旧尾矿库尾矿铅锌综合回收研究与应用
摘要
我国铅锌资源丰富,根据美国地质调查局资料,中国已成为世界最大的铅锌资源国家[1,21。随着经济的发展,对产品的需求量大幅增加,矿业开发规模也随之增大。选矿厂排放大量的尾矿和废水已成为制约企业可持续发展,危及矿区及周边生态环境的重要因素。在矿石日渐枯竭、环境意识日益增强的今天,铅锌尾矿已随选矿技术的发展,具备了一定的经济开发价值,对尾矿的二次开发利用已成为必然趋势。
某企业尾矿库中堆积了长年生产的老尾矿,保守估计有上百万吨。尾矿中含有的铅品位约0.7%左右,锌品位约2.5%左右,有价金属近3万吨,价值可观。经过前期的探索试验研究表明,这部分金属经过合理的选矿,可以综合回收利用,使尾矿变废为宝。符合国家的资源和产业政策。但是尾矿中的锌主要以氧化物的形式存在,氧化锌在工业生产中的选矿指标往往较差,本项目的最终目标是达到生产应用。
本文通过合理工艺流程研究,全部采用2000吨/日铅锌选厂未经处理的高钙废水作为现在尾矿再选选厂的用水,在不用新水的条件下,达到锌回收率高的尾矿资源的再回收利用。
通过采用各种选矿工艺流程,最终推荐不脱泥全浮选流程回收尾矿中的氧化锌矿,试验指标达到氧化锌精矿品位25%左右,回收率70%以上；工业试验指标达到氧化锌精矿品位25%左右,回收率55%以上。
Lead-zinc mineral resources are abundant in China; data from the USGS (United States Geological Survey) shows that China possesses the maximum amount of lead and zinc resources in the world. With the booming economy and demand for products, exploitation scale of China mining has expanded accordingly. Nevertheless, effluent and tailings from concentrators are intemperately discharged, which has greatly undermined substantial development and endangered ecological environment throughout mining areas. In the wake of growing environmental awareness, alone with gradual exhaustion of ores, owing to the development of mineral processing technology, recycling and reusing lead-zinc tailings has become an inexorable trend, since it brings certain profit.
An enterprise keeps at least a million tons tailings in the tailing pound for years of producing. The tailings contain about 0.7wt% Pb、2.5wt% Zn and 30,000 tons valuable metals, which, through a primary analysis and study, can be recovered by using an advisable beneficiation method. Zinc oxide dominates the zinc in these tailings; however, separation indicator is commonly unfavorable under the very circumstances. The ultimate goal of this project focuses on production and application.
A reasonable process is introduced in this paper that all process water of the new tailings concentration plant is supplied with raw high calcium effluent from the lead-zinc concentrator (2000 tons per day), in order to economically recycle and reuse zinc of the tailings with a high recovery rate.
Having conducted various beneficiation tests, full flotation without deslimed is highly recommended as the optimum process for recycling zinc oxide ore from the tailings. The lab flotation results show that zinc oxide concentrate with grade of 25.00% and recovery of over 70.00% were obtained; the pilot plant flotation results show that zinc oxide concentrate with grade of 25.00% and recovery of over 55.00% were obtained.
某企业尾矿库中堆积了长年生产的老尾矿,保守估计有上百万吨。尾矿中含有的铅品位约0.7%左右,锌品位约2.5%左右,有价金属近3万吨,价值可观。经过前期的探索试验研究表明,这部分金属经过合理的选矿,可以综合回收利用,使尾矿变废为宝。符合国家的资源和产业政策。但是尾矿中的锌主要以氧化物的形式存在,氧化锌在工业生产中的选矿指标往往较差,本项目的最终目标是达到生产应用。
本文通过合理工艺流程研究,全部采用2000吨/日铅锌选厂未经处理的高钙废水作为现在尾矿再选选厂的用水,在不用新水的条件下,达到锌回收率高的尾矿资源的再回收利用。
通过采用各种选矿工艺流程,最终推荐不脱泥全浮选流程回收尾矿中的氧化锌矿,试验指标达到氧化锌精矿品位25%左右,回收率70%以上；工业试验指标达到氧化锌精矿品位25%左右,回收率55%以上。
Lead-zinc mineral resources are abundant in China; data from the USGS (United States Geological Survey) shows that China possesses the maximum amount of lead and zinc resources in the world. With the booming economy and demand for products, exploitation scale of China mining has expanded accordingly. Nevertheless, effluent and tailings from concentrators are intemperately discharged, which has greatly undermined substantial development and endangered ecological environment throughout mining areas. In the wake of growing environmental awareness, alone with gradual exhaustion of ores, owing to the development of mineral processing technology, recycling and reusing lead-zinc tailings has become an inexorable trend, since it brings certain profit.
