郭莉2,
姚瑛瑛1,
杜冬云1
1.中南民族大学资源与环境学院，环境科学与工程研究所，武汉 430074
2.中国地质大学武汉环境学院，生物地质与环境地质国家重点实验室，武汉 430074
基金项目: 湖北省科技支撑计划项目（2014BEC029）
Selective separation of arsenic and valuable metals in copper smelting dust by Na2S-NaOH leaching assisted with ball milling
HU Zhongqiu1,,GUO Li2,
YAO Yingying1,
DU Dongyun1
1.Institute of Environment Engineering and Science, College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan 430074, China
2.State Key Laboratory of Biological Geology and Environmental Geology, School of Environmental Studies, China University of GeosciencesWuhan, Wuhan 430074, China
-->
摘要
HTML全文
图
参考文献
相关文章
施引文献
资源附件
访问统计
摘要:为开发高效的铜冶炼烟灰选择性脱砷技术，采用球磨辅助NaOH-Na2S浸取体系选择性分离As与有价金属，在NaOH、Na2S与烟灰质量比0.4:1、球磨转速350 r·min?1、料球比0.6、液固比20:1、填充系数0.45、反应时间60 min条件下，As浸出率可达85%，Cu、Pb、Cd和Zn浸出率均较低；与传统水浴浸出体系相比，As浸出率提高了11%。SEM表明，球磨后烟灰粒径减小、比表面积增大，表面呈剥蚀状，As浸出过程传质速率增加，反应活性位点增多；XPS表明，球磨后烟灰中6.73% As(III)被氧化为As(V)，进一步促进其浸出；XRD表明，浸出残余固体中Pb、Zn主要为硫化物，球磨可将烟灰中PbSO4转化为PbS，从而加快As选择性分离，故球磨可强化As与有价金属在碱浸体系中的选择性分离，为铜冶炼产生的含砷材料的无害化及资源化提供了理论基础。
关键词: 铜冶炼烟灰/
球磨/
砷选择性浸出/
有价金属
Abstract:In order to develop high-efficiency selective arsenic removal technology from copper smelting soot, a NaOH-Na2S leaching system assisted with ball milling was used to selectively separate As and valuable metals. The highest As leaching rate up to 85% was obtained at rotating speed of 350 r·min?1, liquid-solid ratio of 20:1, material-to-ball ratio of 0.6, volume filling coefficient of 0.45, mass ratio of soot and NaOH of 0.4:1, mass ratio of soot and Na2S of 0.4:1 and 60 min leaching. Meanwhile, Cu, Pb, Cd and Zn showed very low leaching rates. Compared with the leaching process by using conventional water bath, milling ball assist led to 11% increase in As leaching rate. SEM images of ball milled soot particles showed decreased size, increased specific surface area and erosion surface, which caused the increase of the mass transfer rate in As leaching process and active sites for reaction. XPS spectra showed that 6.73% As(III) was oxidized to As(V) in ball milled soot, and As leaching was promoted. XRD patterns showed that the sulphides of Pb and Zn were identified in the residues of copper smelting soot after leaching, which implied that part of the PbSO4 in the soot was converted into PbS by ball milling and subsequently the selective separation of As and valuable metals in the alkali leaching system was enhanced. This study provided a theoretical basis for the harmlessness and resource utilization of arsenic-containing materials produced by copper smelting.
