Method for isolating rare earths and/or adjacent metal element(s) contained in the magnetic phase of permanent magnets

Patent metadata

Field	Value
Publication number	US-10167532-B2
Application number	US-201314438506-A
Country	US
Kind code	B2
Filing date	Oct 21, 2013
Priority date	Oct 24, 2012
Publication date	Jan 1, 2019
Grant date	Jan 1, 2019

Abstract

A isolating method including: (i) arranging material forming a magnetic phase as a demagnetised powder, having an average particle size no larger than 700 μm without particles not making up the magnetic phase; (ii) dissolving the powder of step (i) in an acid medium with at least one oxidising agent in the presence of hydroxide ions, at a pH strictly lower than 7; (iii) precipitating the adjacent metal element(s) in the hydroxide state by adding to the solution obtained at the end of step (ii) an effective amount of hydroxylated base; (iv) isolating the metal hydroxide precipitate formed at the end of step (iii) and, when necessary, recovering same; (v) precipitating the rare earth elements in the oxalate state in the solution without adjacent metal element(s) and obtained at the end of step (iv); and (vi) recovering the rare earths in the precipitated state of rare earth oxalate.

First claim

The invention claimed is:

1. A process for isolating rare earth metals and ancillary metal element(s) distinct from rare earth metals present in a magnetic phase of magnets or derived products, comprising:
(i) having a material forming said magnetic phase available in the form of a demagnetized powder, with a mean particle size of less than or equal to 700 μm, devoid of contamination with nonconstituent particles of said magnetic phase;
(ii) dissolving said powder from stage (i) in an acid medium comprising a first quantity of acid and supplemented with at least one oxidizing agent capable of adjusting the ancillary metal element(s) to an oxidation state compatible with their consecutive precipitation in stage (iii), in the presence of hydroxide ions, at a pH strictly of less than 7, to form a first solution;
(iii) precipitating the ancillary metal element(s) in the hydroxide state to form a metal hydroxide precipitate by adding at least one hydroxylated base to the first solution obtained on conclusion of stage (ii), under pH conditions such that the rare earth metals are in a dissolved form;
(iv) isolating the metal hydroxide precipitate formed on conclusion of stage (iii), and optionally recovering it, leaving a second solution that is depleted in, and optionally devoid of, ancillary metal element(s);
(v) precipitating the rare earth metals in an oxalate state from the second solution obtained on conclusion of stage (iv) by adding a second quantity of acid comprising an oxalic acid to said second solution; and
(vi) recovering said rare earth metals in a form of a precipitate of rare earth metal oxalate,
wherein the process does not include an oxidation heat treatment step.

2. The process as claimed in claim 1 , in which the powder in stage (i) has a mean particle size ranging from 10 to 500 μm.

3. The process as claimed in claim 1 , in which said oxidizing acid medium of stage (ii) comprises one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, and their mixture.

4. The process as claimed in claim 1 , in which said oxidizing agent is selected from the group consisting of H 2 O 2 , NaS, NaClO, and their mixtures.

5. The process as claimed in claim 1 , in which said hydroxylated base added in stage (iii) is selected from the group consisting of NaOH, NH 4 OH, KOH, and other hydroxylated organic bases.

6. The process as claimed in claim 1 , in which the pH of the solution is adjusted in stage (iii) to a value strictly of less than 7.

7. The process as claimed in claim 1 , for isolating rare earth metals and/or iron.

8. The process as claimed in claim 7 , in which the acid medium in stage (ii) is supplemented with at least one oxidizing agent capable of oxidizing iron in a form of iron(III).

9. The process as claimed in claim 1 , for isolating rare earth metals and/or cobalt.

10. The process as claimed in claim 9 , in which the acid medium in stage (ii) is supplemented with at least one oxidizing agent capable of oxidizing cobalt in a form of cobalt(III).

11. The process as claimed in claim 1 , further comprising, prior to stage (v), one or more stage(s) of washing the metal hydroxide precipitate isolated in stage (iv) and incorporating aqueous wash liquors from the washing into the second obtained on conclusion of stage (iv).

12. The process as claimed in claim 1 , in which the powder of stage (i) is obtained from a magnetic material in bulk form via a hydridation-dehydridation treatment.

13. The process as claimed in claim 1 , in which the powder in stage (i) is formed from a magnetic product via at least the stages comprising:
(a) having available a magnetic product formed of magnetic material in bulk form and, optionally, a protective coating of metal alloy positioned at a surface of said magnetic material;
(b) demagnetizing the magnetic product to be treated if it is magnetized;
(c) if existing, cracking said protective coating,
(d) fragmenting said magnetic material to form a powder of particles with a mean size of less than or equal to 700 μm by exposure to a hydridation-dehydridation treatment; and
(e) recovering the powder, in a form isolated from remnants of the protective coating.

14. A process for the recycling of rare earth metals present in magnets or derived products, comprising isolating rare earth metals from magnets or derived products by the process of claim 1 .

15. The process as claimed in claim 1 , in which the powder in stage (i) has a mean particle size less than or equal to 200 μm.

16. The process as claimed in claim 1 , in which the pH of the solution is adjusted in stage (iii) to a value ranging from 0.8 to strictly less than 7.

17. The process as claimed in claim 1 , for isolating neodymium and/or iron present in the magnetic phase of a magnet of Neodymium-Iron-Boron type.

18. The process as claimed in claim 7 , in which the at least one oxidizing agent in stage (ii) comprises H 2 O 2 .

19. The process as claimed in claim 1 , for isolating samarium and/or cobalt present in the magnetic phase of a magnet of Samarium-Cobalt type.

20. The process as claimed in claim 9 , in which the at least one oxidizing agent in stage (ii) comprises NaClO.

21. The process as claimed in claim 13 , in which step (b) is performed by exposure to a heat treatment at a temperature of less than 350° C.

22. The process as claimed in claim 13 , in which step (c) is performed by mechanical shredding of the magnetic product.

23. The process as claimed in claim 13 , in which step (e) is performed by sieving.

Assignees

• Commissariat Energie Atomique
• Commissariat Energie Atomique

Inventors

• Laucournet Richard
• Lecorre Céline

Classifications

• H01F41/0253

  for manufacturing permanent magnets · CPC title

• C22B7/006

  Wet processes · CPC title

• C22B7/007

  by acid leaching · CPC title

• C22B59/00 Primary

  Obtaining rare earth metals · CPC title

• C22B3/00

  Extraction of metal compounds from ores or concentrates by wet processes · CPC title