Effect of Slag Chemistry on the Desulfurization Kinetics in Secondary Refining Processes

Abstract

Desulfurization behavior was investigated based on a wide slag composition and working temperature range. Moreover, the rate-controlling step (RCS) for desulfurization with regard to the ladle-refining conditions and the transition of the RCS by changing the slag composition was systematically discussed. The desulfurization ratio reached an equilibrium value within approximately 15 minutes irrespective of the CaO/Al2O3 (=C/A = 1.3 to 1.9) and CaO/SiO2 (=C/S = 3.8 to 6.3) ratios. However, the desulfurization behavior of less basic slags (C/A = 1.1 or C/S = 1.9) exhibited a relatively sluggish [S]-decreasing rate as a function of time. The equilibrium S partition ratio increased with an increase in slag basicity (C/A and C/S ratio), not only due to an increase in sulfide capacity but also due to a decrease in oxygen activity in the molten steel. There was a good correlation between the calculated and measured S partition ratios at various slag compositions. However, the measured S partition ratio increased by adding 5 pct CaF2, followed by a constant value. Multiphase slag exhibited a relatively slow desulfurization rate compared to that of fully liquid slag, possibly due to a decrease in the effective liquid slag volume, interfacial reaction area, and a relatively slow slag initial melting rate due to a high melting point. The activation energy of the desulfurization process was estimated to be 58.7 kJ/mol, from which it was proposed that the desulfurization reaction of molten steel via CaO-Al2O3-SiO2-MgO-CaF2 ladle slag was generally controlled by the mass transfer of sulfur in the metal phase. However, there was a transitional period associated with the rate-controlling mechanism due to a change in the physicochemical properties of the slag. For slag with a viscosity greater than about 1.1 dPa center dot s and an equilibrium S partition ratio lower than about 400, the overall mass-transfer coefficient was affected by the slag properties. Hence, it was theoretically and experimentally confirmed that the RCS of the desulfurization process under secondary refining conditions was strongly dependent on thermodynamic driving forces as well as the viscosity of the slag. (C) The Minerals, Metals Materials Society and ASM International 2017