Synchronous enrichment of copper and arsenic has become a newly emerging and significant problem during copper smelting slag (CSS) flotation, which affects environmental safety and CSS utilization. This study on CSS and its flotation products revealed the factors that affect the flotation enrichment of copper and arsenic from a mineralogy perspective. Mineralogical characteristic studies revealed that copper existed primarily in the form of matte with excellent floatability, whereas arsenic was primarily dissolved or wrapped in glassy silicates without floatability. The second occurrence phase of copper and arsenic, copper–arsenic alloy, was closely embedded with gangue minerals, which increased the difficulty of enriching copper and arsenic. Sequential extraction and X-ray photoelectron spectroscopy analysis indicated that the floatability of copper was better than that of arsenic. Flotation tests showed that copper recovery could reach 82.79%, whereas arsenic recovery was only 40.83%, which further confirmed that copper and arsenic could not be enriched synchronously. Mineral phase reconstruction was proposed as a potential scheme to enhance arsenic recovery. Arsenic was released from glassy silicates and combined with a copper-bearing phase to form copper–arsenic alloy during mineral phase reconstruction, which significantly increased arsenic recovery by 39.34% and slightly increased copper recovery. The synchronous enrichment of copper and arsenic effectively reduces the total arsenic emission during copper pyrometallurgy, thereby alleviating the pressure of environmental pollution caused by CSS flotation tailings. This work provides a scientific reference for CSS processing toward recycling and harmlessness.

铜和砷的同步富集已成为铜冶炼渣（CSS）浮选过程中新出现的重大问题，影响环境安全和CSS利用。对 CSS 及其浮选产品的研究从矿物学角度揭示了影响铜和砷浮选富集的因素。矿物学特征研究表明，铜主要以无浮性的锍形式存在，而砷主要溶解或包裹在玻璃状硅酸盐中，不具有可浮性。铜砷第二赋存期铜砷合金与脉石矿物紧密嵌合，增加了铜砷富集难度。连续萃取和X射线光电子能谱分析表明，铜的可浮性优于砷。浮选试验表明，铜回收率可达82.79%，而砷回收率仅为40.83%，进一步证实了铜和砷不能同步富集。提出了矿物相重建作为提高砷回收率的潜在方案。在矿物相重构过程中，砷从玻璃状硅酸盐中释放出来并与含铜相结合形成铜砷合金，使砷回收率显着提高了 39.34%，铜回收率略有提高。铜和砷的同步富集有效降低了铜火法冶炼过程中的总砷排放，从而缓解CSS浮选尾矿造成的环境污染压力。该工作为CSS处理向回收和无害化提供了科学参考。