Iron Oxide Direct Reduction and Iron Nitride Formation Using Ammonia: Review and Thermodynamic Analysis

The steel industry is one of the main contributors to global greenhouse gas emissions, responsible for about 7 to 9% of the world’s total output. The steel sector is under pressure to move toward net-zero emissions by reducing its consumption of coke as the main method of reducing iron-rich feed materials to iron. Due to its well-developed synthesis process, high supply chain, straightforward handling technologies, and highly developed long-standing infrastructure, ammonia has the potential to become a replacement for coke as a future iron ore reductant. This work reviews previous research on ammonia direct reduction of iron oxides and the possible formation of iron nitrides. A thermodynamic assessment using FactSage 8.2 thermochemical software was carried out examining the behavior of ammonia gas as the reductant upon heating, detailed evaluations of the stable phases present under different reaction conditions and using different feed materials, and the formation and stability of iron nitride phases. The results suggest that the reduction of hematite with ammonia occurs in two steps below 570 °C and three steps above 570 °C. The ratio of Fe₂O₃/NH₃ was predicted to affect the reduction reactions by promoting a greater reduction degree and simultaneously lowering the initial temperature needed for reduction, while the excess gas concentration can suppress FeO formation. A predominance area diagram was developed showing the main areas of stable phases as a function of the partial pressure of NH₃ and temperature. The formation of iron nitrides during the process was predicted and these were not expected to cause issues for the formation of iron due to their instability under the conditions studied. This analysis can be used to inform further experimental studies regarding ammonia reduction of iron oxide.

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