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| Influence of Impurities Arsenic, Antimony and Bismuth on Copper Electrolytic Refining and Advances in Purification and Removal Technologies |
| Received:November 21, 2024 |
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| DOI：10.20237/j.issn.1007-7545.2025.06.009 |
| KeyWord:copper electrolytic refining; arsenic; antimony; bismuth; impurity removal |
| Author | Institution |
| HE En |
云南铜业股份有限公司 西南铜业分公司，昆明 ;昆明理工大学 冶金与能源工程学院，昆明 |
| WANG Yu |
昆明理工大学 冶金与能源工程学院，昆明 ;云南省中老能矿分析与技术创新国际联合研发中心，昆明 |
| ZHU Pengchun |
云南铜业股份有限公司 西南铜业分公司，昆明 |
| CHEN Fuguang |
云南铜业股份有限公司 西南铜业分公司，昆明 |
| BAN Qing |
云南铜业股份有限公司 西南铜业分公司，昆明 |
| IN Yan |
昆明理工大学 冶金与能源工程学院，昆明 ;云南省中老能矿分析与技术创新国际联合研发中心，昆明 ;省部共建复杂有色金属资源清洁利用国家重点实验室，昆明 |
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| 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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