RI 8930 - Hydrogen Chloride Sparging Crystallization of the Chloride Salts of Cobalt, Manganese, and Nickel

The Bureau of Mines investigated the effects of HCI concentration and solution temperature on the solubility and crystal form of the chlorides of Co, Mn, and Ni when sparged with HCI gas at temperatures of 20°, 40°, and 60° C. Increasing HCI concentration in solution caused the chlo-rides of Co, Mn, and Ni to crystallize (salt out) because of the common ion effect. The salting-out crystallization was most effective for NiCI2, which had a solubility of 0.7 pct at 20° C and maximum HCI concentration. COCl2 salted out to a minimum solubility of 9.4 pct at 20° C and 22 pct HCI concentration and increased in solubility at greater HCI concentrations because of the formation of chloride complexes. MnCl2 was intermediate in behavior. The effect of temperature on solubility was greatest for CoCl2 and least for NiCI2, 15 and 7 pct change, respectively, over the temperature range of 20° to 60° C. The salted-out chlorides of cobalt and nickel formed the hexahydrates and those of manganese formed the tetrahydrate in saturated metal chlo-ride solutions at 20° C and low concentrations of HCI. Increasing the temperature or the HCI concentration caused a 108s in waters of hydra-tion. At 60° C, the salted-out crystals of NiCl2 formed the tetrahydrate in HCI concentrations up to 18 pct and the dihydrate at higher concentrations, while cobalt and manganese chlorides formed the dihydrates, even in water.