Electrolytic Recovery of High Purity Zr from Radioactively Contaminated Zr Alloys in Chloride Salts

It has been believed that high purity Zr metal is hard to be prepared from Zr alloys in LiCl-KCl salts since Zr has various redox reactions in LiCl-KCl including insoluble ZrCl formation and disproportionate reaction between Zr and Zr4+. We examined electrolytic Zr recovery from Zircaloy-4 by controlling anodic potential at five concentrations of ZrCl4 in LiCl-KCl salts. Anode potential of - 0.9 V (vs. Ag/AgCl) was applied to prevent the elements except Zr being dissolved from the anode into the electrolyte. Experimental results showed Zr with purity of over 99.9% was recovered and all alloying elements were analyzed below their detection limit in ICP-MS. In addition, at low ZrCl4 concentrations of 0.1 and 0.5 wt.%, the chemical form of the cathode deposits was Zr metal without ZrCl while only ZrCl without Zr metal was recovered at the high ZrCl4 concentration, 2.0 and 4.0 wt.%. At the ZrCl4 concentration of 1.0 wt.%, both Zr metal and ZrCl were recovered. Therefore, preparation of high purity Zr metal from Zr alloys is feasible in LiCl-KCl at low concentration of ZrCl4.