Solution Purification of Copper Electrorefining Electrolyte – A Novel Way to Recover Precious Metals

Additonal authors: Hannula, P.. Book title: Proceedings of the 58th Conference of Metallurgists Hosting Copper 2019. Chapter: . Chapter title:

Proceedings, Vol. Proceedings of the 58th Conference of Metallurgists Hosting Copper 2019, 2019

Lundström, M.

Typical copper electrorefining electrolyte contains tens of grams of copper, some nickel and a wide variety of impurities. Some of these impurities comprise trace amounts of dissolved precious metals like Ag, Pd and Pt that currently are not fully exploited. This study presents an electrochemical method to recover precious metals via a combined electrodeposition-redox replacement (EDRR) process, where energy is used only to deposit copper during the ED-step, while the RR-step relies on the spontaneous replacement of copper by the precious metals (i.e. cementation). In order to conduct the recovery successfully, process parameters such as deposition potential (EDE), deposition time (tDE), redox replacement time (tRR) and the number of cycles (n) was adjusted. Investigations performed in synthetic electrolyte (40 g/L Cu, Ag = 10 ppm) proved the possibility to recover a high purity silver. Short deposition times (tDE) were found to result in small Cu particles that provided a suitably high surface area for silver cementation. In addition, experiments performed in real industrial electrolytes containing 44 g/L Cu and 54 ppb Ag (Boliden Harjavalta, Pori), demonstrated that EDRR could attain Ag recoveries of between 46–67% in an energy efficient, additive-free manner. INTRODUCTION The raw materials used in the state-of-art primary and secondary copper smelters contain mainly base metals, but also notable amounts of Ag, Pt and other precious metals. These valuable metals distribute mostly into the copper matte during the pyrometallurgical treatment (Tirronen et al., 2017) and end up into the cast anodes. During the electrorefining stage, metals more noble than copper such as gold and platinum, are not dissolved but enrich into the anode slimes. In contrast, silver may dissolve slightly and thus, minor chloride addition is used to retain silver in the slime as sparingly soluble AgCl. Moreover, other metals less noble than copper may also dissolve, such as nickel. Therefore the electrolytes used in electrorefining typically contain substantial amounts of copper, nickel and even arsenic as well as minor metals such as antimony and bismuth. In the Boliden electrorefinery these were reported to be in the magnitude of 51.2– 60.4 g/L of Cu, 10.9–15.8 g/L Ni, 7.2–15.9 As, 0.2–0.4 Sb and 0.1–0.4 Bi with an associated sulfuric acid concentration of 139–155 g/L (Lehtiniemi et al., 2018). Copper is the most noble of the dominating base metals in the electrolyte and is thus deposited on the cathode as 99.99% purity LME-A grade. Anode slimes are collected and subjected to precious metals treatment e.g. via pressure leaching—selenium recovery— Doré smelting—Ag refining—Au/Pt/Pd leaching and reduction process (Ludvigsson & Larsson, 2003). The Pori refinery, operating in Finland since 1941, not only produces 133 000 t Cu cathode and 2300 t nickel sulphate annually but also 66 t silver, 4.6 t gold and palladium and platinum (in year 2017).
Keywords: Copper 2019, COM2019