Reaction mechanisms in the reduction of Winterveld chrome spinel with graphite and carbon

The reduction of mixtures of various sizes of gangue-free Winterveld chrome spinel and graphite under an argon atmosphere at 1300 degrees Celsius was studied by use of a recording thermobalance. The partially reduced material was examined by scanning electron microscopy, and the observations were analysed in terms of reaction mechanism. A four-stage sequence was deduced, as follows. In the first stage, the ferric iron is reduced to ferrous iron with no metallization. This stage is inherently variable and is controlled by the random packing of particles of reducing agent round the chromite. The second stage starts with a burst of metal nucleation, which is also inherently variable. This is followed by the reaction of carbon monoxide with the relatively highly reducible oxide at the perimeters of the metal nuclei, and is controlled by the regeneration of carbon monoxide by the Boudouard reaction. The second stage merges into the third, with no change in the form of the product until the removal of iron decreases the reducibility of the remaining oxide to such an extent that the activity of the carbon monoxide is not sufficient for reduction to proceed. Reduction is then accomplished by the carbon dissolved in the reduced metallic product, the rate of reduction being limited by the rate of carburization of the metal. The fourth stage is reached at a reduction of about 50 per cent. In that stage the rate is controlled by the diffusion of chromium ions in the oxide, and the reduced product becomes saturated with carbon as the mixed (Fe,Cr)7C3 carbide