An enterprise keeps at least a million tons tailings in the tailing pound for years of producing. The tailings contain about 0.7wt% Pb、2.5wt% Zn and 30,000 tons valuable metals, which, through a primary analysis and study, can be recovered by using an advisable beneficiation method. Zinc oxide dominates the zinc in these tailings; however, separation indicator is commonly unfavorable under the very circumstances. The ultimate goal of this project focuses on production and application.
A reasonable process is introduced in this paper that all process water of the new tailings concentration plant is supplied with raw high calcium effluent from the lead-zinc concentrator (2000 tons per day), in order to economically recycle and reuse zinc of the tailings with a high recovery rate.
Having conducted various beneficiation tests, full flotation without deslimed is highly recommended as the optimum process for recycling zinc oxide ore from the tailings. The lab flotation results show that zinc oxide concentrate with grade of 25.00% and recovery of over 70.00% were obtained; the pilot plant flotation results show that zinc oxide concentrate with grade of 25.00% and recovery of over 55.00% were obtained.
引文
[1]戴自希.世界铅锌资源和开发利用现状[J].世界有色金属,2004(3)：22-29.
[2]U.S.Geological Survey, Mineral Commodity Summaries, January 2007.
[3]彭新平,陈伟,吴兆清.硫化铅锌矿选矿废水处理与回用技术研究[J].湖南有色金属,2010(4)：40-44.
[4]邓敬石,张宗华,陈家栋.浅谈含重金属离子的铅锌矿尾矿废水危害及治理[J].云南冶金,2002(4)：20-24.
[5]湖南有色金属研究院.云南会泽铅锌矿选矿废水回用及治理[R].长沙：湖南有色金属研究院,2001.
[6]张美钦.铅锌选矿厂尾矿综合利用途径浅析[J].化学工程与设备,2008(8)：104-109.
[7]罗洪涛.会理铅锌矿选矿废水的利用研究[J].矿产保护与利用.1999(4)：48-50.
[8]严群,罗仙平,赖兰萍等.会东铅锌矿选矿废水净化回用工艺的试验研究[J].工业水处理,2008(3)：57-60.
[9]张艳,戴晶平,张康生.凡口矿选矿废水处理与利用试验研究[J].矿冶工程,2008(3)：45-48.
[10]常前发,矿山固体废物的处理与处置[J].矿广保护与利用.2005(5)：38-42.
[11]曾懋华,颜美凤,奚长生,蒋荣华,方振鹏.从凡口铅锌矿尾矿中回收硫精矿的研究[J].冶金工程.2007(1)：36-42.
[12]王毓华.从铅锌浮选尾矿中回收氧化铅锌矿物的研究[J].金属矿山.2002(10)：154-158.
[13]周怡玫,严志明,汤小军,邱允武.尾矿中回收氧化锌的选矿工艺研究[J].有色金属(选矿部分)2008(1).
[14]余艳平,童雄,张桂芳,高西平.某氧化铅锌尾矿浮选试验研究[J].有色金属(选矿部分)2008(2).
[15]李亮,袁启东,王炬.从铅锌矿尾矿中回收锰的工艺研究[J].矿业快报.2008(11)：20-23.
[16]汪顺才,王方汉,曹维勤.废弃尾矿中碳酸锰矿铵盐焙烧富集工艺研究[J].金属矿山.2008(3)：144-149.
[17]金吉梅,曾娟,刘亮.铅锌尾矿回收自钨试验研究[J].矿业工程.2009(6)：23-28.
[18]朱建平,宫晨琛,兰祥辉,李东旭.用铅锌尾矿和页岩制备高C3S硅酸盐水 泥熟料的研究[J],硅酸盐通报.2006(10)：10-18.
[19]宣庆庆,朱建平,李东旭,邢锋.铅锌尾矿制备中热水泥熟料的研究[J],硅酸盐通报2007(10)：929-932.
[20]孙伟.有色金属矿山尾矿综合回收与利用[J].有色金属(选矿部分)1999(3)：44-47.
[21]徐光荣,王建斌.矿山尾矿资源化与整体综合利用[J].陕西地质.2006(12)：87-92.
[22]赵新科,郭雯.南沙沟铅锌尾矿综合利用试验研究[J].矿产保护与利用.2010(2)：52-55.
