Thermodynamic Assessment of Reactions in the Sodium-Oxide Fluxed Aluminothermic Reduction of Manganese Ore with Si, Cr, and Cu Collector Metals

This study investigates the reaction thermodynamics of the sodium oxide-fluxed aluminothermic reduction of pyrolusite-based manganese ore under self-propagating high-temperature synthesis (SHS) conditions, using Si, Cr, and Cu as collector metals. The experimental results are compared with thermochemical equilibrium calculations using FactSage 7.3 thermochemistry software. Experimental mixtures were prepared with controlled additions of aluminium, sodium silicate, calcium oxide, and collector metals and heated to the ignition temperature in a muffle furnace preheated to 1350 °C. The resulting alloys and slags were analysed for bulk composition. Collector metals significantly influence alloy carbon saturation and manganese recovery. The individual reaction’s Gibbs free energy values and the gas–slag–metal equilibrium were calculated. Discrepancies between the experimental and equilibrium-predicted results highlight the kinetic factors of SHS processes, particularly with respect to aluminium uptake and manganese volatilisation. The main difference is the alloy’s aluminium uptake. The difference between the calculated and experimental aluminium levels is, in part, due to the higher partial oxygen pressure predicted in the gas–slag–metal equilibrium calculations, compared with that of the likely Al–Al2O3 governing reaction equilibrium. Short-circuiting of aluminium to the alloy is also a possible contributing factor. The findings provide insights into optimising feed formulations and process parameters for improved manganese recovery.