# US 4,394,357 A · Separation of cobalt and nickel by oxidative precipitation with peroxymonosulfuric acid > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,394,357 A - Document ID: US4394357A - Status: Granted - Kind: A - Application number: 06/321,575 - Filed: 1981-11-16 - Granted: 1983-07-19 - Earliest claimed: 1980-12-05 - Assignees: Interox Chemicals Limited - Inventors: Diana M. Mounsey; David B. Mobbs - Web page: https://patentgrep.com/patent/US4394357A ## CPC - C22B 23/0484: {in acidic type solutions} - C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS ## Abstract The invention relates to the preferential precipitation of cobalt from aqueous acidic sulphate solutions of nickel and cobalt. The separation is carried out by introducing at least a stoichiometric amount of Caro's Acid containing no more than a small amount of hydrogen peroxide into the nickel/cobalt solution progressively over a period of at least an hour, while maintaining the solution of a pH from 3.1 or 3.5 up to 4.7 by addition of an alkali metal hydroxide carbonate or bicarbonate, or at 4.3 to 4.7 with the corresponding ammonium compound, and, thereafter separating the precipitate from the aqueous cobalt depleted solution. In preferred features, the Caro's Acid solution used contains hydrogen peroxide in a mole ratio to peroxomonosulphuric acid of not more than 1:10; the Caro's Acid solution is introduced continuously or in increments of less than 1% of the total over a period of at least an hour; the Caro's Acid is produced by reaction between 93-98% sulphuric acid and 65-72% aqueous hydrogen peroxide in a mole ratio of 2.7:1 to 3.5:1; the Caro's Acid solution is diluted before use; and particular amounts of Caro's Acid are used depending upon the nature of the nickel/cobalt solution, the mode of treatment, and the nature of the neutralizing agent. Further separation can be effected by subsequent water and particularly not acid washing of the precipitate. ## Claims ### Claim 1 In a process for the separation of cobalt and nickel from an aqueous acidic sulphate solution thereof in which Caro's Acid is introduced into said aqueous solution, and is at least partially neutralised by introduction of a neutralising agent, resulting in a cobalt-containing precipitate, and the resultant precipitate is separated from the residual aqueous phase, the improvement which comprises employing at least a stoichiometric amount of Caro's Acid based on the amount of peroxomonosulphuric acid required theoretically to oxidise all the cobalt in solution to cobalt (III), said Caro's Acid containing not more than 1 mole of hydrogen peroxide per 8 moles of peroxomonosulphuric acid, maintaining the aqueous solution of cobalt and nickel at a pH of not more than pH 4.7 and at a minimum pH ranging from pH 3.1 when the nickel to cobalt mole ratio in the solution before Caro's Acid introduction is 1:1 or lower up to pH 3.5 when said mole ratio is 40:1 or higher, by introduction thereinto of an alkali metal hydroxide or carbonate, for a period of at least 2 hours after introduction of Caro's Acid solution commences, during which period cobalt hydroxide precipitates out of solution. ### Claim 2 (depends on 1) A process according to claim 1 wherein the Caro's Acid is introduced continuously or in increments each of less than 1% of the total amount added. ### Claim 3 (depends on 1, 2) A process according to claim 1 or 2 wherein the Caro's Acid used is produced by reaction between 93 to 98% by weight sulphuric acid and 65 to 72% by weight aqueous hydrogen peroxide solution in a mole ratio of H.sub.2 SO.sub.4 :H.sub.2 O.sub.2 of from 2.7:1 to 3.5:1. ### Claim 4 (depends on 3) A process according to claim 3 wherein the Caro's Acid is diluted to below 15% by weight concentration of peroxomonosulphuric acid before introduction into the cobalt solution. ### Claim 5 (depends on 1) A process according to claim 1 wherein the nickel/cobalt solution has a high nickel and low cobalt concentration and is treated with 2.3 to 3.5 times the stoichiometric amount of Caro's Acid based on the cobalt in a batch process. ### Claim 6 (depends on 1) A process according to claim 1 wherein the nickel/cobalt solution has a similar nickel and cobalt concentrations or is cobalt-rich and is treated with up to 1.8 times the stoichiometric amount of Caro's Acid based on the cobalt in a batch process. ### Claim 7 (depends on 6) A process according to claim 6 wherein the neutralisation agent used is sodium carbonate. ### Claim 8 (depends on 5, 6) A process according to claim 5 or 6 wherein the Caro's Acid is introduced progressively during a period of at least 1 hour in a batch process. ### Claim 9 (depends on 8) A process according to claim 8 wherein the residence time is from 3 to 6 hours. ### Claim 10 (depends on 1) A process according to claim 1 wherein the nickel/cobalt solution has a high nickel and low cobalt concentration and is treated with 1.6 to 2.3 times a stoichiometric amount of Caro's Acid in a continuous process. ### Claim 11 (depends on 5, 10) A process according to claim 5 or 10 wherein the nickel cobalt solution is maintained at a pH from 3.9 to 4.5. ### Claim 12 (depends on 1) A process according to claim 1 wherein nickel/cobalt solution has a similar nickel and cobalt concentrations and is treated with 2 to 2.5 times a stoichiometric amount of Caro's Acid in a continuous process. ### Claim 13 (depends on 10, 12) A process according to claim 10 or 12 wherein the residence time is from 8.25 to 12 hours. ### Claim 14 (depends on 1, 4, 7) A modification of the process according to claim 1, 4 or 7 wherein the pH of the solution is maintained at from pH 4.3 to 4.7 and the neutralising agent is ammonium hydroxide, bicarbonate or carbonate. ### Claim 15 (depends on 14) A process according to claim 14 wherein the nickel/cobalt solution has a high nickel and low cobalt concentration and is treated with 2.3 to 3.5 times the stoichiometric amount of Caro's Acid based on the cobalt in a batch process. ### Claim 16 (depends on 15) A process according to claim 15 wherein the greater part of the cobalt is precipitated from a solution containing less than 20 gpl ammonium sulphate. ### Claim 17 (depends on 5, 7, 10) A process according to claim 5, 7, 10, or 12 wherein the Caro's Acid used is produced by reaction between 93 to 98% by weight sulphuric acid and 65 to 72% by weight aqueous hydrogen peroxide solution in a mole ratio of H.sub.2 SO.sub.4 :H.sub.2 O.sub.2 of from 2.7:1 to 3.5:1 then is introduced continuously or in increments each of less than 1% of the total amount added and is diluted to below 15% by weight. ### Claim 18 (depends on 17) A process according to claim 17 wherein the precipitate is acid washed. ### Claim 19 (depends on 14) A process according to claim 14 wherein the Caro's Acid used is produced by reaction between 93 to 98% by weight sulphuric acid and 65 to 72% by weight aqueous hydrogen peroxide solution in a mole ratio of H.sub.2 SO.sub.4 : H.sub.2 O.sub.2 of from 2.7:1 to 3.5:1 then is introduced continuously or in increments each of less than 1% of the total amount added and is diluted to below 15% by weight.