Minerals Beneficiation - Chlorination of Manganiferous Iron Ores

Chlorination behaviors of pure iron and manganese oxides were investigated by combining a thermogravimetric analysis (TGA) technique with batch-boat roasting followed by leaching. Ferrous and manganous oxides could be chlorinated readily, but, in the absence of a reductant, the higher oxides of both iron and manganese were dificult to chlorinate. Thermogravimetric analysis curves were drawn to illustrate the complexities of the reactions, and the possible mechanisms were discussed. Then three manganif-erous materials from the Cuyuna Range of Minnesota were treated by a process involving the selective chlorination of manganese followed by leaching. The results were interpreted in the light of the chlorination mechanisms observed on the pure iron and manganese oxides. One of the unsolved problems challenging Minnesota's mining industry is the development of an economic process to utilize the manganiferous iron ores of the Cuyuna Range. Although these ores constitute one of the major domestic reserves of manganese (estimated at 432 million tons'), their grade is too low for them to be mined solely for manganese. The nearly exclusive dependence of the U.S. steelmaking industry on foreign manganese ores has stimulated research over the years in treating the low-grade Cuyuna ores. As a result, a number of processes have been proposed.'-' Among these processes is chlorination. Chlorination is the high-temperature conversion of metallic oxides to chlorides by either chlorine or hydrogen chloride gas, or by solid chlorides of sodium, calcium, or magnesium. The metallic chlorides are then recovered by either vaporization or leaching. Although chlorination is an old art, it has become popular in recent years for the recovery of such new metals as titanium, zirconium, and niobium; for the removal of impurities like copper, lead, and zinc from pyrite cinder for ironmaking raw materials;' and for the segregation roasting of coppera and nickel' ores. The chlorination processes proposed for manganifer-ous iron ores have been relatively few (hydrogen chloride chloridization-leaching, hydrogen chloride and calcium chloride chloridization-volatilization,' and chlo-rination-selective condensation6), due presumably to the economics and to the corrosion problems involved. However, the successful application of chlorination processes to other ores will undoubtedly contribute to technological advancements in the chlorination of man-