A Contribution to Chloride Hydrometallurgy: Regeneration of Superazeotropic Strength HCL via Reactive Crystallization

The feasibility of chloride leaching processes depends on interfacing them with cost-effective HCl regeneration technologies. This paper summarizes the most important findings of research conducted in the past 3 years concerned with a novel process to regenerate high-strength HCl from concentrated CaCl2 solutions at temperatures below 100°C, via reaction of CaCl2 with H2SO4 resulting in the formation of calcium sulfate phases (gypsum, a-hemihydrate or anhydrite). From constant supersaturation semi-batch experiments in pure solution it was found that the crystal growth rate of hemihydrate, and hence the particle size, was influenced by the rate of reagent (Ca2+, SO4 2-) supply to the reactor. Additionally, growth studies of DH in presence of impurities (K+, Mg2+, Sr2+, Ba2+, Fe2+/3+, Al3+, La3+, Y3+, F- and PO4 3-) showed that specifically Sr2+ and PO4 3- are taken up during crystal growth. Furthermore, it was found that decreasing water activity (via different HCl/CaCl2 concentrations) and increasing temperature reduce the metastable life-time of DH and HH by increasing the phase transformation speed. The DH/HH transformation was identified to be dissolution-precipitation based, while HH to AH is a topochemical process. Finally, continuous experiments on bench scale are underway to confirm the feasibility of the process to obtain super-azeotropic strength HCl with up to 9 mol/L (~30wt.%) from 5 mol/L CaCl2 (~40wt.%) solution.