New Findings In Research Of Solid Phase Reactions In Chromite Ore Reduction Processes

Reduction interactions in solid phases are widespread and occur in most complex metallurgical processes. Among these processes, reactions between oxides and carbon have a special importance. The authors conducted experiments for comparison of reduction by different reducing agents of impregnated chromite ores, in which grains of the reducible chromite spinel are isolated from direct contact with the reducing agent by layers of non-ore material. The results of the experiments have revealed that the beginning of reduction is preceded by thermal and impurity order-disorder transformation of the oxide lattice whilst the transformation of the oxide lattice into the metal lattice takes place as a result of removal of oxygen anions from the zone of metal germ nucleation. Since anions are charge carriers, increase of their mobility can be monitored by changes in electrical conductivity of oxides. Respective measurements of electrical resistance of ores of different metals and a number of pure refractory oxides under heating have indicated that the beginning of reduction coincides with the time of drastic (tens of thousands times) increase of conductivity of the oxides. Besides, the temperature of the beginning of carbon-thermal reduction is in line with the Tammann temperature, i.e. the temperature of transition from the predominantly surface diffusion to volume diffusion. Segregation of metals from the oxide lattice occurs as a result of merging of anion vacancies with defect electrons on defects of the oxide lattice. The transformation of the oxide lattice into the metal lattice requires a certain concentration of anion vacancies and inflow of electrons from the reducing agent to the site of metal segregation. Such inflow has no difficulties due to the mixed anion-electron nature of high-temperature conductivity of oxides. Thus, the reduction is not determined by oxygen diffusion, it is determined by oxygen vacancies diffusion whose speed exceeds the speed of oxygen diffusion by orders of magnitude. This determines that the kinetics of reduction considerably exceeds the kinetics of oxidation at similar temperatures since oxidation proceeds by means of mass transfer of oxygen through the layer of the generated oxide.