Kinetics of chromium oxide reduction from a basic steelmaking slag by silicon dissolved in liquid iron

Abstract

The reduction of chromium oxide from a basic steelmaking slag (45 wt pct CaO, 35 wt pct SiO₂, 10 wt pct MgO, 10 wt pct A1₂O₃) by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-limiting steps. The reduction is described by the reactions: (Cr₂O₃) + Si = (SiO₂) + (CrO) + Cr [1] and 2 (CrO) +Si = (SiO₂) + 2 Cr [2] The experiments were carried out under an argon atmosphere in a vertical resistance-heated tube furnace. The slag and metal phases were held in zirconia crucibles. The course of the reactions was followed by periodically sampling the slag phase and analyzing for total chromium, divalent chromium, and iron. Results obtained by varying stirring rate, temperature, and composition defined the rate-limiting mechanism for each reaction. The rate of reduction of trivalent chromium (reaction [1] above) increases with moderate increases in stirring of the slag, and increases markedly with increases in temperature. The effects of changes in composition identified the rate-limiting step for Cr⁺³ reduction as diffusion of Cr⁺³ from the bulk slag to the slag-metal interface. The rate of reduction of divalent chromium does not vary with changes in stirring of the slag, but increases in temperature markedly increase the reaction rate. Thus, this reaction is limited by the rate of an interfacial chemical reaction. The reduction of divalent chromium is linearly dependent on concentration of divalent chromium, but is independent of silicon content of the metal phase.