Fundamental Studies on Direct Chromium Alloying by Chromite Ore with Designed Alloying Precursor

Sammanfattning: Chromium is an important alloying element for stainless steels and other Cr-bearing steels. During the steelmaking process chromium is added to the steels mainly in the form of ferrochrome, which is largely produced by the energy-intensive smelting reduction process of chromite ore in the submerged arc furnace. To reduce the overall energy consumption during the ferrochrome production process and the chromium alloying process, direct chromium alloying by chromite ore has been proposed. The application of this process will integrate the processes for ferrochrome production and chromium alloying, and thus has the potential to cut the production costs of the Cr-bearing steels by avoiding, or at least partially avoiding, the usage of ferrochrome. Further, this new alloying process has the capacity to improve the recovery of chromium from chromite ore. This thesis presents fundamental studies on the carbothermic reduction of synthetic iron chromite (FeCr2O4) and chromite ore, which aim at designing a direct alloying precursor to be applied in the industrial process. Thermogravimetric Analysis (TGA) experiments have been carried out to investigate the carbothermic reduction processes of FeCr2O4 in the absence/presence of metallic iron, and of chromite ore in the absence/presence of mill scale. In the case of using the mixture ‘FeCr2O4 + iron powder + graphite’, it is found that the presence of metallic iron enhances the reduction of FeCr2O4, and this enhancing effect increases with increasing iron addition. The enhancing effect of iron addition on the reduction of FeCr2O4 is due to the fact that the reduction of component Cr2O3 in FeCr2O4 is enhanced, and this effect is attributed to the presence of solid iron which can decrease the activity of chromium by having chromium in situ dissolved in the iron. In the case of using the mixture ‘chromite ore + petcoke’, it is found that the reduction of iron ions in the chromite ore starts before that of chromium ions in the ore and the reduction of iron ions and chromium ions in the ore overlaps to some degree. (Cr,Fe)7C3 is found to be the intermediate phase during the reduction and a chromium gradient is found in the spinel phase of the fractional reduced sample at 1673 K. A four-stage reduction process is proposed: one stage involving the reduction of iron ions in the chromite ore and three stages involving the reduction of chromium ions in the ore. The activity aspects of component FeCr2O4 and component MgCr2O4 in the chromite ore have been considered. The difficulty in the reduction of the chromite ore is attributed to the fact that, as the reduction proceeds, the activity of component MgCr2O4 in the fractional reduced ore will decrease to a very low level, which makes the further reduction very difficult. In the case of using the mixture ‘chromite ore + mill scale + petcoke’, it is found that mill scale is reduced to iron before 1573 K. The asreduced iron is disseminated around chromite ore particles and, at the same time, some carbon is dissolved in the iron via diffusion. Reduction of chromite ore is enhanced with the addition of mill scale at temperatures higher than 1623 K, and the enhancing effect increases with increasing mill scale addition. The enhancing effect, in this case, is attributed to the presence of molten Fe-Cr-C phase in the vicinity of chromite ore, which can decrease the activity of chromium by having chromium in situ dissolved into the melt. Induction furnace experiments have been carried out to investigate the effectiveness of some different alloying mixtures. The experimental results have confirmed the necessity of adjusting the composition of the slag to ensure high chromium yield in the final product and the experimental results show that, by using iron scrap, chromium yield can reach 90%. The present findings have led to the proposal of using ‘chromite ore + mill scale + petcoke’ as alloying precursor for direct chromium alloying. The effectiveness of this alloying precursor needs to be further explored by induction furnace experiments, followedby full scale Electric Arc Furnace experiments.