Thermodynamic Study of H2-FeO Based on the Principle of Minimum Gibbs Free Energy

Abstract

Studies have shown that the reduction of wustite is the limiting factor in the ironmaking process, whether in hydrogen-based shaft furnaces, hydrogen-rich blast furnaces or smelting reduction vessels. The study of the thermodynamic conditions for the reduction of molten wustite by hydrogen is of great significance for the optimization of the ironmaking process, energy saving and emission reduction. Previous studies have mostly focused on the thermodynamic study of the reduction at a lower temperature, but the data at high temperatures are different, which makes the calculation of thermodynamics difficult. Moreover, it is difficult to obtain experimental evidence for the data at high temperature, so calculation is needed to verify its feasibility. In this paper, a thermodynamic calculation model for the reduction of molten wustite by hydrogen based on the principle of minimum Gibbs free energy is developed. The enthalpy changes of the reaction at different temperatures and the partial pressure of hydrogen required for the reaction to occur are calculated, and the energy change during the reaction is analyzed. The results show that the partial pressure of hydrogen for the reduction of molten wustite by hydrogen at high temperatures decreases from 0.67 at 1650 K to about 0.65 at 2000 K. The enthalpy changes of reaction at 1873 K are only 1/4 to 1/3 of that at 1173 K compared with that at the corresponding temperature between hydrogen for the reduction of molten wustite (1873 K) and hydrogen-based shaft furnace reaction (1173 K). Interestingly, the thermodynamic calculations show that the effect of energy absorption in the gas–liquid reaction of hydrogen with wustite at high temperatures is much lower than in the gas–solid reaction zone at low temperatures. These results indicate that the energy change of the reduction of molten wustite by hydrogen at high temperatures is better than that of hydrogen reduction at low temperatures, and the thermodynamic conditions are more favorable, with slightly different results from different thermodynamic databases, but the general trend is the same. The results of this study will provide fundamental data to support new hydrogen metallurgy technologies in the future. If its correctness can be verified experimentally in the future, this result will be promoted to the development of a new alternative ironmaking technology, hydrogen-based smelting reduction.