Key words:copper smelting dust/
ball milling/
arsenic selective leaching/
valuable metals.
| [1] | MANDAL B K, SUZUKI K T.Arsenic round the world: A review[J].Talanta, 2002, 58(1):201-235 10.1016/S0039-9140(02)00268-0 |
| [2] | BASHA C A, SELVI S J, RAMASAMY E, et al.Removal of arsenic and sulphate from the copper smelting industrial effluent[J].Chemical Engineering Journal, 2008, 141(1): 89-98 10.1016/j.cej.2007.10.027 |
| [3] | GUO X, YU Y I, JING S H I, et al.Leaching behavior of metals from high-arsenic dust by NaOH-Na2S alkaline leaching[J].Transactions of Nonferrous Metals Society of China, 2016, 26(2): 575-580 10.1016/S1003-6326(16)64118-3 |
| [4] | MIAO M A, HUANG Y, GUO Y, et al.Determination of speciation in white ash and acid leaching arsenic removal technique[J].Chinese Journal of Applied Chemistry, 2015, 32(10):1208-1214 10.11944/j.issn.1000-0518.2015.10.150012 |
| [5] | XU Z, QIANG L I, NIE H P.Pressure leaching technique of smelter dust with high-copper and high-arsenic[J].Transactions of Nonferrous Metals Society of China, 2010, 20: 176-181 10.1016/S1003-6326(10)60035-0 |
| [6] | MONTENEGRO V, SANO H, FUJISAWA T.Recirculation of high arsenic content copper smelting dust to smelting and converting processes[J].Minerals Engineering, 2013, 49: 184-189 10.1016/j.mineng.2010.03.020 |
| [7] | YIN Z, LU W, XIAO H.Arsenic removal from copper–silver ore by roasting in vacuum[J].Vacuum, 2014, 101: 350-353 10.1016/j.vacuum.2013.10.005 |
| [8] | CHEN Y, LIAO T, LI G, et al.Recovery of bismuth and arsenic from copper smelter flue dusts after copper and zinc extraction[J].Minerals Engineering, 2012, 39: 23-28 10.1016/j.mineng.2012.06.008 |
| [9] | RUIZ M C, GRANDON L, PADILLA R.Selective arsenic removal from enargite by alkaline digestion and water leaching[J].Hydrometallurgy, 2014, 150: 20-26 10.1016/j.hydromet.2014.09.004 |
| [10] | 白猛. 铜冶炼伴生元素砷, 锑, 铋, 铼的增值冶金新方法研究[D]. 长沙:中南大学, 2013 |
| [11] | 易宇, 石靖, 田庆华,等. 高砷烟尘氢氧化钠-硫化钠碱性浸出脱砷[J]. 中国有色金属学报, 2015, 25(3):806-814 |
| [12] | ERASMUS E, JOHNSON O.Parameters affecting arsenic recovery from copper smelting[J].Lecture Notes in Engineering & Computer Science, 2014, 2212(1)：1499-1502 |
| [13] | LI Y, LIU Z, LI Q, et al.Alkaline oxidative pressure leaching of arsenic and antimony bearing dusts[J].Hydrometallurgy, 2016, 166:41-47 10.1016/j.hydromet.2016.07.010 |
| [14] | REYNOLDS J E, COLTRINARI E L.Process for recovering arsenic compounds by sodium hydroxide leaching:US 4244927A[P]. 1981-06-13 |
| [15] | 郑军福, 孙留根, 于英东,等. 镍冶炼转炉烟灰碱浸脱砷试验研究[J]. 中国资源综合利用, 2014, 32(4):21-23 |
| [16] | GUO X, SHI J, YI Y, et al.Separation and recovery of arsenic from arsenic-bearing dust[J].Journal of Environmental Chemical Engineering, 2015, 3(3):2236-2242 10.1016/j.jece.2015.06.028 |
| [17] | 王倩, 郭莉, 吴晨捷,等. 微波作用下氧化碱浸铜冶炼烟灰脱砷的动力学[J]. 环境工程学报, 2017, 11(11):6072-6077 10.12030/j.cjee.201701101 |
