IP Library Granted Patent US 11,149,356
Granted Patent B2
US 11,149,356 · App. 15/847,757 · Granted Oct 19, 2021

Methods of forming metals using ionic liquids

Inventors: Donna L. Baek (Idaho Falls, ID); Robert V. Fox (Idaho Falls, ID); Tedd E. Lister (Lewisville, ID)
Assignee: Battelle Energy Alliance, LLC
C25C3/34C25C7/06
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Quick Facts
Patent No.
US 11,149,356
App. No.
15/847,757
Granted
Oct 19, 2021
Kind
B2
Abstract

A method of forming an elemental metal (e.g., a rare-earth element) includes forming a multicomponent solution comprising an ionic liquid, a secondary component, and a metal-containing compound. The multicomponent solution is contacted with at least a first electrode and a second electrode. A current is passed between the first electrode to the second electrode through the multicomponent solution. The metal-containing compound is reduced to deposit the elemental metal therefrom on the first electrode.

Claims (39)

1. A method of recovering an elemental metal, the method comprising:

forming a multicomponent solution comprising an ionic liquid, a secondary component comprising a ligand different from the ionic liquid, and a metal-containing compound, the secondary component selected to increase a solubility of the metal-containing compound in the ionic liquid and decrease a viscosity of the multicomponent solution, a concentration of the metal-containing compound in the multicomponent solution higher than a solubility limit of the metal-containing compound in the ionic liquid alone, the ligand selected from the group consisting of an organophosphorus ligand and a sulfur-oxide ligand;

contacting the multicomponent solution with at least a first electrode and a second electrode;

passing a current between the first electrode and the second electrode through the multicomponent solution; and

reducing the metal-containing compound to deposit metal therefrom on the first electrode.

2. The method of claim 1 , wherein the secondary component comprises a material selected from the group consisting of a gas, a liquid, a salt, and a supercritical fluid.

3. The method of claim 1 , wherein the secondary component further comprises another ionic liquid.

4. The method of claim 1 , wherein forming a multicomponent solution comprises forming the multicomponent solution to comprise the ionic liquid, the secondary component, the metal-containing compound, and an anolyte.

5. The method of claim 4 , wherein the anolyte comprises a material selected from the group consisting of formic acid, ammonia, oxalic acid, acetic acid, carboxylic acids, and phthalic acid.

6. The method of claim 4 , further comprising oxidizing the anolyte at the second electrode.

7. The method of claim 1 , wherein forming a multicomponent solution comprises dissolving the metal-containing compound in the ionic liquid.

8. The method of claim 1 , wherein the metal-containing compound comprises a compound containing a rare-earth element, and wherein the metal deposited comprises the rare-earth element.

9. The method of claim 1 , wherein the metal-containing compound comprises a metal species selected from the group consisting of a metal oxide, a metal nitrate, a metal triflate, a metal carbonate, a metal bistriflimide, a metal-ligand complex, an ionic-liquid-bound metal, and a dissolved metal.

10. The method of claim 1 , wherein reducing the metal-containing compound to deposit metal therefrom on the first electrode comprises depositing the metal onto the first electrode at a temperature of less than 200° C.

11. The method of claim 1 , wherein reducing the metal-containing compound to deposit metal therefrom on the first electrode comprises depositing the metal onto the first electrode at a temperature between 0° C. and 100° C.

12. The method of claim 1 , wherein reducing the metal-containing compound to deposit metal therefrom on the first electrode comprises depositing at least one metal selected from the group consisting of Nd, Pr, Eu, Dy, Sm, Ho, Sc, Y, La, Ce, Pm, Gd, Tb, Er, Tm, Yb, and Lu onto the first electrode.

13. The method of claim 1 , further comprising separating the multicomponent solution from the first electrode and the second electrode after reducing the metal-containing compound.

14. The method of claim 13 , further comprising regenerating the ionic liquid after separating the multicomponent solution from the first electrode and the second electrode.

15. The method of claim 14 , further comprising recycling the regenerated ionic liquid directly to a vessel including the first electrode and the second electrode.

16. The method of claim 1 , wherein reducing the metal-containing compound to deposit metal therefrom on the first electrode comprises depositing at least one metal selected from the group consisting of transition metals, actinides, and alloys and mixtures thereof onto the first electrode.

