The thermodynamics and kinetics of ethanol antisolvent crystallization of rare earths from sulfate solutions has been explored, with a view towards separating the rare earths as part of a NdFeB magnet recycling process. The solubility of single and binary metal (Nd, Pr, Fe) phases in aqueous ethanol solutions has been determined. The impact of Fe and Pr on the crystallization of Nd is evaluated, the oxidation kinetics of Fe(II) to Fe(III) quantified, and the influence of Fe oxidation state on the thermodynamics and kinetics of crystallization investigated. Oxidation to Fe(III) is slow, with a half life of approx. 600 h. For pure Nd, the solubility of the obtained, stable sulphate octahydrate decreases exponentially with increased molar organic:aqueous (O/A) ratio, and is well described by the OLI model until O/A=0.2. Pr crystallizes as an isostructural octahydrate with similar solubility. Fe(II) precipitates as a mixed solid phase, with a solubility approximately 40 times higher than the rare earths at O/A=0.2. Fe(III) solutions exhibit liquid–liquid phase separation without precipitation at all evaluated concentrations. Nd and Pr coprecipitate together in proportion to their relative concentrations, with Pr precipitating at concentrations well below its pure component solubility. Fe(II) does not precipitate with Nd at O/A≤0.2 even at high concentration, with significant precipitation as separate particles at higher O/A for all concentrations. The crystallization kinetics and the morphology of the Nd phase is affected by the Fe oxidation state. The work highlights the potential of antisolvent crystallization for selective and efficient separation of REE from Fe.

Rare earth elements (REEs) are important for permanent magnets used in for example wind turbines and motors. There is an imbalance in supply and demand of this commodity and the REE have been identified as critical raw materials by the European Union. This study focuses on recovery of REEs from sulfuric acid solutions using antisolvent crystallization in recycling of magnet waste. Ethanol is used as an antisolvent to crystallize Nd2(SO4)3∙8H2O and (Nd/Dy)2(SO4)3∙8H2O. The impact of the presence of Fe in ferrous and ferric states, and of different seeding strategies, on the quality of the crystal product in terms of purity, crystal size, morphology and agglomeration has been investigated. Higher purity (above 99%) is obtained for seeded experiments and the purity is higher for higher seed loading and lower antisolvent dosing rate. Furthermore, Fe(III) has a higher tendency to be incorporated into the pure Nd phase compared to the Nd phase containing 10% of Dy, while Fe(II) is not detected in any of the phases. By balancing the addition of antisolvent and seed loading the optimum conditions in terms of high purity and productivity can be found. The results provide insights to improve the recovery of REEs as a pure concentrate.

Rare earth elements (REE) are recognized as critical raw materials because of their crucial role in vital components of numerous green and high-tech applications. In the present study, antisolvent crystallization of REE sulfate hydrates of industrial interest (Nd (III), Pr (III), and Dy (III)) from sulfuric acid solutions by the addition of ethanol has been studied. Crystallization of REEs in the presence of Fe (II) and Fe (III) as major impurities along with Al (III), Cu (II), Co (II), and B (III) as trace elements is investigated. The incorporation of impurities and its effect on the growing REE phase is examined. The effect of controlled supersaturation generation rate on the product quality (e.g. purity) and crystal phase is investigated. The solid phases are characterized using optical microscopy, SEM-EDX, powder-XRD, and ICP-OES. The findings can offer significant insights to understand and optimize the recovery of REEs from leach liquor in the recycling of magnet waste.