Non-Topochemical reduction of iron oxides

Non-topochemical behavior was studied during reduction of porous spheres of hematite by stages through the intermediate oxides and also continuously to iron by CO/CO₂ mixtures at temperatures of 600 to 900°C (873 to 1173 K). The behavior became more nearly topochemical as temperature increased. Shrinking occurred during the reduction of hematite to magnetite and of magnetite to wüstite, whereas swelling was observed during the reduction of wiistite to iron. Shrinking was greater, and swelling less, at higher temperatures. The total surface area of the solid decreased with increasing extent of reduction during each of the three stages. A non-topochemical model was developed which satisfies, better than previously proposed models, the reduction data for the single reactions and the three reactions occurring simultaneously. The model provides for variation in particle size and local changes in porosity and effective diffusivity. An empirical “sintering exponent” was introduced to describe changes in reacting surface area.