Metallurgical grade alumina is produced worldwide through the well-known Bayer process, which unavoidably generates bauxite residue (BR, also known as red mud) in almost equal amounts to alumina. This study aims the valorization of BR through a smelting-reduction process to obtain calcium aluminate slags that can be a proper feed for alumina recovery via the Pedersen process. It investigates the thermodynamics and characteristics of the slags and pig iron produced from mixtures of BR, a bauxite beneficiation byproduct, and lime. In this context, the evolution of the different phases in the slags is studied with advanced analytical techniques and thermodynamic calculations. According to the results, a CaO/Al₂O₃ mass ratio within 1.3 to 1.4 in the slags can yield more Al₂O₃-containing leachable phases, such as CaO·Al₂O₃ and 12CaO·7Al₂O₃. The cooling dictates the amount and the characteristics of these phases, and the slower cooling rate yields improved slag characteristics. The distribution of the elements between the slag and metal phases shows that iron is separated, and the majority of the P, Cr, Ni, and V are distributed in the produced pig iron, while S, Ti, and Si are mostly concentrated in the slags.

The carbothermic reduction of 38.7 pct MnO-12.1 pct CaO-5.4 pct MgO-9.3 pct Al₂O₃-24.1 pct SiO₂-10.4 pct FeO slag in Ar at 1600 °C was studied using the sessile drop wettability technique. Pure graphite, coke, and charcoal were used as the carbon material substrates. The reduction rates were evaluated by sampling at different reduction times and by analyzing the chemical compositions of the reduced slag and the produced metal. The carbothermic FeO reduction from slag is initially fast followed by a much slower reduction rate. However, the rate of the MnO reduction is slow in the fast FeO reduction stage, and it starts to increase significantly during the slow FeO reduction stage. The kinetics of FeO and MnO reduction are affected by the type of carbonaceous materials. Moreover, the rate of the carbon dissolution/transfer into the produced metal phase and the amount of the transferred manganese to the metal phase depend on the type of carbon. Based on the experimental observations and the thermodynamic calculations, a mechanism for MnO reduction was proposed. According to this mechanism, MnO is mainly reduced through a metallothermic reduction by Fe and the rate of MnO reduction is controlled by the rate of the consumption of FeO from the slag, which takes place simultaneously. In contrast, the rate of FeO reduction in the fast initial reduction stage is controlled by the rate of the carbon dissolution/transfer into the metal phase. However, at the second slow FeO reduction stage, it is reduced mainly by the solid carbon.