Simple chemical method for the separation of rare earth metals
View Patent ↗A method is provided for separating mixtures of different rare earth metals using a ligand having a size-sensitive molecular aperture. The present invention meets the needs in the field by providing method of separating and purifying rare earth metals. The object of this invention is to separate and purify rare earth metals, e.g., the more valuable Dy away from Nd, in mixtures containing such metals using a simple chemical process without the need for countercurrent liquid-liquid separations.
1. A method for separating, one from another, different metals combined in a source thereof, said metals being selected from the group of rare earth metals consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, the method comprising:
a) establishing a chemical equilibrium in a polar solvent between complexes of the metals sought to be separated, each complex comprising a rare earth metal ion and a ligand capable of binding to said rare earth metal ion, said complexes including a monomer comprising a rare earth metal ion having a relatively smaller ionic radius and a dimer comprising a different rare earth metal ion having a relatively larger ionic radius when the ionic radii of the rare earth metal ions are compared; and either:
b1) replacing the polar solvent with a non-polar solvent, thereby resulting in a solid-liquid mixture, the solid component of the mixture comprising predominantly the rare earth metal having the smaller ionic radius, and the liquid component of the mixture comprising predominantly the rare earth metal having the larger ionic radius; and
b2) separating said solid component from said liquid component; or
c1) applying an oxidizing electrochemical potential or a chemical oxidizing agent to the complexes of the metals sought to be separated, dissolved in a polar solvent, to selectively oxidize the complex having an earlier rare earth metal ion; and
c2) separating the oxidized, earlier rare earth metal ion complexes through differences in solubility or chemical properties using precipitation-filtration or liquid-liquid extraction.
2. The method of claim 1 , wherein the metal having the smaller ionic radius is recovered from the solid component.
3. The method of claim 1 , wherein the recovered metal is Dy.
4. The method of claim 1 , wherein the metal having the larger ionic radius is recovered from the liquid component.
5. The method of claim 1 , wherein the recovered metal is Nd.
6. The method of claim 1 , wherein said polar solvent is an aprotic polar solvent.
7. The method of claim 1 , wherein said source is a rare earth metal-containing magnet, or scrap or waste material generated in the production of said magnet.
8. The method of claim 1 , wherein said ligand is a (2-( t BuNOH)CH 2 -C 6 H 4 ) 3 N ligand.
9. The method of claim 1 , wherein said ligand has the formula:
wherein R 1 , R 2 , and R 3 may be independently selected from the group consisting of alkyl, aryl, heteroaryl, and a heteroatom.
10. The method of claim 9 , wherein the R 1 , R 2 , and R 3 comprise an alkyl substituent.
11. The method of claim 9 , wherein the ligand comprises H 3 [(2-( t BuNO) CH 2 -C 6 H 4 ) 3 N].
12. The method of claim 9 , wherein the separation factor is greater than 5.
13. The method of claim 9 , wherein the solid component has an enrichment factor of at least 9.
14. The method of claim 9 , wherein the liquid component has an enrichment factor of at least 9.
15. The method of claim 1 , wherein step a) comprises establishing a chemical equilibrium in a polar solvent between a monomeric rare earth metal complex and a dimeric rare earth metal complex, at least one of the monomeric and dimeric rare earth metal complexes comprising the selected rare earth metal and a ligand, wherein each of the monomeric and dimeric rare earth metal complexes comprise an aperture defined by a monomeric % buried volume (% V bur ); and wherein step b1) comprises replacing the polar solvent with a non-polar solvent to provide a mixture comprising a solid fraction and a liquid fraction, the solid fraction comprising predominantly the monomeric rare earth metal complex and the liquid fraction comprising predominantly the dimeric rare earth metal complex, wherein the monomeric % V bur of the dimeric rare earth metal complex aperture is less than the monomeric % V bur of the monomeric rare earth metal complex aperture.
16. The method of claim 15 , wherein at least one of the monomeric % V bur of the dimeric rare earth metal complex and monomeric metal complex is 50% to 100%.
17. The method of claim 15 , wherein the ligand comprises H 3 [(2-( t BuNO) CH 2 -C 6 H 4 ) 3 N].