Sustainable Pre-reduction of Ferromanganese Oxides with Hydrogen: Heating Rate-Dependent Reduction Pathways and Microstructure Evolution

Abstract

The reduction of ferromanganese ores into metallic feedstock is an energy-intensive process with substantial carbon emissions, necessitating sustainable alternatives. Hydrogen-based pre-reduction of manganese-rich ores offers a low-emission pathway to augment subsequent thermic Fe-Mn alloy production. However, reduction dynamics and microstructure evolution under varying thermal conditions remain poorly understood. This study investigates the influence of heating rate on the hydrogen-based direct reduction of natural Nchwaning ferromanganese ore and a synthetic analog. Non-isothermal thermogravimetric analysis revealed a complex multistep reduction process with overlapping kinetic regimes. Isoconversional kinetic analysis showed increased activation energy with reduction degree, indicating a transition from surface-reaction to diffusion-controlled reduction mechanisms. Interrupted X-ray diffraction experiments suggested that slow heating enables complete conversion to MnO and metallic Fe, while rapid heating promotes Fe- and Mn-oxides intermixing. Thermodynamic calculations for the Fe-Mn-O system predicted the equilibrium phase evolution, indicating Mn stabilized Fe-containing spinel and halite phases. Microstructural analysis revealed that slow heating rate yields fine and dispersed Fe particles in a porous MnO matrix, while fast heating leads to sporadic Fe-rich agglomerates. These findings suggest heating rate as a critical parameter governing reduction pathway, phase distribution, and microstructure evolution, thus offering key insights for optimizing hydrogen-based pre-reduction strategies towards more efficient and sustainable ferromanganese production.