子工艺技术.2006,27(6):348-351
[34]胡张喜.基于超临界流体技术的印刷线路板回收实验及机理研究[D].硕士学位论文,安徽合肥:合肥工业大学,2007
[35]孙路石,陆继东,王世杰等.印刷线路板废弃物热解实验研究[J].化工学报,2003,54(3):408-412
[36]杨若明.环境中有毒有害化学物质的污染与监测[M].北京:中央民族大学出版社,2001.4
[37]名鲜花.从烂版废液中回收硫酸铜实验的改进[J].雁北师范学院学报,2003,19(2):35-36
[38]黄一石,乔子荣主编.定量化学分析[M].北京:化学工业出版社,2004:29-40
[39]王秋长,赵鸿喜,张守民,李一峻编.基础化学实验[M].北京:科学出版社.2003:220-222
[40]PC.Rem,S.Zhang,E.Forssberg,T.P.R.de Jong.Investigation of separability of particles smaller than 5mm by Eddy-current separation technology—partⅡ.Novel design concepts[J].Magnet.Elect,2000,12:85-90
[41]S.Zhang,E.Forssberg.Optimization of electrodynamic separation for metals recovery from electronic scrap[J].Resources,Conservation and Recycling,1998,22:143-162
[42]Shunli Zhang,Eric Forssberg,Bo Arvidson,William Moss.Aluminum recovery from electronic scrap by High-Force eddy-current separators[J].Resources,Conservation and Recycling,1998,23:225-240
[43]王勇,李国建.含铜有机废物的处理与回收[J].再生资源研究,1997,6:26-28
[44]Shunli Zhang,Eric Forssberg.Intelligent liberation and classification of electronic scrap[J].Powder Technology,1999,105:295-301
[45]汪群惠.固体废物处理及资源化[M].北京:化学工业出版社,2004:115-117
[46]《选矿学》实验指导书[M].徐州:中国矿业大学出版社:1-4
[47]朱萍,古国榜.从印刷线路板废料中回收金和铜的研究[J].稀有金属,2002,26(3):214-216
[2]电阻的基础知识.http://jinfengab.51.net/dzyl-1.htm
[3]王晖,顾帼华.报废电子器件处理技术进展[J].环境污染与防治,2003,25(4):218-220
[4]Klaus Gockmann.Recycling of copper[M].CIM BULLETIN,VOLUME 85.1992.3
[5]Legarth J.B.Environmental decision making for recycling options[J].Resources Conservation and Recycling,1997,19:109-135
[6]刘子卫.印刷线路板制造业废弃物之回收与处理.工业污染防治报导[J].1995,8(85):1-3
[7]张洪建,赵跃民,王全,段晨龙.湿法破碎在废弃线路板资源化中的应用[J].环境工程.2006,24(5):60-63
[8]Shunli Zhang.Elic Forssberg.Resources,Conservation and Recycling[J].1997,21,247-269
[9]祝大同.亚洲印制电路板业的现状和发展[J].电子工艺技术,1997,9:175-178
[10]中国电了工业年鉴[M].第一版,北京:1998.12
[11]辜信实.印制电路用覆铜箔层压板[M].北京:化学工业出版社材料科学与工程出版中心北京,2002
[12]闻芹堂,刘梅生.我国印制电路板配套用化工材料的现状及发展趋势[J].江苏化工,1998 26(4):4-6
[13]温雪峰.物理法回收废弃电路板中金属富集体的研究[D].博士学位论文,江苏徐州:中国矿业大学.2004
[14]Wang JW,Xu JQ.Environmental Implications of PCB Manufacturing in China[C].IEEE International Symposium on Electronics and the Environment,2004,USA:156-158
[15]邱胜鹏.国内电子废弃物处理现状[J].能源环境与环境,2006 1:61-63
[16]沈志刚.废印刷线路板回收处理技术进展[J].新材料产业,2006;10:43-46
[17]郑智和.印刷线路板废板边料资源化技术及设备[M].台湾环保产业,2002
[18]Bemardes A.,Bohlinger I,Rodriguez D.,Milbrandt H.,Wuth W.Recycling of printed circuit boards by melting with oxidizing/reducing top blowing process[C].TMS Annual Meeting,9 a13 de fevereiro de 1997,Orlando,Florida,EU
