Preparation of Metallic Zr from ZrO via Carbothermal and Electrochemical Reduction in Molten Salts.

Zirconium, a critical rare metal with exceptional corrosion resistance and nuclear applications, is conventionally produced via the energy-intensive Kroll process. The electrolysis of ZrCO soluble anodes has been extensively investigated due to its advantages in having a short process flow and resulting in high-quality products. In particular, during the electrolysis of zirconium oxycarbide with a C:O molar ratio of 1:1, gaseous CO can be released, and no residual anodes are generated, which is extremely appealing. In this regard, this paper explores the feasibility of preparing zirconium metal through high-temperature vacuum reduction to produce zirconium oxycarbide using ZrO as the raw material, followed by direct molten-salt electrolysis. Firstly, the reduction products were characterized using an X-ray diffractometer (XRD) and a scanning electron microscope (SEM). The results showed that under a vacuum of <10 Pa at 1750 °C, the reduction products mainly consisted of ZrCO and a small amount of ZrO, and they exhibited good electrical conductivity (0.0169 Ω·cm). Subsequently, the cyclic voltammetry test results of the reduction products revealed the reversible redox behavior of ZrCO. There were characteristic oxidation peaks at -0.53 V and -0.01 V (vs. Pt), corresponding to the formation of Zr and Zr, respectively, and a reduction peak at -1.51 V, indicating the conversion from Zr to Zr. Finally, -zirconium metal with a purity of 99.2 ± 0.3 wt.% was obtained through potentiostatic electrolysis, and its quality met the R60704 grade specified in ASTM B551-12 (2021). This study offers a novel approach for the short-flow preparation of zirconium metal, which is conducive to expanding its applications.