Solubility of Rhodium in Doré Metal

"The solubilities of rhodium (Rh) in a molten silver alloy in doré-smelting conditions for treating copper refinery slime at temperatures of 1,000 to 1,300 °C were measured using a high-temperature equilibration-quenching technique and direct phase analysis by electron probe X-ray microanalysis. The results obtained indicate that the solubility of rhodium in molten silver is very limited: only 0.04 to 0.26 weight percent at 1,000 and 1,300 °C, respectively. The thermodynamic properties of rhodium in molten silver were estimated from the solubility data. The compositions of the solid rhodium alloys in equilibrium with molten silver-rich doré metal were also measured in this study. The excess rhodium in the doré alloy will precipitate during the refining as solid, greater than 99 weight percent Rh.IntroductionSilver refining is a core step of the processes of anode slime treatment and precious metals recovery in copper refineries (Hait, Jana and Sanyal, 2009; Ludvigsson and Larsson, 2003). It separates the oxidic materials, such as nickel oxide (NiO) and barium sulfate (BaSO4), from metallics after the de-coppering and de-selenation steps of the anode slime, and refines the silver bullion from the undesired elements present (Cooper, 1990; Hyvärinen, Lindroos and Yllö, 1989). Doré metal is a silver-rich alloy which after the smelting step will be refined electrolytically, and the remaining constituents of gold as well as the platinum group metals (PGM) will be subsequently recovered in their own processing stages.Because of low concentrations of PGMs in copper, they are typically soluble in the doré metal in anode slime treatment. This can be concluded from their binary phase diagram data with silver (Massalski et al., 2007). One exception is sometimes encountered in the anode slime smelting operations if the smelter feedstock is rich in rhodium, as may be the case if the raw materials contain secondary raw materials such as e-scrap. The solubility of rhodium in solid silver is less than 0.04 weight percent (Królas and Sternik, 1995), and its solubility in molten silver is highly uncertain. The only experimental information in the literature (Królas et al., 1993; Elliott, 1985) suggests that the silver-rhodium alloy system at 960 °C forms a eutectic, which locates less than 2 °C below the melting point of pure silver (Arblaster, 2015). Early observations (Rössler, 1900) propose that rhodium is insoluble in molten silver even if solid silver-rhodium solutions have been recently produced on a nanoscale (Kusada et al., 2010).The aim of this study is to measure experimentally the solubility of rhodium in molten silver at doré metal smelting and refining temperatures. The silver alloy used to mimic the doré alloy contained silver and about 1 weight percent of the alloying elements copper, gold, palladium, rhodium and tellurium. The experiments were carried out in metal-slag equilibria with nitrogen-oxygen mixtures as the atmosphere, employing an equilibration-quenching technique and using direct phase composition analysis by electron probe X-ray microanalysis (EPMA) (Jak, Hayes and Lee, 1995)."