Patent GB-775788-A (GB)
Title: Improvements in or relating to a process for recovering nickel-free cobalt solutionsfrom liquor containing nickel and cobalt
IPC: C01G53/00
Filed: 1954-12-14
Abstract: A substantially nickel-free cobalt solution is obtained from a solution containing dissolved cobalt and nickel by adjusting the solutes content to provide an ammonia concentration sufficient to form the pentammines but not the hexammines of said metals and a sulphate concentration at least sufficient to satisfy the cobalt in its trivalent state and the nickel in its bivalent state; oxidizing the adjusted liquor with a sulphur-free oxygen-bearing oxidizing gas; acidifying the resultant liquor with sulphuric acid to a pH at which the nickel ammonium sulphate is precipitated; and separating the precipitate from the nickel-free solution.  The initial solution may be obtained from materials such as ores, concentrates or plant by-products and need not be a sulphate solution an example refers to a nitrate solution and chloride solutions are referred to: moreover the Co/Ni ratio in the starting solution is not critical although the invention is particularly effective when it is greater than 1.  The adjustment of the ammonia content may be made by adding ammonia as a gas or in aqueous solution or as ammonium sulphate; ammonium sulphate may also be used to supply the sulphate concentration.  It is preferred to carry out the oxidation at room temperature (i.e. without applying heat) although higher temperatures may be employed: sufficient oxidizing gas should be employed to convert the cobalt to the trivalent state without forming cobaltic peroxide.  After oxidizing the liquor, it may be heated to and maintained at the boiling point whereby optimum conversion to cobaltic pentammine is obtained.  It is preferred to raise the temperature slowly, e.g. over a period of 30-60 mins., and to continue boiling gently for 15-25 mins.  Boiling may take place under reduced pressure.  Particularly when the concentration of cobalt is more than 1 mol/1., it is desirable to subject the oxidized liquor to the action of steam, subsequently to the heating and boiling treatment, to increase the solubility of the cobaltic compound.  The treatment may alternatively be performed by bubbling steam into the liquor (thus accomplishing boiling at the same time) and should be sufficient to increase the cobalt solubility without precipitating the oxide.  After this treatment, the liquor is acidified, preferably to a pH less than 6 but not less than that equivalent to 2.0 per cent sulphuric acid aq., preferably with 5-70 per cent sulphuric acid.  In order to lower the solubility of the nickel ammonium sulphate, the ammonium sulphate concentration may be increased above that stoichiometrically necessary for the oxidation of the cobalt to the cobaltic state, when the initial adjustment is made, or after acidification, in which latter case a further quantity of (cobalt-contaminated) precipitate is formed.  Alternatively, or in addition, the solubility of the nickel may be reduced by the presence of cobaltous ions, and these may be provided by incomplete oxidation or by adding a cobaltous compound (preferably the sulphate, e.g. a solution obtained in the practice of the invention) after oxidation, preferably after acidification to obtain a second precipitate.  The precipitate thus obtained is a cobalt-nickel-ammonium triple salt.  After removal, e.g. by filtration, the precipitated nickel salt may be washed and the washings recycled.  Nickel may be recovered by dissolving to form an acid solution and reducing with hydrogen and the cobalt solution may be similarly reduced to metal.  Examples showing the effect of the above-mentioned factors are given: conditions leading to the production of cobalt ammine peroxide and "black cobaltic oxide" (Co3O4) are described by way of comparison.  Reference is also made in the Specification to the precipitation of cobaltic hexammine sulphate after oxidation if too great a concentration of ammonia is present or during oxidation if the temperature is too high, e.g. 100 DEG C.  The nickel-free liquors of the invention may be used to remove elemental cobalt deposits formed on the walls of reduction vessels during gaseous reduction of cobalt liquors.  By this process the liquor is at the same time reduced to the cobaltous state and is thus more amenable to recovery of cobalt by reduction.  A preferred leaching process involves the use of a solution comprising 5-60, better 20-30 gms./1. cobalt, 150-200 gms./1. ammonium sulphate and at least 50, preferably 70-95 gms./1. of "free" ammonia (i.e. as ammonium hydroxide or combined with metal in the form of complex ions) at a temperature of 40-60 DEG C. (up to 100 DEG C. is possible) and with a partial pressure of oxygen, derived e.g. from oxygen itself, oxygen-enriched air, or air, of 30-75 p.s.i.g.  Examples of this process are also given.