Herein, a new clean extraction technology for the decomposition of bastnasite concentrate by utilizing the microwave radiation is proposed, which prevented Ce(III) from being oxidized to its tetravalent form. The process includes microwave radiation roasting to nonoxidatively decompose the bastnasite concentrate, mechanism analysis of Ce(III) not being oxidized to Ce(IV), hydrochloric acid leaching of the nonoxidative roasted ore, and kinetics analysis of the leaching process. The experiments were carried out concentrating on the effect of roasting temperature and holding time on the decomposition rate of the bastnasite concentrate and the oxidation rate of cerium and the effect of acidity, liquid–solid ratio, leaching temperature, and stirring rate on the leaching kinetics of the nonoxidative roasting ore. When the roasting temperature is 1100 °C, the holding time is 20 min, and the m (C)/m (REFCO_(3)) ratio is 0.2, the results show that the leaching efficiency of rare earths can reach 85.45% under the conditions 3 mol/L HCl, 90 °C, 60 min, 9 mL/g liquid–solid ratio, and 300 rpm stirring rate. The X-ray diffraction and scanning electron microscopy analyses of the samples before and after acid leaching show that the rare earth oxides were completely leached and Ce(III) was not oxidized to its tetravalent form. The apparent activation energies of leaching rare earths were calculated as 14.326 kJ/mol, and the HCl leaching process can be described by a new variant of the shrinking-core model, in which both the interfacial transfer and the diffusion through the product layer influenced the reaction rate. Furthermore, a semiempirical rate equation was created to describe the leaching process of the nonoxidative roasted ore.
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