[23]宋雪娟.尾矿贮存方式的一种趋势-干堆技术[J].新疆有色金属,2007：73-76.
[24]邢万芳,金英豪,姚香.黄金尾矿干堆技术若干问题探讨[J].有色金属(矿山部分),2008(1)：48-51.
[25]付永祥.大型山谷型尾矿干堆场设计理念与实例[J].金属矿山,2009(10)：1-5.
[26]Hongyu Liu, Anne Probst, Bohan Liao.Metal contamination of soils and crops affected by the Chenzhou lead-zinc mine spill(Hunan,China) [J].Science of The Total Environment,2005(3):Pages 153-166.
[27]Joan O.Grimalt,Miguel Ferrer, Enrique Macpherson.The mine tailing accident in Aznalcollar[J].The Science of The Total Environment,1999(12):Pages 3-11.
[28]Karen A.Hudson-Edwards,Mark G.Macklin,Heather E.Jamieson,Paul A. Brewer,Tom J.Coulthard,Andy J.Howard, Jon N.Turner.The impact of tailings dam spills and clean-up operations on sediment and water quality in river systems [J].Applied Geochemistry,2003(2):Pages 221-239.
[29]谭欣,李长根.国内外氧化铅锌矿浮选研究进展(Ⅱ)[J].国外金属矿选矿,2000,37(4)：2-6.
[30]M. Rey, P.Raffinot. The flotation of oxidized zinc ore[J].IMM,1953,511-579
[31]张锎.浮选药剂的组合使用[M].北京：冶金工业出版社,1994,106-107
[32]Fa Keqing, J.D.Miller, Jiang Tao, et al. Sulphidization flotation for recovery of lead and zinc from oxide-sulfide ores[J].Transactions of Nonferrous Metals Society of China,2005,15(5):1138-1144.
[33]A.H.N.Kashani, F.Rashchi. Reagents in zinc reeovery from Pb-flotation tailings of Dandy mineral proeessing plant[J].Joumal of Faculty of Engineering,2008,41(8):1103-1110.
[34]王淑秋,罗琳,张心平等.难选氧化铅锌矿浮选工艺研究[J].有色金属(选矿部分),199(3)：17-20.
[35]丁玉仙.兰坪铅锌矿南厂灰岩氧化矿选矿工艺研究[J].云南冶金：科学技术版,1990,19(3)：25-27.
[36]G.onal, G.Bulut, A.Gul, et al. Flotation of Aladag oxide lead-zinc ores[J]. Minerals Engineering,2005(18):279-282.
[37]陈晔.阳离子胺类捕收剂浮选异极矿氧化锌及其作用机理研究：[硕士学位论文]南宁：广西大学,2006.
[38]刘军.氧化铅锌矿的浮选[J].矿业快报,2006(10)：26-29.
[39]S.H.Hosseini, Eric Forssberg. Physicochemical studies of smithsonite flotation using mixed anionic/cationic collector[J]. Minerals Engineering,2007,20(6):621-624.
[40]徐晓军,周廷熙.有色金属矿产资源的开发及加工技术[M].昆明：云南科技出版社,2000,50-51.
[41]W.Janusz, M.Szymula, J.Szczypa. Flotation of synthetic zinc carbonate using potassium ethylxanthate[J]. International Journal of Mineral Processing, 1983,11(2):79-88.
[42]张覃.氧化锌矿石活化浮选行为的观察[J].贵州工业大学学报：自然科学版,1998,27(3)：89-91.
[43]张俊辉.浅谈氧化铅锌矿的浮选现状[J].四川有色金属,2004(4)：13-17,22.
[44]S.H.Hosseini, Eric Forssberg. Adsorption studies of smithsonite flotation using dodecylamine and oleic acid[J]. Minerals and Metallurgical Processing,2006,23 (2):87-96.
[45]A.M.Gaudin, Flotation, Second Edition, McGraw-Hill, New York,1957.
[46]朱龙华,薛玉兰,朱建光.氧化铅锌矿浮选研究进展[J].江西有色金属,1997,11(4)：19-22.
[47]Zygmunt Sadowski, Izabela Polowczyk. Agglomerate flotation of fine oxide particles[J]. International Journal of Mineral Processing,2004,74(1-4):85-90.
[48]蒲雪丽.云南某低品位氧化锌矿浮选试验研究：[硕士学位论文].昆明：昆明理工大学,2008.
[49]S.Quaresima, K.Sivadasanb, A.M.Marabini, et al. Behavior of colloidal suspensions of zinc carbonate in the presence of copolymers designed for selective flocculation[J] Journal of Colloid and Interface Science,1991,6(1):159-164.
