铜电解液净化除杂研究进展

doi:10.16085/j.issn.1000-6613.2025-0851

摘要/Abstract

摘要：

铜电解液净化对确保阴极铜产品质量及有价金属资源的高效回收至关重要。但现有除杂技术普遍存在能耗偏高、易造成二次污染或分离效率不足等问题。本文综述了包括电积、沉淀、离子交换、吸附、溶剂萃取及膜分离等主流净化方法的原理与应用现状，并对比分析了各类方法在工业化应用中的优势与局限性。分析表明，循环电积法是目前国内外大型阴极铜生产企业应用最为广泛的除杂方法，该技术具备处理高浓度铜及杂质离子的能力，且剧毒气体AsH₃的析出风险较低。然而，该除杂方法在能耗与流程整合方面仍存在优化空间，可采用机械式蒸汽再压缩（MVR）技术以显著降低蒸汽消耗，并构建在线监测与人工智能（AI）优化系统，实现对关键工艺参数的精准控制。其除杂技术可作为辅助净化手段，与电积法组合成多技术耦合工艺，未来应重点开发高性能除杂功能材料，推进废酸与有价金属高效回收体系，最终实现铜电解液高效、低耗与绿色的深度净化目标。

关键词: 净化, 分离, 铜电解精炼, 电解液, 除杂

Abstract:

The purification of copper electrolyte is crucial for ensuring the quality of cathode copper and the efficient recovery of valuable metal resources. However, existing impurity removal technologies generally suffer from issues such as high energy consumption, tendency to cause secondary pollution and insufficient separation efficiency. This review systematically summarized the principles and application status of mainstream purification methods including electrowinning, precipitation, ion exchange, adsorption, solvent extraction and membrane separation, while providing a comparative analysis of their advantages and limitations in industrial applications. Analysis indicated that the cyclic electrowinning process was the most widely used impurity removal method in large-scale cathode copper production enterprises worldwide owing to its ability to treat high concentrations of copper and impurity ions and its low risk of releasing highly toxic AsH₃ gas. Nevertheless, there remained room for optimization in terms of energy consumption and process integration for this method. The adoption of mechanical vapor recompression (MVR) technology could significantly reduce steam consumption, and the establishment of online monitoring and artificial intelligence (AI) optimization systems enabled precise control of key technical parameters. Other impurity removal technologies could serve as auxiliary purification means combined with the electrowinning method to form integrated multi-technology processes. Future efforts should focus on developing high-performance functional materials for impurity removal and advancing efficient recycling systems for waste acid and valuable metals, ultimately achieving the goal of deep purification of copper electrolyte with high efficiency, low consumption and environmental sustainability.

Key words: purification, separation, electrolytic refining of copper, electrolyte, impurity removal

中图分类号:

TQ151.8

邹先志, 廖亚龙, 杨双宇. 铜电解液净化除杂研究进展[J]. 化工进展, 2025, 44(S1): 492-503.

ZOU Xianzhi, LIAO Yalong, YANG Shuangyu. Research progress on purification and impurity removal in copper electrolyte[J]. Chemical Industry and Engineering Progress, 2025, 44(S1): 492-503.

图/表 10

参考文献 67

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种类	特性	杂质	在电解液中的行为
第一类	电位比铜负	Zn、Fe、Ni、Pb、Sn等	以离子形式随阳极溶解进入电解液或以硫酸盐沉淀等形式进入阳极泥
第二类	电位比铜正	Au、Ag、Pt、Pd等	不溶解，以沉淀形式进入阳极泥
第三类	非金属元素	O、S、Se、Te等	大部分存在于阳极泥中
第四类	电位与铜近	As、Sb、Bi等	电解过程中既能与铜一起溶解进入电解液形成“漂浮阳极泥”，同时存在与铜在阴极上共同析出

种类	特性	杂质	在电解液中的行为
第一类	电位比铜负	Zn、Fe、Ni、Pb、Sn等	以离子形式随阳极溶解进入电解液或以硫酸盐沉淀等形式进入阳极泥
第二类	电位比铜正	Au、Ag、Pt、Pd等	不溶解，以沉淀形式进入阳极泥
第三类	非金属元素	O、S、Se、Te等	大部分存在于阳极泥中
第四类	电位与铜近	As、Sb、Bi等	电解过程中既能与铜一起溶解进入电解液形成“漂浮阳极泥”，同时存在与铜在阴极上共同析出

元素	进入电解液	形成漂浮阳极泥	进入沉降阳极泥	主要存在形态
As	高	中等	较低	离子形态[As(Ⅲ)、As(Ⅴ)]溶解较多，部分水解
Sb	中等	高	中等	极易水解形成胶体（如Sb₂O₅·nH₂O）
Bi	中等	较低	高	易与铅等形成不溶化合物（如铋酸铅）

元素	进入电解液	形成漂浮阳极泥	进入沉降阳极泥	主要存在形态
As	高	中等	较低	离子形态[As(Ⅲ)、As(Ⅴ)]溶解较多，部分水解
Sb	中等	高	中等	极易水解形成胶体（如Sb₂O₅·nH₂O）
Bi	中等	较低	高	易与铅等形成不溶化合物（如铋酸铅）

方法类型	特点
静电吸引	与带负电的砷（AsO₃³⁻、AsO₄³⁻）、铋（BiCl₄⁻）等阴离子相互吸引，作用范围相对较远，是初始吸附的重要步骤
离子交换	吸附剂中的可交换阴离子（如Cl⁻、OH⁻）与溶液中的杂质阴离子进行交换，可逆性相对较高
表面络合/化学键合	吸附剂表面的Sb原子（路易斯酸）与杂质阴离子（路易斯碱）形成内层表面络合物或特定化合物（如Sb-Bi结合物），选择性高，结合牢固，通常是化学吸附，吸热、熵增的自发过程
共沉淀与表面沉积	被吸附的杂质与吸附剂溶解组分或直接在表面形成难溶化合物（如焦锑酸铋）并沉积
物理筛分（孔道）	吸附剂的纳米级孔道选择性容纳尺寸匹配的杂质离子