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    含铜蚀刻废液资源化综合利用研究进展

    Advances in Comprehensive Resource Utilization of Spent Copper-Containing Etchants

    • 摘要: 含铜蚀刻废液是冶金、化工过程产生的典型危险废物,具有腐蚀性强、盐分高及铜含量高(质量分数达10%)等特点,对其开展资源化处理是实现铜回收与废水减排的关键。本文基于含铜蚀刻废液的特征,系统综述了电解法、萃取法、金属置换法、化学沉淀法等资源化技术的最新研究进展,分析从含铜蚀刻废液回收铜的原理,梳理铜回收的关键节点和发展趋势。分析认为,电解法常用于酸性含铜蚀刻废液的回收,铜纯度可达99.99%,其中氯气控制和产品纯度提升是技术的关键;萃取法主要用于碱性蚀刻废液的再生,并富集提纯铜,萃取率可达99.9%,该方法结合电解、沉淀等技术可制备高纯铜、硫酸铜等产品;金属置换法主要用于处理酸性蚀刻废液,产品为海绵铜,纯度相对较低(约80%),且尾液需进一步处理;化学沉淀法在含铜蚀刻废液处理中应用最广泛,可用于回收硫酸铜、碱式氯化铜等多种产品。基于蚀刻液中铜赋存形态和废液特征,未来技术应进一步加强梯级利用工艺与一体化设备开发,进一步提高铜的回收率,同步开发新型、高价值的铜产品类型,提升含铜蚀刻废液的潜在经济价值。

       

      Abstract: Spent copper-containing etchants produced in metallurgical and chemical processes are classified as typical hazardous wastes. These effluents are highly corrosive and characterized by high copper (Cu) concentrations (up to 10 wt.%) and high salinity. Comprehensive resource utilization is crucial for the effective treatment and Cu recovery of these spent etchants. This paper reviews the latest research advances in technologies for the comprehensive utilization of such wastewater, including electrowinning, solvent extraction, metal replacement, and chemical precipitation. The mechanisms of Cu recovery are elucidated, and key processes and development trends are analyzed. Among these technologies, electrochemical deposition is frequently employed for the in situ recovery of Cu and etchant regeneration from acidic spent etchants. The Cu recovery efficiency and purity can be as high as 100% and 99.99%, respectively. Future development of this technology should focus on mitigating chlorine gas emissions and further improving product purity. Solvent extraction is primarily utilized for the regeneration of alkaline spent etchants, as well as the extraction and enrichment of Cu, with extraction rates reaching 99.9%. Furthermore, combining extraction with other methods (e.g., electrochemical deposition and neutralization-precipitation) enables the recovery of various high-value products, such as high-purity copper and copper sulfate. Metal replacement using iron and aluminum is commonly applied for the recovery of sponge copper from spent acidic etchants. However, the purity of the resulting sponge copper is relatively lower (approximately 80%). Moreover, the pH of the post-reaction wastewater is typically less than 3, and the residual copper concentration remains around 1 wt.%, necessitating further treatment. Chemical precipitation is the most widely applied technology for treating both acidic and alkaline spent etchants, facilitating the recovery of various products (e.g., copper sulfate and basic copper chloride). Considering the characteristics of spent etchants, such as copper speciation, concentration, and pH, future research should focus on: (1) intergrating multiple technologies (e.g., solvent extraction and electrochemical deposition) to achieve stepwise resource utilization and comprehensive wastewater treatment, (2) developing corresponding reaction equipment to promote the industrial application of these technologies, and (3) exploiting new, high-value copper products to increase the potential economic benefits from spent etchant recovery.

       

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