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The influence of NaCl-CaCl2 on thermal decomposition of REPO4 (RE: Ce, La, Nd, Th) with CaO was studied.The heat decomposing process of REPO4 was tested with TG-DTA experiments.The results showed that the decomposition temperature of REPO4 with CaO was reduced because of adding NaCl-CaCl2 mixture (NaCl:CaCl2=1:1).The influence of the addition of NaCl-CaCl2, roasting temperature and roasting time on decomposition ratio of REPO4 with CaO was studied.The results showed that the decomposition ratio of REPO4with CaO was 79% when the addition percentage of NaCl-CaCl2 was 10%, the roasting temperature was 750℃, and the roasting time was 1 h.