A theoretical approach to the sublimation separation of zirconium and hafnium in the tetrafluoride form

The 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.