[50]V.Bertini, M.Poccia, A.M.Marabini, et al.3,4-(Methylenedioxy)benzyl acrylate/acrylic as selective pH-controlled flocculants for finely divided titanium minerals[J].Colloids and Surfaces,1991,11 (60):413-421.
[51]杨敖,石道民,朱从杰.兰坪水锌矿的选择性絮凝研究[J].云南冶金：科学技术版,1991,20(5)：16-22.
[52]杨敖,石道民,兰培林.兰坪氧化锌矿—脉石体系分散与选择性絮凝研究[J].昆明工学院学报,1992,17(1)：30-38.
[2]U.S.Geological Survey, Mineral Commodity Summaries, January 2007.
[3]彭新平,陈伟,吴兆清.硫化铅锌矿选矿废水处理与回用技术研究[J].湖南有色金属,2010(4)：40-44.
[4]邓敬石,张宗华,陈家栋.浅谈含重金属离子的铅锌矿尾矿废水危害及治理[J].云南冶金,2002(4)：20-24.
[5]湖南有色金属研究院.云南会泽铅锌矿选矿废水回用及治理[R].长沙：湖南有色金属研究院,2001.
[6]张美钦.铅锌选矿厂尾矿综合利用途径浅析[J].化学工程与设备,2008(8)：104-109.
[7]罗洪涛.会理铅锌矿选矿废水的利用研究[J].矿产保护与利用.1999(4)：48-50.
[8]严群,罗仙平,赖兰萍等.会东铅锌矿选矿废水净化回用工艺的试验研究[J].工业水处理,2008(3)：57-60.
[9]张艳,戴晶平,张康生.凡口矿选矿废水处理与利用试验研究[J].矿冶工程,2008(3)：45-48.
[10]常前发,矿山固体废物的处理与处置[J].矿广保护与利用.2005(5)：38-42.
[11]曾懋华,颜美凤,奚长生,蒋荣华,方振鹏.从凡口铅锌矿尾矿中回收硫精矿的研究[J].冶金工程.2007(1)：36-42.
[12]王毓华.从铅锌浮选尾矿中回收氧化铅锌矿物的研究[J].金属矿山.2002(10)：154-158.
[13]周怡玫,严志明,汤小军,邱允武.尾矿中回收氧化锌的选矿工艺研究[J].有色金属(选矿部分)2008(1).
[14]余艳平,童雄,张桂芳,高西平.某氧化铅锌尾矿浮选试验研究[J].有色金属(选矿部分)2008(2).
[15]李亮,袁启东,王炬.从铅锌矿尾矿中回收锰的工艺研究[J].矿业快报.2008(11)：20-23.
[16]汪顺才,王方汉,曹维勤.废弃尾矿中碳酸锰矿铵盐焙烧富集工艺研究[J].金属矿山.2008(3)：144-149.
[17]金吉梅,曾娟,刘亮.铅锌尾矿回收自钨试验研究[J].矿业工程.2009(6)：23-28.
[18]朱建平,宫晨琛,兰祥辉,李东旭.用铅锌尾矿和页岩制备高C3S硅酸盐水 泥熟料的研究[J],硅酸盐通报.2006(10)：10-18.
[19]宣庆庆,朱建平,李东旭,邢锋.铅锌尾矿制备中热水泥熟料的研究[J],硅酸盐通报2007(10)：929-932.
[20]孙伟.有色金属矿山尾矿综合回收与利用[J].有色金属(选矿部分)1999(3)：44-47.
[21]徐光荣,王建斌.矿山尾矿资源化与整体综合利用[J].陕西地质.2006(12)：87-92.
[22]赵新科,郭雯.南沙沟铅锌尾矿综合利用试验研究[J].矿产保护与利用.2010(2)：52-55.
[23]宋雪娟.尾矿贮存方式的一种趋势-干堆技术[J].新疆有色金属,2007：73-76.
[24]邢万芳,金英豪,姚香.黄金尾矿干堆技术若干问题探讨[J].有色金属(矿山部分),2008(1)：48-51.
[25]付永祥.大型山谷型尾矿干堆场设计理念与实例[J].金属矿山,2009(10)：1-5.
[26]Hongyu Liu, Anne Probst, Bohan Liao.Metal contamination of soils and crops affected by the Chenzhou lead-zinc mine spill(Hunan,China) [J].Science of The Total Environment,2005(3):Pages 153-166.
