We conducted a mechanistic and experimental study on zinc fluoride roasting for the recovery of NdFeB waste to address the difficulties faced during this pyrometallurgical recovery process, such as the high dependence on the quality of raw materials, the high energy consumption involved in roasting transformations, and the low added value of mixed rare earth products. Thermodynamic calculations showed the feasibility of fluorinating rare earths in NdFeB waste, and one-factor experiments were performed. The results showed that at a roasting temperature of 850 °C, a reaction time of 90 min, and 100% ZnF2 addition, the fluorination rate of rare earths could reach 95.69%. In addition, after analyzing the mesophase composition of a clinker under different roasting temperature conditions, it was found that, when the roasting temperature exceeded 850 °C, the fluorination rate of rare earths was reduced, which was consistent with the thermodynamic results. On this basis, response surface methodology (RSM) was used to carry out experiments to investigate in depth the effects of various factors and their interactions on the fluorination rate of rare earths, which provides a sufficient experimental basis for the recovery of NdFeB waste via fluorination roasting. The results of this study show that ZnF2 addition had the greatest influence on the rare earth fluorination reaction, followed by roasting temperature and roasting time. According to the optimization results of the model, the optimal roasting conditions were determined as follows: 119% ZnF2 addition at 828 °C, a roasting time of 91 min, and a rare earth element fluorination rate of 97.29%. The purity of the mixed fluorinated rare earths was as high as 98.92% after leaching the roasted clinker with 9 M hydrochloric acid at a leaching temperature of 80 °C, a liquid–solid ratio of 4 mL/g, and a leaching time of 2.5 h. This study will lay the foundation for promoting the application of pyrometallurgical technology in the recycling of NdFeB waste.
