脱铜泥回收梯铋及砷处理工艺的研究

中图分类号：TF817；TF818 文献标志码：A 文章编号：1004-4345（2025）02-0016-04

Research on the Recovery of Antimony and Bismuth from Depleted Copper Slime and Arsenic Treatment Process

GUO Yaxin1²，LI Tao1，2

（1. Zijin Copper Co.，Ltd.Shanghang，Fujian 3642Oo，China; 2.FujianKeyLaboratoryforGreen ProductionofCopperand Comprehensive Utilization of Associated Resources， Shanghang， Fujian 3642Oo， China）

AbstractInresponseto the problem of goldandsilverlosscausedbyantimonyandbismuth recoveryduring the leaching of depleted copper anode slime in the“sulfuricacid+sodium chloride”system，the paper puts forward a processroute of \"pre- neutralizationof leachingsolution-cascadehydrolysis-alkali leachingforarsenicremoval-causticizationforalkalirecycling”to achieveeficientseparatioofrsenic，antionyandbismuthandandcompletetheharmlesstreatmentofarsenic.Teesearchresults indicatethatunder theoptialconditions，theuseof imemilkforpre-neutralizatinoftheleachingsolutioncanreducethesilver ρ（Ag） content to 0.02mg/L in the leaching solution and obtain undetectable ρ（Au） .Pre-neutralization post solution was diluted 8 times with water for hydrolysis，the hydrolysis rate of Sb is 96.01% ，and the precipitation rate of bismuth is less than 5% . Sodium hydroxide is added intoantimonyprecipiationostsolution tocontrolpHvalueto2.5forbismuthprecipitation，theBiprecipitationratefBi reaches 98.23% ，and the arsenic precipitation rate is 50.48% .Alkali leaching is carried out in bismuth precipitation post solution for arsenic removal， with an arsenic removal rate of 89.89 % and the arsenic mass fraction of arsenic in the alkali leaching residue of only 1.95 % . Causticization treatment generates calcium arsenate residue， which contains 26.72% arsenic and has an arsenic precipitation rate of 98.21%

Keywordsdepleted copper anode slime; pre-neutralizationtreatment; arsenic harmlesstreatment;antimony and bismuth classifying recovery

铜阳极泥作为铜电解精炼的副产物，因其富含大量金、银、铜、铂、钯等贵金属以及硒、碲、锑、铋等稀散元素[1-3]，已成为稀贵金属资源化利用的重要研究对象。为提升资源综合利用效率，学界已开发出多种铜阳极泥处理工艺回收其中的稀贵金属，主要包括“硫酸化焙烧—湿法浸出\"工艺、“加压氧化浸出—卡尔多炉熔炼\"工艺、“硫酸化焙烧—转炉熔炼\"工艺和“浸出—浮选—冶炼\"工艺等[4-I0]。这些工艺路线通常可根据铜阳极泥的成分特点和生产实际情况进行适应性优化。以紫金铜业有限公司稀贵厂为例，其采用的加压氧化浸出一卡尔多炉熔炼工艺虽能有效回收铜阳极泥中的金、银、铜、铂、钯等贵金属及硒、碲等稀散元素，但锑、铋在冶炼过程中会以硅酸锑、锑酸铅和铋酸铅等化合物形式进入熔炼渣体系。由于该熔炼渣需返回闪速炉循环处理，导致锑、铋元素持续富集而无法有效分离回收。

这一技术瓶颈的形成机理在于：卡尔多炉吹炼过程中添加了二氧化硅、氧化铅等辅料，这些辅料在造渣阶段与锑、铋形成了硅酸锑、锑酸铅、铋酸铅等稳定化合物；更关键的是，基于硅酸凝胶理论，硅酸及其盐类在熔炼渣浸出过程中会快速形成凝胶状物质，致使矿浆过滤性能显著恶化[1I-4]。因此，现有聚焦于通过“盐酸一硫酸一氯化钠\"三元浸出体系回收卡尔多炉熔炼渣中锑、铋的相关实验研究结果并不理想。这使回收脱铜泥中的锑铋是成为近年来的研究热点，主要技术路径包括氯化浸出、生物浸出、萃取及离子交换等[15-17]。……