Abstract: Spent cathode carbon block (SCCB) is considered to be a kind of hazardous waste, because it contains a large amount of soluble fluoride salts and toxic cyanides. The life of an aluminum electrolytic cell is generally 5?8 years, and the SCCB would be produced during the overhaul of the cell. Currently, most SCCBs are piled in landfills or stored for disposal in China. The unreasonable disposal of SCCBs will cause serious pollution and damage to the ecological environment, and wastage of valuable carbon material and fluoride salts. The key to the safe disposal and resource utilization of SCCBs is to separate the carbon and fluoride salts deeply. In this study, SCCB was treated by the pyrometallurgical process, and the characteristics of volatilization temperature of fluoride salts were firstly experimentally determined. For a laboratory-scale self-designed high temperature resistance furnace, a three-dimensional model was built and numerical calculation was performed. The heat transfer characteristics, temperature control law and effective volatilization region of fluoride salts were analyzed in detail. The experimental results demonstrate that the effective volatilization temperature of fluoride is higher than 1700 ℃, and the volatilization rate is higher than 93.1%. By simulating the evolution of the temperature field in the furnace under different power supply modes, it is obtained that under the power supply condition of heating at 12 V for 24 h and holding 9 V for 12 h, the maximum temperature in the furnace during the heating phase can reach 2250 ℃, and the theoretical volatilization volume of fluoride salts can reach 98%. After optimization, a step-by-step decreasing mode of power supply can improve the efficiency of treating SCCBs. Moreover, the treating temperature can be maintained for 20 h at 1700 ℃, which is beneficial to the deep separation of carbon material and fluoride salts in SCCB.