The effect of antisolvent selection on rare earth sulfate crystallisation, J. Du Plessis, J. Chivavava, and A.E. Lewis

Current metallurgical processes lack selective and efficient REE recovery from aqueous leach liquors. Antisolvent crystallisation is used to selectively recover pure inorganic salts from aqueous solutions without excessive chemical use in ambient conditions. Yttrium sulfate octahydrate (Y2(SO4)3.8H2O) was used as a representative rare earth salt to investigate the effect of antisolvent selection on the crystal morphology and size distribution of the final crystalline product produced through antisolvent crystallisation. The antisolvents of choice were short length alcohols that are water miscible i.e. methanol, ethanol, 2-propanol and t-butanol. All experimental parameters except the type of antisolvent were kept constant under isothermal conditions. The large reduction in solubility of the salt by the antisolvent creates high supersaturations. This leads to high product yields as observed in this study at > 91%. In general, a variety of morphologies were successfully formed in each individual alcohol including; rods, plates, prismatic cubes and starburst clusters. The powder X-ray diffraction (XRD) analysis indicated that Y2(SO4)3.8H2O was the only species present for all final products. There was a change observed from the starburst and rod structures for the shorter alcohols towards prismatic cubes for the longer alcohols due to different strengths in the solute-antisolvent interaction at the crystal growth faces. The crystal sizes increased with an increase in the alcohol chain length because of the lower supersaturation conditions due to a limit in the mass transfer induced by the bulkier alcohol structure. In conclusion, it has been shown that the particle morphology and size can be greatly affected by the selection of antisolvent even under high supersaturation conditions, contributing to understanding the effect of different antisolvents on the final particle characteristics. The engineering of favoured product characteristics can therefore be achieved by antisolvent crystallisation, presenting a viable alternative process for the recovery of REE. Keywords: Antisolvent crystallisation, rare earth elements, morphology, particle size