Chloridizing roasting studies of spent NdFeB magnets for recovery of rare earth values

Abstract

The increased demand for rare earth elements in advanced technological applications and supply shortages call for metal recovery from secondary sources. Permanent magnet (Nd₂Fe₁₄B or NdFeB) may serve as a potential secondary source due to its high rare earth (Nd+Pr+Dy: ∼30 %) content and its vast application. The present study utilizes a chloridizing roasting (CaCl₂.2 H₂O) pre-treatment process followed by water leaching, acid leaching (0.5 M HCl, S/L =1/10 g/ml, 90 °C, 3 h), oxalic acid precipitation and calcination (850 °C, 2 h) to obtain mixed rare earth oxides. The process was optimized based on temperature (400–700 °C), dosage (CaCl₂.2H₂O: NdFeB=0.5:1–2.5:1), and time (30–120 min) on the rare earth dissolution. The theoretical activation energy for the chloridizing roasting process is estimated as 22.3 (OFW) and 16.7 kJ/mol (KAS), while the experimental activation energy for Nd and Dy dissolution was determined to ∼29.3 and ∼17.7 kJ/mol, respectively depicting product layer diffusion-controlled kinetics. Higher dosages of CaCl₂.2H₂O (1.5:1 and 2:1) favored NdOCl formation, thereby, higher dissolution; however, further higher dosage (2.5:1) leads to reduced Nd dissolution due to higher CaO formation and acid consumption by Ca during leaching. Incomplete oxidation at lower temperatures (400 °C) and iron dissolution impair the Nd dissolution and selectivity. Excessive oxidation at >700 °C favors the formation of NdFeO₃, decreasing Nd dissolution. The maximum dissolution of Nd was ∼89 %, while for Dy, it was ∼88 % at optimum conditions of 600 °C, 90 min, 2:1. Water leaching post-roasting leads to ∼87 % Ca removal and the precipitation efficiency of rare earth oxalates was 99 %. The overall extraction for rare earth elements was ∼89 %, and 1 kg of NdFeB powder can yield ∼285 g of rare earth oxides (∼239 g Nd₂O₃, ∼14 g Dy₂O₃) with 96 % purity. Further, this study demonstrates that using CaCl₂.2 H₂O as a solid chlorinating agent in chlorination roasting enhances recovery rates of mixed rare earth oxides while providing a safer and more environment-friendly alternative for industrial applications.