Process for mutual separation of platinum group metals

• US 7,291,202 B2
• Filed: 09/21/2004
• Issued: 11/06/2007
• Est. Priority Date: 09/26/2003
• Status: Active Grant

• Current Assignee: Sumitomo Metal Mining Company Limited
• Original Assignee: Sumitomo Metal Mining Company Limited
• Inventors: Asano, Satoshi, Heguri, Shinichi, Manabe, Yoshiaki, Kurokawa, Harumasa, Kasai, Masushi
• Primary Examiner(s): King; Roy
• Assistant Examiner(s): MCNELIS, KATHLEEN A
• Application Number:
  US10/944,753
• Publication Number:
  US 20050066774A1
• Time in Patent Office: 1,141 Days
• Field of Search: 757/44, 757/41
• US Class Current: 75/741
• CPC Class Codes: C22B 11/04 by wet processes extraction of metal compounds by leaching in organic solutions C22B3/16; treatment or purification of solutions by liquid-liquid extraction C22B3/26
• CPC Class Codes: C22B 3/10 Hydrochloric acid , other halogenated acids or salts thereof
• CPC Class Codes: C22B 3/3846 Phosphoric acid, e.g. (O)P(OH)3
• CPC Class Codes: C22B 3/44 by chemical processes treatment or purification of solutions by liquid-liquid extraction C22B3/26, by ion-exchange extraction C22B3/42
• CPC Class Codes: Y02P 10/20 Recycling

Abstract

A process for mutual separation of platinum group metals (PGM), wherein highly stable compounds and steps are used to efficiently remove impurity elements while preventing increase of impurity content relative to that of the PGM in the mother liquor and also preventing decomposition of a chloro complex, and palladium, platinum, iridium, ruthenium and rhodium are separated mutually in such a way that each of the separated PGM has a sufficient purity to be a commercial product.

A process for mutual separation of PGM, comprising the first step for leaching a raw material containing PGM and impurity elements, second step for removing the impurity elements from the leach liquor by solvent extraction, third step for recovering palladium from the raffinate, fourth step for removing cationic impurity elements from the raffinate by solvent extraction, fifth step for recovering platinum from the raffinate by hydrolysis, sixth step for recovering ruthenium from the precipitate by leaching, and seventh step for recovering iridium by solvent extraction to prepare the stripping liquor containing iridium and raffinate containing rhodium.

Claims

1. A process for mutual separation of platinum group metals (PGM) from a raw material which also contains impurity elements, comprising the following steps:

(1) first step, wherein the raw material containing PGM is leached in the presence of an oxidant while being suspended in a hydrochloric acid solution to prepare a leach liquor containing the PGM,

(2) second step, wherein the leach liquor prepared in the first step is separated by solvent extraction with diethylene glycol dibutyl ether into the organic phase containing impurity elements and a raffinate,

(3) third step, wherein the raffinate prepared in the second step is treated by solvent extraction with an alkyl sulfide to extract palladium and the resulting loaded solvent is then treated by stripping, to prepare a stripping liquor containing palladium and raffinate,

(4) fourth step, wherein the raffinate prepared in the third step is separated by solvent extraction with bis(2-ethylhexyl)phosphoric acid into the organic phase containing cationic impurity elements and raffinate,

(5) fifth step, wherein the raffinate prepared in the fourth step is hydrolyzed in the presence of an oxidant, after being adjusted at a pH of 5 to 12, to prepare a precipitate containing iridium, ruthenium and rhodium, and aqueous solution containing platinum,

(6) sixth step, wherein the precipitate prepared in the fifth step is leached in the presence of an oxidant in a strongly alkaline aqueous solution kept at a pH of 12 or more, to prepare a residue containing iridium and rhodium, and leach liquor containing ruthenium, and

(7) seventh step, wherein the residue prepared in the sixth step is dissolved in a hydrochloric acid solution to prepare an aqueous solution containing iridium and rhodium, the aqueous solution is treated by solvent extraction with tributyl phosphate to extract iridium, and the resulting loaded solvent is then treated by stripping, to prepare a stripping liquor containing iridium and raffinate containing rhodium.

2. The process according to claim 1 for mutual separation of PGM, wherein the oxidant for the first step is at least one selected from the group consisting of nitric acid, hydrogen peroxide and chlorine.

3. The process according to claim 1 for mutual separation of PGM, wherein the leach liquor for the second step contains hydrochloric acid at 4 to 9 mols/L.

4. The process according to claim 1 for mutual separation of PGM, wherein each of the impurity elements in the organic phase of the second step is at least one selected from the group consisting of an element which can form a lipophilic chlorocomplex, trivalent arsenic, tetravalent selenium, and tetravalent tellurium.

5. The process according to claim 1 for mutual separation of PGM, wherein the alkyl sulfide for the third step is selected from the group consisting of dihexyl and dioctyl sulfide.

6. The process according to claim 1 for mutual separation of PGM, wherein the raffinate prepared in the second step for the third step is adjusted at a pH of 0.5 to 2.5 before being treated with the alkyl sulfide.

7. The process according to claim 1 for mutual separation of PGM, wherein the fourth step is carried out at a pH of 2.5 to 4.5.

8. The process according to claim 7 for mutual separation of PGM, wherein an alkali metal salt of bis(2-ethylhexyl)phosphoric acid is used as a pH adjusting agent.

9. The process according to claim 1 for mutual separation of PGM, wherein the fifth step is carried out at a temperature 60 to 100°

C.

10. The process according to claim 1 for mutual separation of PGM, wherein the fifth step is carried out at an oxidation-reduction potential of 100 to 700 mV, determined using a silver/silver chloride reference electrode.

11. The process according to claim 1 for mutual separation of PGM, wherein the sixth step is carried out at an oxidation-reduction potential of 100 to 300 mV, determined using a silver/silver chloride reference electrode.

12. The process according to claim 1 for mutual separation of PGM, wherein the hydrochloric acid solution for the seventh step contains hydrochloric acid at 3 to 7 mols/L.

13. The process according to claim 1 for mutual separation of PGM, wherein the aqueous solution containing iridium and rhodium is kept at an oxidation-reduction potential of 700 to 1200 mV, determined using a silver/silver chloride reference electrode, for the solvent extraction in the seventh step.

14. The process according to claim 1 for mutual separation of PGM, wherein the aqueous solution for the stripping in the seventh step contains an alkali metal salt.

15. The process according to claim 1 for mutual separation of PGM, wherein a ruthenium refining step is further included to treat the leach liquor containing ruthenium from the sixth step in two stages a reduction stage in the presence of a reductant to prepare the ruthenium containing precipitate and a crystallization stage to prepare the ruthenium compound crystal by dissolving the precipitate.

16. The process according to claim 15 for mutual separation of PGM, wherein the crystallization stage incorporates an aqueous solution of the ruthenium-containing precipitate dissolved in hydrochloric acid with potassium chloride or ammonium chloride to prepare the ruthenium compound crystal.

17. The process according to claim 1 for a mutual separation of PGM, wherein an iridium refining step is further included to treat the stripping liquor from the seventh step in two stages, athe reduction stage in the presence of metallic bismuth to prepare an alloy containing PGM other than iridium and an aqueous solution containing iridium and a crystallization stage to prepare an iridium containing crystal from the aqueous solution.

18. The process according to claim 17 for mutual separation of PGM, wherein the crystallization stage incorporates the iridium-containing aqueous solution, oxidized beforehand in the presence of an oxidant, with potassium chloride or ammonium chloride to prepare the iridium-containing crystal.