Additonal authors: Moats, Michael. Book title: Proceedings of the 58th Conference of Metallurgists Hosting Copper 2019. Chapter: . Chapter title:
Antimony and bismuth in copper electrorefining electrolytes can cause cathode contamination, leading to the careful control of their concentrations. This study examined the laboratory scale removal of bismuth and antimony from an electrorefining electrolyte using a solvent extraction mini-pilot plant. The ability of a proprietary phosphonic acid ester extractant (REX-2) in a commercial diluent was studied in a simulated commercial setting. Antimony and bismuth were both extracted effectively from the electrolyte (72% Bi and 70% Sb removed) and Bi was effectively stripped (92% Bi recovered) with 400 g/L sulfuric acid. A final strip solution was obtained from the SX circuit containing 0.36 g/L Bi, 0.043 g/L Sb, 1.3 g/L Cu, and 0.18 g/L As. Unfortunately, most of the extracted Sb remained in the organic phase. Following the pilot study, experiments were performed to examine the precipitation of bismuth from the aqueous strip phase and the removal of antimony loaded on to REX-2.
For many years, antimony and bismuth have been some of the most problematic impurities in copper electrorefining (ER) (Bardwell & Lapee, 1933). Along with surface roughening, high concentrations of Sb and Bi can contaminate the copper cathode and precipitate at the copper grain boundaries. This drastically reduces the drawing ability of the metal (Bender & Emmerich, 2016). For these reasons, it is necessary to control Sb and Bi concentration in the cathode, which is done by controlling their concentration in the electrolyte.
Conventionally, Sb and Bi concentrations are controlled by maintaining a proper As/(Sb+Bi) molar ratio in the anode and arsenic concentration in the electrolyte. Antimony and bismuth are removed during electrolyte purification using liberators (electrowinning cells) and/or ion exchange.
Liberators treat an electrolyte bleed stream from the ER circuit and electrodeposit increasingly impure copper as the copper concentration of the solution decreases. Traditionally, first stage liberators reduce the copper concentration from ~45 g/L to ~15 g/L and produce saleable copper. Second stage liberators decrease the copper concentration to ~8 g/L (Biswas & Davenport, 1980) which results in contaminated cathode that is returned to anode production (Biswas & Davenport, 1980; Wang, 2004). Further electrolyte purification is not always required but third stage liberators can be used to reduce copper concentration below 2 g/L which results in significant removal of As, Sb and Bi and very impure deposits which are recycled to a smelter or used for As production. However, liberators do not have very high energy efficiency (Acharya, 2014; Ando & Tsuchida, 1997) and below 0.5 g/L copper, highly toxic arsine gas may form (Biswas & Davenport, 1980).