高铋铅阳极泥碱性氧化浸出渣熔炼-电解提铋研究
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摘要
以高铋铅阳极泥碱性氧化浸出渣为原料,采用碳热还原熔炼-电解工艺提取铋,同时富集金银.热力学分析表明金属碳热还原的初始温度由低到高依次为:铜、铋、铅、锑、锡;铋氧化物在800℃以上可获得足够大的还原热力学推动力.熔炼粗铋合金的最佳温度为800℃,碳用量为浸出渣质量的5%,四硼酸钠用量为浸出渣质量的15%,熔炼时间为1.5 h.在此条件下,粗铋合金中铋、金、银的平均含量分别为84.29%,39.62 g/t和6 519 g/t,相比于铅阳极泥原料,金银分别被富集1.8倍.采用公斤级粗铋合金板为阳极,在BiCl_3-NaCl-HCl体系中分别电解24 h、48 h、72 h、112 h,阴极产物中铋平均含量>98%,电流效率>96%,铋电解阳极泥中金、银平均含量分别为222.94 g/t,34 287.6 g/t,相比铅阳极泥原料,金银平均被富集到9.54倍和10.13倍.
Alkaline oxidative leaching residues of bismuth-rich lead anode slime were adopted to extract bismuth and enrich gold and silver by using carbothermal reduction casting and electrolysis process.Thermodynamics analysis indicates that the initial carbothermal reduction temperature of metal oxides from low to high are Cu, Bi, Pb, Sb, Sn. Bismuth oxides can obtain enough reduction thermodynamic driving force w hen the temperature excesses 800 ℃. The optimum technical conditions are as follows: temperature, 800 ℃;carbon addition, 5 % of the mass of leaching residue; Na2 B4 O7 addition, 15 % of the mass of the leaching residue; time duration,1.5 h. Under such conditions the average contents of bismuth, gold and silver were84.29 %, 39.62 g/t and 6519 g/t, respectively. Compared with the raw lead anode slime, the content of gold and silver were enriched 1.8 times respectively. Kilogram-scale crude bismuth alloys were electrolyzed in HCl-NaCl-BiCl_3 system as anodic plates for 24 h, 48 h, 72 h, 112 h. The results indicated that the content of bismuth in the cathodal products exceeded 98 %, the current efficiency, 96 %, and the average content of gold and silver content were 222.94 g/t, 34287.6 g/t, respectively. Compared with the raw lead anode slime, the content of gold and silver were enriched 9.54 times and 10.13 times, respectively.
Alkaline oxidative leaching residues of bismuth-rich lead anode slime were adopted to extract bismuth and enrich gold and silver by using carbothermal reduction casting and electrolysis process.Thermodynamics analysis indicates that the initial carbothermal reduction temperature of metal oxides from low to high are Cu, Bi, Pb, Sb, Sn. Bismuth oxides can obtain enough reduction thermodynamic driving force w hen the temperature excesses 800 ℃. The optimum technical conditions are as follows: temperature, 800 ℃;carbon addition, 5 % of the mass of leaching residue; Na2 B4 O7 addition, 15 % of the mass of the leaching residue; time duration,1.5 h. Under such conditions the average contents of bismuth, gold and silver were84.29 %, 39.62 g/t and 6519 g/t, respectively. Compared with the raw lead anode slime, the content of gold and silver were enriched 1.8 times respectively. Kilogram-scale crude bismuth alloys were electrolyzed in HCl-NaCl-BiCl_3 system as anodic plates for 24 h, 48 h, 72 h, 112 h. The results indicated that the content of bismuth in the cathodal products exceeded 98 %, the current efficiency, 96 %, and the average content of gold and silver content were 222.94 g/t, 34287.6 g/t, respectively. Compared with the raw lead anode slime, the content of gold and silver were enriched 9.54 times and 10.13 times, respectively.
引文
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[2]FERNANDEZ M A,SEGARRA M,ESPIELL F.Selective leaching of arsenic and antimony contained in the anode slimes from copper refining[J].Hydrometallurgy,1996,41(2/3):255-267.
[3]HAN J,LIANG C,LIU W,et al.Pretreatment of tin anode slime using alkaline pressure oxidative leaching[J].Separation and Purification Technology,2017,174(1):389-395.
[4]LUDVIGSSON B,LARSSON S.Anode slimes treatment:the boliden experience[J].Journal of the Minerals,Metals and Materials Society,2003,55(4):41-44.
[5]王光忠,陈海军.铅阳极泥富氧底吹熔炼实践[J].湖南有色金属,2012,28(1):37-39.
[6]周洪武.铅阳极泥冶炼技术简评和电热连续熔炼的可行性[J].有色冶炼,2002,31(4):7-11.
[7]刘吉波,吴文花.某铅锌冶炼厂铅阳极泥湿法预处理新工艺[J],有色金属工程,2014,4(5):38-39.
[8]周云峰,王少龙,李昌林,等.铅阳极泥脱砷预处理研究现状与进展[J].新技术新工艺,2011(10):67-69.
[9]QIU K Q,LIN D Q,YANG X L.Vacuum evaporation technology for treating antimony-rich anode slime[J].Journal of the Minerals,Metals and Materials Society,2012,64(11):1321-1325.
[10]LI L,TIAN Y,LIU D C,et al.Pretreatment of lead anode slime with low silver by vacuum distillation for concentrating silver[J].Journal of Central South University of Technology,2013,20(3):615-621.
[11]LIN D Q,QIU K Q.Removing arsenic from anode slime by vacuum dynamic evaporation and vacuum dynamic flash reduction[J].Vacuum,2012,86(8):1155-1160.
[12]郭瑞.全湿法处理含铋铅阳极泥工艺及铁片置换海绵铋动力学研究[D].长沙:中南大学,2013.
[13]支波.高锑铅阳极泥制备五氯化锑及其水解过程的研究[D].杭州:浙江工业大学,2006.
[14]陈进中.高锑铅阳极泥制备三氯化锑和锑白研究[D].长沙:中南大学,2012.
[15]CAO H Z,CHEN J Z,YUAN H J,et al.Preparation of pure SbCl3from lead anode slime bearing high antimony and low silver[J].Transactions of Nonferrous Metals Society of China,2010,20(12):2397-2403.
[16]杨学林,丘克强,张露露,等.利用高锑铅阳极泥制备三氧化二锑的工艺研究[J].现代化工,2004,4(2):44-46.
[17]何云龙,徐瑞东,何世伟,等.铅阳极泥处理技术的研究进展[J].有色金属科学与工程,2017,8(5):40-51.
[18]叶大伦.胡建华.实用无机物热力学数据手册[M].2版.北京:冶金工业出版社,2002.
[19]张作良.高铝铁矿石气基直接还原基础研究[D].沈阳:东北大学,2014.
[20]郭宇峰.钒钛磁铁矿固态还原强化及综合利用研究[D].长沙:中南大学,2007.
[21]黄丹.钒钛磁铁矿综合利用新流程及其比较研究[D].长沙:中南大学,2012.
[22]戴永年.二元合金相图集[M].北京:科学出版社,2009.
[23]王传龙.铅渣中有价金属铜铁铅锌锑综合回收工艺及机理研究[D].北京:北京科技大学,2017.