| [18] | 郝士涛. 铜冶炼烟灰碱浸脱砷预处理及有价金属综合回收[D]. 赣州: 江西理工大学, 2012 |
| [19] | LEWIS A E.Review of metal sulphide precipitation[J].Hydrometallurgy, 2010, 104(2):222-234 10.1016/j.hydromet.2010.06.010 |
| [20] | 吴玉林, 徐志峰, 郝士涛. 炼铜烟灰碱浸脱砷的热力学及动力学[J]. 有色金属 (冶炼部分), 2013 (4):3-7 |
| [21] | LI Y, LIU Z, LI Q, et al.Removal of arsenic from arsenate complex contained in secondary zinc oxide[J].Hydrometallurgy, 2011, 109(3):237-244 10.1016/j.hydromet.2011.07.007 |
| [22] | BALá? P.Mechanical activation in hydrometallurgy[J].International Journal of Mineral Processing, 2003, 72(1):341-354 10.1016/S0301-7516(03)00109-1 |
| [23] | LI M G, SUN C J, GAU S H, et al.Effects of wet ball milling on lead stabilization and particle size variation in municipal solid waste incinerator fly ash[J].Journal of Hazardous Materials, 2010, 174(1): 586-591 10.1016/j.jhazmat.2009.09.092 |
| [24] | CHEN S.Mechanical activation and its application to leaching process[J].Shanghai Nonferrous Metals,1998,19(2):91-96 |
| [25] | KUKURUGYA F, KIM E, NIELSEN P, et al.Effect of milling on metal leaching: Induction of galvanic effect in a secondary lead smelter matte by prolonged milling[J].Hydrometallurgy, 2017, 171:245-253 10.1016/j.hydromet.2017.05.018 |
| [26] | SURYANARAYANA C.Mechanical alloying and milling[J].Progress in Materials Science, 2004, 46(1):1-184 10.1016/S0079-6425(99)00010-9 |
| [27] | WELHAM N J, LLEWELLYN D J.Mechanical enhancement of the dissolution of ilmenite[J].Minerals Engineering, 1998, 11(9):827-841 10.1016/S0892-6875(98)00070-3 |
| [28] | CHEN Y, WILLIAMS J S, CAMPBELL S J, et al.Increased dissolution of ilmenite induced by high-energy ball milling[J].Materials Science & Engineering A, 1999, 271(1/2):485-490 10.1016/S0921-5093(99)00441-4 |
| [29] | 李高兰, 杜长山, 吕莉,等. 热酸球磨浸出攀枝花钛铁矿[J]. 钢铁钒钛, 2012, 33(4):1-6 |
| [30] | 苑文仪, 李金惠, 张承龙,等. 机械活化对CRT锥玻璃浸出动力学的影响[J]. 环境工程学报, 2014, 8(8):3390-3394 |
| [31] | 王一雍, 金辉, 李继东,等. 球磨-浸出工艺处理三水铝石矿的研究[J]. 有色金属(冶炼部分), 2011(4):19-22 |
| [32] | 高强. 基于离散元法的搅拌球磨机磨矿分析与研究[D]. 昆明:昆明理工大学, 2016 |
| [33] | NASU T, NAGAOKA K, TAKAHASHI S Y, et al.SEM observation on solid state amorphization of Ni–Nb alloy by ball milling[J].Materials Transactions, 2007, 30(8):620-623 10.2320/matertrans1989.30.620 |
| [34] | FROST R L, KRISTóF J, éVA MAKó, et al.A DRIFT spectroscopic study of potassium acetate intercalated mechanochemically activated kaolinite[J].Spectrochimica Acta Part A, 2003, 59(6):1183-1194 |
| [35] | 高孟华, 公明明, 于建国. 机械球磨对煤矸石反应活性的影响[J]. 中国矿业, 2008, 17(2):72-74 |
| [36] | FENG L, LEE S H, WANG H L, et al.Nanostructured HfC–SiC composites prepared by high-energy ball-milling and reactive spark plasma sintering[J].Journal of the European Ceramic Society, 2016, 36(1):235-238 10.1016/j.jeurceramsoc.2015.09.024 |
| [37] | WEEBER A W, BAKKER H.Amorphization by ball milling:A review[J].Physica B：Condensed Matter, 1988, 153(1):93-135 10.1016/0921-4526(88)90038-5 |