[27]Joan O.Grimalt,Miguel Ferrer, Enrique Macpherson.The mine tailing accident in Aznalcollar[J].The Science of The Total Environment,1999(12):Pages 3-11.
[28]Karen A.Hudson-Edwards,Mark G.Macklin,Heather E.Jamieson,Paul A. Brewer,Tom J.Coulthard,Andy J.Howard, Jon N.Turner.The impact of tailings dam spills and clean-up operations on sediment and water quality in river systems [J].Applied Geochemistry,2003(2):Pages 221-239.
[29]谭欣,李长根.国内外氧化铅锌矿浮选研究进展(Ⅱ)[J].国外金属矿选矿,2000,37(4)：2-6.
[30]M. Rey, P.Raffinot. The flotation of oxidized zinc ore[J].IMM,1953,511-579
[31]张锎.浮选药剂的组合使用[M].北京：冶金工业出版社,1994,106-107
[32]Fa Keqing, J.D.Miller, Jiang Tao, et al. Sulphidization flotation for recovery of lead and zinc from oxide-sulfide ores[J].Transactions of Nonferrous Metals Society of China,2005,15(5):1138-1144.
[33]A.H.N.Kashani, F.Rashchi. Reagents in zinc reeovery from Pb-flotation tailings of Dandy mineral proeessing plant[J].Joumal of Faculty of Engineering,2008,41(8):1103-1110.
[34]王淑秋,罗琳,张心平等.难选氧化铅锌矿浮选工艺研究[J].有色金属(选矿部分),199(3)：17-20.
[35]丁玉仙.兰坪铅锌矿南厂灰岩氧化矿选矿工艺研究[J].云南冶金：科学技术版,1990,19(3)：25-27.
[36]G.onal, G.Bulut, A.Gul, et al. Flotation of Aladag oxide lead-zinc ores[J]. Minerals Engineering,2005(18):279-282.
[37]陈晔.阳离子胺类捕收剂浮选异极矿氧化锌及其作用机理研究：[硕士学位论文]南宁：广西大学,2006.
[38]刘军.氧化铅锌矿的浮选[J].矿业快报,2006(10)：26-29.
[39]S.H.Hosseini, Eric Forssberg. Physicochemical studies of smithsonite flotation using mixed anionic/cationic collector[J]. Minerals Engineering,2007,20(6):621-624.
[40]徐晓军,周廷熙.有色金属矿产资源的开发及加工技术[M].昆明：云南科技出版社,2000,50-51.
[41]W.Janusz, M.Szymula, J.Szczypa. Flotation of synthetic zinc carbonate using potassium ethylxanthate[J]. International Journal of Mineral Processing, 1983,11(2):79-88.
[42]张覃.氧化锌矿石活化浮选行为的观察[J].贵州工业大学学报：自然科学版,1998,27(3)：89-91.
[43]张俊辉.浅谈氧化铅锌矿的浮选现状[J].四川有色金属,2004(4)：13-17,22.
[44]S.H.Hosseini, Eric Forssberg. Adsorption studies of smithsonite flotation using dodecylamine and oleic acid[J]. Minerals and Metallurgical Processing,2006,23 (2):87-96.
[45]A.M.Gaudin, Flotation, Second Edition, McGraw-Hill, New York,1957.
[46]朱龙华,薛玉兰,朱建光.氧化铅锌矿浮选研究进展[J].江西有色金属,1997,11(4)：19-22.
[47]Zygmunt Sadowski, Izabela Polowczyk. Agglomerate flotation of fine oxide particles[J]. International Journal of Mineral Processing,2004,74(1-4):85-90.
[48]蒲雪丽.云南某低品位氧化锌矿浮选试验研究：[硕士学位论文].昆明：昆明理工大学,2008.
[49]S.Quaresima, K.Sivadasanb, A.M.Marabini, et al. Behavior of colloidal suspensions of zinc carbonate in the presence of copolymers designed for selective flocculation[J] Journal of Colloid and Interface Science,1991,6(1):159-164.
[50]V.Bertini, M.Poccia, A.M.Marabini, et al.3,4-(Methylenedioxy)benzyl acrylate/acrylic as selective pH-controlled flocculants for finely divided titanium minerals[J].Colloids and Surfaces,1991,11 (60):413-421.
[51]杨敖,石道民,朱从杰.兰坪水锌矿的选择性絮凝研究[J].云南冶金：科学技术版,1991,20(5)：16-22.
[52]杨敖,石道民,兰培林.兰坪氧化锌矿—脉石体系分散与选择性絮凝研究[J].昆明工学院学报,1992,17(1)：30-38.