[19]韩洁,聂永丰,王晖.废印刷线路板的回收利用[J].城市环境与城市生态,2001,14(6)6:11-14
[20]Chien Y.,Wang H.P.,Lin K.S.,Huang Y.J.,Yang Y.W.Fate of bromine in pyrolysis of printed circuit board wastes[J].Chemosphere,2000,40:383-387
[21]查建宁.电子废弃物的环境污染及防治对策[J].污染防治技术,2002,15(3):35-36
[22]丘波,彭琳.电子废弃物回收拆解业工人健康调查[J].环境与健康,2005,22(6):419-421
[23]彭琳,霍霞.电子废物回收拆解污染对儿童血铅的影响[J].汕头大学医学院学报,2005,18(1):48-50
[24]段晨龙,赵跃民,温雪峰,叶璀玲,王全.废弃电路板破碎中热解气体的研究[J].中国矿业大学学报.2005,34(6):730-734
[25]孙路石.废弃印刷线路板的热解机理及产物回收利用的试验研究[D].博士学位论文,湖北武汉:华中科技大学,2004
[26]罗志华.火法冶金工艺处理电子线路板并富集贵稀金属的试验研究[D].同济大学工学硕士学位论文.2007.3
[27]朱雯.废电脑及配件的材料回收南京理工大学硕士学位论文[D].2004.2
[28]杨玉芬,盖国胜,徐盛明,陈清如.废印刷线路板中稀贵金属的回收现状[J].稀有金属.2004,28(4):716-719
[29]Yokoyama S,IjiM.Recycling Of Printed Writing Board waste[J].Proceedings of 1993IEEE/Tsukuba.Intenaational Workshop on Advance-d Robotics.IEEE,1993.55-58
[30]Shunli Zhang,Eric Forssberg.Intelligent liberation and classification electronic scrap[J].Powder Technology,1999,(105):295-301
[31]Melchiorre M.Jakob R.Electronic scrap Recycling[J].Micro electronic Janoumal,IEEE,1996,28(8-10):ⅹⅹⅱ-ⅹⅹⅳ.
[32]Zhang Shunli,Forssberg Eric,Arvidson Bo,et al.Aluminum Recovery from Electronic Scrap by High-Force Eddy Current Separation[J].Resources,Conservation and Recycling,1998(23):225-241
[33]丁涛,夏志东,毛倩瑾,雷永平.废弃印刷线路板的气流分选研究.电子工艺技术.2006,27(6):348-351
[34]胡张喜.基于超临界流体技术的印刷线路板回收实验及机理研究[D].硕士学位论文,安徽合肥:合肥工业大学,2007
[35]孙路石,陆继东,王世杰等.印刷线路板废弃物热解实验研究[J].化工学报,2003,54(3):408-412
[36]杨若明.环境中有毒有害化学物质的污染与监测[M].北京:中央民族大学出版社,2001.4
[37]名鲜花.从烂版废液中回收硫酸铜实验的改进[J].雁北师范学院学报,2003,19(2):35-36
[38]黄一石,乔子荣主编.定量化学分析[M].北京:化学工业出版社,2004:29-40
[39]王秋长,赵鸿喜,张守民,李一峻编.基础化学实验[M].北京:科学出版社.2003:220-222
[40]PC.Rem,S.Zhang,E.Forssberg,T.P.R.de Jong.Investigation of separability of particles smaller than 5mm by Eddy-current separation technology—partⅡ.Novel design concepts[J].Magnet.Elect,2000,12:85-90
[41]S.Zhang,E.Forssberg.Optimization of electrodynamic separation for metals recovery from electronic scrap[J].Resources,Conservation and Recycling,1998,22:143-162
[42]Shunli Zhang,Eric Forssberg,Bo Arvidson,William Moss.Aluminum recovery from electronic scrap by High-Force eddy-current separators[J].Resources,Conservation and Recycling,1998,23:225-240
[43]王勇,李国建.含铜有机废物的处理与回收[J].再生资源研究,1997,6:26-28
[44]Shunli Zhang,Eric Forssberg.Intelligent liberation and classification of electronic scrap[J].Powder Technology,1999,105:295-301
[45]汪群惠.固体废物处理及资源化[M].北京:化学工业出版社,2004:115-117
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