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投稿时间:2024-11-21
投稿时间:2024-11-21
中文摘要: 砷、锑、铋是铜矿的典型伴生杂质,在阳极铜中主要以复杂氧化物形态存在,在铜电解精炼过程可在阳极发生酸溶蚀和电化学溶解,并进一步氧化生成高价态金属离子。杂质砷、锑、铋对铜电解过程的影响主要包括:1)杂质离子在电解液中循环富集,在高电流密度和铜离子局部贫化明显时,将与铜在阴极共沉积;2)电解液中不同价态的砷、锑、铋离子相互结合生成对应的砷酸盐或锑酸盐复合沉淀,产生漂浮阳极泥并机械包埋进阴极铜,造成阴极铜表面长粒子和杂质超标;3)当阳极铜含较高的砷、锑含量时,如浇铸冷却曲线控制不当,可能形成Cu3As或Cu3Sb等杂质析出相,而较高的铋含量则造成杂质银的局部富集,均可诱发阳极钝化。在探讨砷、锑、铋对铜电解影响机制的基础上,详细介绍了现行电解液净化脱除砷、锑和铋的技术进展,对比分析了电沉积法、吸附法、离子交换法、沉淀法、萃取法和电解液自净化法等除杂方法,并提出精准调控阳极铜中核壳结构杂质析出相的生成,可同步实现有价元素富集和多元杂质协同脱除,是铜电解精炼实现精细控制的发展路径之一。
Abstract:Arsenic, antimony and bismuth are typical associated impurities found in copper ore. These elements primarily exist as complex oxides within anode copper and can undergo acid dissolution and electrochemical dissolution during the copper electrolytic refining process. This may lead to their further oxidation, resulting in the formation of high-valence metal ions. The effects of arsenic, antimony and bismuth on the copper electrolysis process are as follows: 1) The impurity ions become enriched in the electrolyte and may co-deposit with copper at the cathode when the current density is high, leading to a significant local depletion of copper ions; 2) Arsenic, antimony and bismuth ions in various valence states present within the electrolyte can interact to form corresponding arsenate or antimonate precipitates. This phenomenon leads to the formation of floating anode slime and mechanical inclusions in cathode copper, which contribute to surface particles and subsequently reduce the purity of cathode copper; 3) If anode copper displays elevated content of arsenic and antimony, coupled with insufficient control over the casting cooling curve, impurity phases such as Cu3As or Cu3Sb may be formed. Additionally, a high bismuth content can result in localized enrichment of silver in anode copper. All these factors may subsequently lead to anode passivation. Based on a discussion of the influence mechanisms of arsenic, antimony and bismuth on copper electrolysis, this paper provides a detailed overview of the current technological advancements in the removal of these elements through electrolyte purification. The methods for impurity removal, including electrodeposition, adsorption, ion exchange, precipitation, extraction, and electrolyte self-purification, have been systematically compared and analyzed. Finally, it is proposed to precisely regulate the formation of the precipitated phase of core-shell impurities in anode copper. This approach aims to enrich valuable elements while effectively removing various impurities, thereby representing a significant direction for the advancement of control in copper electrorefining.
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基金项目:校企联合项目(XNTY-生产-08-2022-0055);云南省建设面向南亚东南亚科技创新中心专项—云南省中老能矿分析与技术创新国际联合研发中心(202303AP140019)
引用文本:
何恩,王雨,朱鹏春,陈福光,班卿,林艳.杂质砷、锑、铋对铜电解精炼的影响及净化脱除技术进展[J].有色金属(冶炼部分),2025(6):83-93.
HE En,WANG Yu,ZHU Pengchun,CHEN Fuguang,BAN Qing,IN Yan.Influence of Impurities Arsenic, Antimony and Bismuth on Copper Electrolytic Refining and Advances in Purification and Removal Technologies[J].Nonferrous Metals (Extractive Metallurgy),2025(6):83-93.
何恩,王雨,朱鹏春,陈福光,班卿,林艳.杂质砷、锑、铋对铜电解精炼的影响及净化脱除技术进展[J].有色金属(冶炼部分),2025(6):83-93.
HE En,WANG Yu,ZHU Pengchun,CHEN Fuguang,BAN Qing,IN Yan.Influence of Impurities Arsenic, Antimony and Bismuth on Copper Electrolytic Refining and Advances in Purification and Removal Technologies[J].Nonferrous Metals (Extractive Metallurgy),2025(6):83-93.

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