The reduction of Winterveld chrome spinel at 1300 degrees Celsius under an argon atmosphere in the presence of carbon

The reduction of a mixture of particles of gangue-free spinel in the size range 106 to 90 μm and particles of graphite in the same size range was studied by the use of a recording thermobalance. The partially reduced material was analysed chemically, as well as by X-ray diffraction, optical microscopy, and electron-microprobe analysis. The reaction is shown to be sequential, the ferric iron being reduced to ferrous iron before a metallic reduction product appears. Almost one-half of the iron is reduced before the reduction of chromium becomes significant, and, by the time about one-half of the chromium has been reduced, almost no unreduced iron remains in the oxide. Carbon appears in the reduced material after the reduction of chromium has started. The carbon content rises as the reaction proceeds, and beyond the stage at which all the iron has been reduced, the reduced product is an iron-chromium carbide. The product is therefore in a state of near equilibrium with the partially reduced spinel. This indicates that, up to about 60 per cent reduction, the transfer of carbon to the oxide is a controlling factor in the reduction. This conclusion is supported by the observation that the reduced product is confined to the surface of the chromite particle, which retains its external shape while becoming progressively more porous as reduction proceeds. Under hydrogen, a metallic reduction product is formed within the internal pores as well as on the surface. The second half of the reduction proceeds at a reproducible decreasing rate that can be modelled on the basis of the diffusion of chromium from within the particle to the surface. The initial reduction rate is slow but accelerating, and is not reproducible. Further investigation of this stage of the reduction process is recommended