Purification of used eutectic (LiCl–KCl) salt electrolyte from pyroprocessing

Abstract The separation characteristics of surrogate rare-earth fission products in a eutectic (LiCl–KCl) molten salt were investigated. This system is based on the eutectic salt used for the pyroprocessing treatment of used nuclear fuel (UNF). The investigation was performed using an integrated rare-earth separation apparatus comprising a precipitation reactor, a solid detachment device, and a layer separation device. To separate rare-earth fission products, a phosphate precipitation method using both Li 3 PO 4 and K 3 PO 4 as a precipitant was performed. The use of an equivalent phosphate precipitant composed of 0.408 molar ratio-K 3 PO 4 and 0.592 molar ratio-Li 3 PO 4 can preserve the original eutectic ratio, LiCl-0.592 molar ratio (or 45.2 wt%), as well as provide a high separation efficiency of over 99.5% under conditions of 550 °C and Ar sparging when using La, Nd, Ce, and Pr chlorides. The mixture of La, Nd, Ce, and Pr phosphate had a typical monoclinic (or monazite) structure, which has been proposed as a reliable host matrix for the permanent disposal of a high-level waste form. To maximize the reusability of purified eutectic waste salt after rare-earth separation, the successive rare-earth separation process, which uses both phosphate precipitation and an oxygen sparging method, were introduced and tested with eight rare-earth (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) chlorides. In the successive rare-earth separation process, the phosphate reaction was terminated within 1 h at 550 °C, and a 4–8 h oxygen sparging time were required to obtain over a 99% separation efficiency at 700–750 °C. The mixture of rare-earth precipitates separated by the successive rare-earth separation process was found to be phosphate, oxychloride, and oxide. Through the successive rare-earth separation process, the eutectic ratio of purified salt maintained its original value, and impurity content including the residual precipitant of purified salt can be minimized.