Influence and role of potassium in the reduction of hematite with CO/CO2

Potassium is known for having a favourable role in the reduction of hematite, either pure or as ore and a detrimental action on the crystals’ mechanical properties. However, several different interpretations have been put forward by previous authors: softening of the gangue, modification of the sintering process, consequences of the alkali penetration into the oxide lattices. Hence new data are desirable and have been recorded, with pure hematite crystals as well as with an hematite ore and with two doping techniques: immersion in a K₂CO₃ solution, or introduction of potassium components in the reducing gas. Microstructure investigation shows that potassium favours porous magnetite growth rather than lamellar growth and concentrates in a sublayer of magnetite at the inner interface. In fully reduced crystals, potassium lies mainly in the core of the particle. When the interface has a so-called topochemical configuration, the shrinking core model provides the rate constants as a function of temperature. Arrhenius plots lead to the conclusion that potassium significantly lowers the activation energy. The proposed interpretation is based on the transient formation of KFe₁₁O¹⁷, which is revealed by 3 different observations. It may act as a nucleation catalyst, thanks to easy epitaxy with Fe₂O₃. This is consistent with the change to porous rather than lamellar domains when potassium is brought into play and with the increased crystal fracturation. Hematite ore is less sensitive to potassium because its silica gangue behaves as a trap for it, as shown by treatment with HF before reduction.