| [38] | 王岩玲,王俊恩,尹鹰. 球磨法制备异质结型光催化剂ZnO/Bi4Ti3O12及催化性能[J]. 化学研究与应用, 2009, 21(12):1612-1617 |
Turn off MathJax -->
点击查看大图计量
文章访问数:633
HTML全文浏览数:543
PDF下载数:62
施引文献:0
出版历程
刊出日期:2018-11-12
-->
球磨辅助碱浸铜冶炼烟灰中砷与有价金属选择性分离
胡中求1,,郭莉2,
姚瑛瑛1,
杜冬云1
1.中南民族大学资源与环境学院，环境科学与工程研究所，武汉 430074
2.中国地质大学武汉环境学院，生物地质与环境地质国家重点实验室，武汉 430074
基金项目: 湖北省科技支撑计划项目（2014BEC029）
关键词: 铜冶炼烟灰/
球磨/
砷选择性浸出/
有价金属
摘要:为开发高效的铜冶炼烟灰选择性脱砷技术，采用球磨辅助NaOH-Na2S浸取体系选择性分离As与有价金属，在NaOH、Na2S与烟灰质量比0.4:1、球磨转速350 r·min?1、料球比0.6、液固比20:1、填充系数0.45、反应时间60 min条件下，As浸出率可达85%，Cu、Pb、Cd和Zn浸出率均较低；与传统水浴浸出体系相比，As浸出率提高了11%。SEM表明，球磨后烟灰粒径减小、比表面积增大，表面呈剥蚀状，As浸出过程传质速率增加，反应活性位点增多；XPS表明，球磨后烟灰中6.73% As(III)被氧化为As(V)，进一步促进其浸出；XRD表明，浸出残余固体中Pb、Zn主要为硫化物，球磨可将烟灰中PbSO4转化为PbS，从而加快As选择性分离，故球磨可强化As与有价金属在碱浸体系中的选择性分离，为铜冶炼产生的含砷材料的无害化及资源化提供了理论基础。
English Abstract
Selective separation of arsenic and valuable metals in copper smelting dust by Na2S-NaOH leaching assisted with ball milling
HU Zhongqiu1,,GUO Li2,
YAO Yingying1,
DU Dongyun1
1.Institute of Environment Engineering and Science, College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan 430074, China
2.State Key Laboratory of Biological Geology and Environmental Geology, School of Environmental Studies, China University of GeosciencesWuhan, Wuhan 430074, China
Keywords: copper smelting dust/
ball milling/
arsenic selective leaching/
valuable metals
Abstract:In order to develop high-efficiency selective arsenic removal technology from copper smelting soot, a NaOH-Na2S leaching system assisted with ball milling was used to selectively separate As and valuable metals. The highest As leaching rate up to 85% was obtained at rotating speed of 350 r·min?1, liquid-solid ratio of 20:1, material-to-ball ratio of 0.6, volume filling coefficient of 0.45, mass ratio of soot and NaOH of 0.4:1, mass ratio of soot and Na2S of 0.4:1 and 60 min leaching. Meanwhile, Cu, Pb, Cd and Zn showed very low leaching rates. Compared with the leaching process by using conventional water bath, milling ball assist led to 11% increase in As leaching rate. SEM images of ball milled soot particles showed decreased size, increased specific surface area and erosion surface, which caused the increase of the mass transfer rate in As leaching process and active sites for reaction. XPS spectra showed that 6.73% As(III) was oxidized to As(V) in ball milled soot, and As leaching was promoted. XRD patterns showed that the sulphides of Pb and Zn were identified in the residues of copper smelting soot after leaching, which implied that part of the PbSO4 in the soot was converted into PbS by ball milling and subsequently the selective separation of As and valuable metals in the alkali leaching system was enhanced. This study provided a theoretical basis for the harmlessness and resource utilization of arsenic-containing materials produced by copper smelting.
