Effect of Fe/SiO2 Ratio and Fe2O3 on the Viscosity and Slag Structure of Copper-Smelting Slags

Secondary copper smelting is an effective means of treating waste resources. During the smelting process, the viscous behavior of the smelting slags is essential for smooth operation. Therefore, the effects of Fe/SiO2 ratio and Fe2O3 contents on the viscous behavior of the FeO−Fe2O3−SiO2−8 wt%CaO−3 wt%MgO−3 wt%Al2O3 slag system were investigated. The slag viscosity and activation energy for viscous flow decrease with increasing Fe/SiO2 from 0.8 to 1.2, and increase as the Fe2O3 content increases from 4 wt% to 16 wt% at Fe/SiO2 ratio of 1.2. However, under the conditions of Fe/SiO2 of 0.8 and 1.0, the viscosity and activation energy for viscous flow show a minimum value at Fe2O3 content of 12 wt%. Fe2O3 exhibits amphoteric properties. In addition, the increase in Fe2O3 content raises the breaking temperature of the slag, while the Fe/SiO2 ratio has the opposite effect. Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy show that increases in Fe/SiO2 ratio lead to simplification of the silicate network structure, while increases in Fe2O3 content improves the formability of the network. This study provides theoretical support for the related research and application of secondary copper smelting.

Study of the Structure of FeOx-CaO-SiO2-MgO and FeOx-CaO-SiO2-MgO-Cu2O-PdO Slags Relevant to Urban Ores Processing through Cu Smelting

Ferrous-calcium-silicate (commonly known as FCS) slags are used in the valuable metal recycling from urban ores through both primary and secondary copper smelting processes. In the present study, the structure of selected FCS-MgO (FCSM) and FCS-MgO-Cu2O-PdO (FCSM-Cu2O-PdO) slags, relevant to the processes, were investigated using Fourier-transform infrared (FTIR) spectrometry. Deconvolution of the FTIR spectra was carried out to calculate the relative abundance of different silicate structural units (Qn), the overall degree of polymerization (DOP) of the slags and the oxygen speciation in the FCS slags. It was observed that, for the slag investigated, the relative intensity of both the high-frequency band ≈ 1100 cm−1 (Q3) and low-frequency band ≈ 850 cm−1 (Q0) were affected by Fe/SiO2 ratio, basicity, temperature (T) and oxygen partial pressure (pO2). The DOP and the average number of bridging oxygen (BO) were found to decrease with increasing both Fe/SiO2 ratio and basicity. Improved semi-empirical equations were developed to relate the DOP of the slags with chemistry, process parameters and partitioning ratio (i.e., the ratio of the amount of element in the slag phase to metal phase, also known as distribution ratio) of Pd and Ge. Possible reactions, expressed as reactions between metal cations and silicate species, as a way to evaluate thermodynamic properties, are presented herein.

Precious metal recoveries in secondary copper smelting with high-alumina slags

Waste electrical and electronic equipment (WEEE) represents a significant urban resource for precious metals. To maximize the recoveries and sustainable use of these metals, their behavior needs to be characterized in the secondary copper smelting of WEEE. The current study experimentally determined the distributions of gold, silver, platinum and palladium between copper alloy and FeOx–SiO2–Al2O3/FeOx–SiO2–Al2O3–CaO slags (LCu/s[M] = [M]Copper/[M]Slag) over the oxygen partial pressure range of 10−5 – 10−10 atm at 1300 °C. In addition, the equilibria of copper alloy, slag and Al–Fe spinel system are presented and discussed. The experiments were conducted employing an equilibration—drop-quenching technique followed by major element analysis with Electron Probe MicroAnalysis (EPMA) and trace element analysis with sensitive Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). The results showed that the distribution coefficient of silver increased from 10 to 103 as a function of decreasing oxygen partial pressure. For gold, platinum and palladium, the distribution coefficients were at minimum 105. Lime addition improved the recovery of silver notably and had a small positive effect on gold recovery into copper. Overall, the precious metals can be recovered very efficiently in copper alloy via secondary copper smelting with alumina-rich iron-silicate slags.

Critical Metals Ga, Ge and In: Experimental Evidence for Smelter Recovery Improvements

High-tech metals, including Ga, Ge and In, are critical for the performance of electrical and electronic equipment (EEE). None of these three metals exist in mineable levels in natural minerals, and thus their availability and production are dependent on the primary and secondary base metals (including Zn, Al and Cu) production. To secure the supply of high-tech metals in the future, their behavior, including distribution coefficients (LCu/s = [wt% M]in copper/(wt% M)in slag), in primary and secondary processes need to be characterized. This study reports three series of copper-slag distribution experiments for Ga, Ge and In in simulated secondary copper smelting and refining process conditions (T = 1300 °C, pO2 = 10−9–10−5 atm) using a well-developed drop–quench technique followed by EPMA and LA-ICP-MS analyses. This study shows how an analytical technique more traditionally applied to the characterization of ores or minerals can also be applied to metallurgical process investigation. The LA-ICP-MS analysis was used for the first time for measuring the concentrations of these minor elements in metallurgical glasses, i.e., slags, and the results were compared to the geological literature. The distribution coefficient of indium increased as a function of decreasing oxygen partial pressure from 0.03 to 10, whereas the distribution coefficient of gallium was 0.1 at 10−9 atm and decreased as the pO2 increased. The concentrations of gallium in slags were between 0.4 and 0.6 wt% and germanium around 1 ppm. Germanium was vaporized almost entirely from the samples.