A Theoretical Approach to the Sublimation Separation of Zirconium and Hafnium in the Tetrafluoride Form

"SynopsisThe separation of zirconium and hafnium is essential in the nuclear industry, since zirconium alloys for this application require hafnium concentrations of less than 100 ppm. The separation is, however, very difficult due to the numerous similarities in the chemical and physical properties of these two elements.Traditional methods for separation of zirconium and hafnium rely predominantly on wet chemical techniques, e.g. solvent extraction. In contrast to the traditional aqueous chloride systems, the AMI zirconium metal process developed by Necsa focuses on dry fluoride-based processes. Dry processes have the advantage of producing much less hazardous chemical waste.In the proposed AMI process, separation is effected by selective sublimation of the two tetrafluorides in an inert atmosphere under controlled conditions, and subsequent selective desublimation. Estimates are made for the sublimation rates of the two tetrafluorides based on the equilibrium vapour pressures. A sublimation model, based on the sublimation rates, was developed to determine if the concept of separation by sublimation and subsequent desublimation is theoretically possible.IntroductionZirconium requires several purification steps to conform to nuclear-grade specifications. Little information is available on the sublimation separation of Zr and Hf compounds, especially in the fluoride form, the majority of which deals with sublimation under vacuum conditions. On the industrial scale, only vacuum sublimation of ZrF4 has been reported. No records were found for the sublimation of ZrF4 in an inert atmosphere. Information on the sublimation rate of ZrF4 or HfF4 in an inert atmosphere is also limited. The rate is assumed to be dependent on several factors, of which temperature, area, and composition are considered the most important."