To reduce the Mn vaporization during recycling rejected electrolytic manganese metal by electroslag remelting, it is proposed to reduce the temperature of molten slag pool, but which leads to the degradation of slag desulfurization. The desulfurization by interaction between CaF2–CaO–Al2O3–Na2O slag and rejected electrolytic manganese metal scrap was studied from the view of thermodynamics in this study. The results show that sulfur distribution ratio decreases with increase of CaF2 content, and increases with the increase of Na2O content and temperature. Na2O increases sulfur distribution ratio of slag by increasing CaO activity. Na2O addition in CaF2–CaO–Al2O3–Na2O slag can enhance desulfurization ability of slag due to the larger sulfur distribution ratio and lower viscosity. Thus, sulfur content in test of slag T3 bearing 45.8 wt% CaF2-23.2 wt% CaO-22.7 wt% Al2O3-8.3 wt% Na2O is much lower than that of slag without Na2O, implying that 45.8 wt% CaF2-23.2 wt% CaO-22.7 wt% Al2O3-8.3 wt%Na2O slag is the promising slag for recycling rejected electrolytic manganese metal by ESR.
