Abstract

In the present research on rare earth extraction from rare earth oxides (REOs), conversion of rare earth oxides into rare earth fluorides with fluoride fluxes is investigated in order to overcome the problem of low solubility of the rare earth oxides in molten fluoride salts as well as the formation of oxyfluorides in the fluorination process. Based on thermodynamic calculations, a series of experiments were performed for converting the rare earth oxides into rare earth fluorides using AlF3, ZnF2, FeF3, and Na3AlF6 as fluorinating agents in a LiF–Nd2O3 system. The formation of neodymium fluoride as a result of the reactions between these fluxes and neodymium oxide is confirmed. The rare earth fluoride thus formed can subsequently be processed through the electrolysis route in the same reactor, and rare earth metal can be produced as the cathodic deposit. In this concept, the REO dissolution in molten fluorides would become unnecessary due to the complete conversion of the oxide into the fluoride, REF3. The results of XRD and EPMA analysis of the reacted samples indicate that AlF3, ZnF2, and FeF3 can act as strong fluorinating agents for the neodymium oxide giving rise to a complete conversion of neodymium oxide into neodymium fluoride.

Highlights

  • Rare earth oxides are among the most stable oxides of the elements in the periodic table

  • Adding an excess amount of AlF3 to the system can result in the complete conversion of neodymium oxide, which needs to be proved in the future research

  • In the case of FeF3, three small peaks in X-ray diffractometry (XRD), corresponding to the neodymium oxyfluoride phase, were identified; in the electron probe microanalysis (EPMA) mapping of this system, neodymium was found to be highly concentrated around the FeO grain boundaries, whereas oxygen and fluorine are were found at very low concentrations

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Summary

Introduction

Rare earth oxides are among the most stable oxides of the elements in the periodic table. Chen et al [1] have developed a direct electrochemical process for the reduction of solid metal oxides into their metals in molten salts, the FFC process. This method has been extensively adopted in metal extraction for a number of elements including rare earth metals (RE = Gd, Tb, Dy, Er, and Ce) [2,3,4]. The efficiency of the oxygen removal by direct electrochemical reduction of oxides is mainly determined by the geometry of the samples, the surface area of the solid sample in contact with the molten salt, and the initial oxygen concentrations. The FFC process has not yet been commercialized, and one of the main challenges is the residual oxygen concentration in the reduced metal

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