Departure from Equilibria in Ilmenite Smelting

"Ilmenite smelting involves partial reduction of iron oxide from a slag consisting mainly of T1O2, T12O3 and FeO, yielding as products iron (with approximately 2% carbon) and titanium slag. Slag purity requirements preclude any fluxing additions, and the aggressive nature of the slag necessitates a furnace freeze lining. Large departures from thermal and chemical equilibrium hold in the smelter, with possible implications for process stability. The slag is approximately 150K. hotter than the metal, which means that the metal temperature is below the slag melting point; this difference in temperature has been shown to lead to formation of a solid TisOs-rich layer between the slag and metal. Recent equilibrium measurements have confirmed that the slag and metal are not in chemical equilibrium either, with significantly more reducing conditions in the metal than in the slag. After solidification, the pseudobrookite slag structure is metastable below approximately 1400K, and may transform upon slight oxidation.IntroductionThe natural mineral ilmenite is the main source of titanium, which is mainly used to produce Ti02-based pigments. Ilmenite has the ideal formula FeTiC>3, but natural minerals can be partially oxidized (to contain some Fe3+), and typically contain MnO and MgO as well, together with associated silicate minerals. Smelting is one of the methods to upgrade ilmenite for subsequent T1O2 pigment production; smelting involves partial reduction of FeO to form metallic iron as a byproduct and titanium slag as the main product. Reduction is typically controlled to yield a slag which contains around 10% FeO, 85% (Ti02+Tij03) and 5% impurity oxides (mainly MnO, AI2O3 and S1O2). An example of a typical average slag composition from reduction of South African ilmenite is shown in Table I. As this indicates, a significant side reaction is reduction of some T1O2 to T12O3. The relative extents of reduction of FeO to Fe and of Ti02 to T12O3 are such that the slag stoichiometry is close to that of the pseudobrookite phase [1]. Pseudobrookite has the structure AB2O5 (where ""A"" and ""B"" are different cation sites); the phase which makes up the bulk of solidified titanium slag has the AB2O5 structure and stoichiometry [2], and can be viewed as a solid solution of FeTi20s, T13O5, ÌçÔÀ2è5, MgTi20s, AI2T1O5 and C^TiOs [1]. This solid-solution phase is referred to as ""pseudobrookite"" or ""M3O5"" in this paper."