Reverse-Polarity Dc Plasma-Driven Electro-Reduction Of Refractory Metals In Molten Oxide Melts

This work is concerned with the extraction of refractory metals using an electro-reduction process, in which a molten oxide melt, instead of halide, is used as the electrolyte. The process may provide an alternative method of producing refractory metals from their ores through use of a reverse-polarity direct current (DC) plasma arc heating process. In such a process, the plasma torch itself acts as an anode, and resulting liquid or solid product metals work as a cathode, whereas the molten oxide melt plays the role of an electron transfer layer. The focus of this study is: the electro-reduction of scheelite; vanadium pentoxide; and chromite. For the vanadium pentoxide, the proposed melt is mainly composed of CaO-V2O5/Li2O-B2O3-V2O5or FeO-CaO-SiO2-V2O5-Li2O with the addition of other alkali and alkaline metal oxides. In the case of scheelite ore, the SiO2-CaO-Li2O-WO3system is used as melt and metal aluminum or nickel could be used as a collecting media. As for the reduction of chromite ore, SiO2-CaO-Cr2O3-Li2O system with trace amount of CaF2is used as the melt. As a demonstration, chromium was successfully produced at a laboratory scale through the plasma driven electro-reduction process. One of the studied slags had a composition of 13.8% CaO; 4.9%CaF2; 36.4% Cr2O3; 6.9% Li2O; and 38.0% SiO2. Two observations are significant in this laboratory scale study. The first one was that the amount of Cr2O3and FeO, which were predominantly electronic conductors in the oxide melt, greatly affected the conducting mechanism of the melt. With high concentration of Cr2O3and FeO in the melt, the current efficiency was fairly low. In this case, chromium was found to be barely reduced because of electronic conducting mechanism. For example, with initial slag of 60% Cr2O3, no chromium was found reduced. With low concentration of Cr2O3and FeO in the studied melt, typically no more than 30% Cr2O3, it was observed that chromium was readily reduced due to the dominant ionic conducting mechanism. The second observation was that the addition of SiO2tothe melt helped to make the oxide melt more ionic, which was apparently desirable to the molten oxide electrolysis. However, high content of silica had a negative effect on the fluidity of the melt. This was resolved by adding trace amounts of CaF2to the melt. Therefore, by judicious selection of oxide melt, refractory metal oxides might be dissolved into it and yet the melt itself retains the required ionicity. A reverse-polarity DC plasma driven molten oxide electrolysis may prove to be a viable alternative route for the extractive metallurgy of refractory metals.