Chlorination of UO2, PuO2 and rare earth oxides using ZrCl4 in LiCl–KCl eutectic melt

A new chlorination method using ZrCl4 in a molten salt bath has been investigated for the pyrometallurgical reprocessing of nuclear fuels. ZrCl4 has a high reactivity with oxygen but is not corrosive to refractory metals such as steel. Rare earth oxides (La2O3, CeO2, Nd2O3 and Y2O3) and actinide oxides (UO2 and PuO2) were allowed to react with ZrCl4 in a LiCl–KCl eutectic salt at 773 K to give a metal chloride solution and a precipitate of ZrO2. An addition of zirconium metal as a reductant was effective in chlorinating the dioxides. When the oxides were in powder form, the reaction was observed to progress rapidly. Cyclic voltammetry provided a convenient way of establishing when the reaction was completed. It was demonstrated that the ZrCl4 chlorination method, free from corrosive gas, was very simple and useful.