17. A method comprising:

providing an anode and a cathode, each in contact with an ionic liquid;

providing a metal-containing compound within the ionic liquid;

providing a secondary component selected from the group consisting of a gas and a supercritical fluid within the ionic liquid; and

passing a current through the anode and the cathode to reduce the metal-containing compound and deposit an elemental metal therefrom onto the cathode.

18. The method of claim 17 , wherein providing a secondary component selected from the group consisting of a gas and a supercritical fluid within the ionic liquid comprises dissolving the dissolved metal-containing compound in the secondary component.

19. The method of claim 17 , further comprising providing an anolyte in the ionic liquid and oxidizing the anolyte at the anode.

20. The method of claim 17 , wherein passing a current through the anode and the cathode comprises depositing the metal onto the cathode at a temperature of less than 200° C.

21. The method of claim 17 , wherein passing a current through the anode and the cathode comprises depositing the metal onto the cathode at a temperature between 0° C. and 100° C.

22. The method of claim 17 , wherein providing a metal-containing compound within the ionic liquid comprises providing a metal species selected from the group consisting of a metal oxide, a metal nitrate, a metal triflate, a metal carbonate, a metal bistriflimide, a metal-ligand complex, and ionic-liquid-bound metal, and a dissolved metal.

23. A method for recovering an elemental rare earth metal, the method comprising:

continuously passing a current through a cathode, an ionic liquid, and an anode to reduce a rare earth metal-containing compound mixed with the ionic liquid and deposit an elemental rare earth metal therefrom onto the cathode, wherein the ionic liquid is substantially free of oxygen and moisture and comprises a dissolved species in addition to the rare earth metal-containing compound.

24. The method of claim 23 , further comprising continuously flowing the ionic liquid through a vessel containing the anode and the cathode.

25. The method of claim 24 , further comprising continuously regenerating a portion of the ionic liquid leaving the vessel.

26. The method of claim 25 , further comprising recycling the regenerated portion of the ionic liquid to the vessel.

27. The method of claim 23 , wherein the dissolved species comprises another ionic liquid.

28. The method of claim 23 , wherein the ionic liquid comprises at least one material selected from the group consisting of N-ethyl-N-methylpyrrolidinium, N-methyl-N-propylpyrrolidinium, N-methyl-N-isopropylpyrrolidinium, N-butyl-N-methylpyrrolidinium, N-isobutyl-N-methylpyrrolidinium, N-secbutyl-N-methylpyrrolidinium, N-methyl-N-pentylpyrrolidinium, N-hexyl-N-methylpyrrolidinium, N-heptyl-N-methylpyrrolidinium, N-methyl-N-octylpyrrolidinium, N-methyl-N-propylpiperidinium, N-butyl-N-ethyl-piperidinium, N-ethyl-N-octylpiperidinium, N-trimethylbutylammonium, N-hexyltriethylammonium, tetrabutylammonium, trimethyl-N-hexylammonium, dimethylethylphenylammonium, triethylmethylammonium, trihexyl(tetradecyl)phosphonium, tetradecyl(trioctyl)phosphonium, triethyl-pentyl-phosphonium, triethyl-octyl-phosphonium, triethyl-dodecyl-phosphonium, bis(trifluoromethanesulfonyl)imide, trifluoromethanesulfonate, and dicyanimide.

29. The method of claim 23 , further comprising mixing the ionic liquid and the rare earth metal-containing compound with a ligand and at least a secondary component.

30. The method of claim 1 , wherein forming a multicomponent solution comprising an ionic liquid, a secondary component comprising a ligand, and a metal-containing compound comprises forming a multicomponent solution comprising a secondary component further comprising supercritical carbon dioxide.

Assignments (4)
CONFIRMATORY LICENSE Recorded Nov 26, 2018
From: BATTELLE ENERGY ALLIANCE/IDAHO NAT'L LAB
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 047620/0368 →
CORRECTIVE ASSIGNMENT TO CORRECT THE INCORRECT APPLICATION NO. 15/847,727. CORRECT APPLICATION NO. IS 15/847,757. PREVIOUSLY RECORDED ON REEL 044584 FRAME 0696. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT OF ENTIRE RIGHT, TITLE AND INTEREST TO BATTELLE ENERGY ALLIANCE, LLC. Recorded May 24, 2018
From: BAEK, DONNA L.; FOX, ROBERT V.; LISTER, TEDD E.
To: BATTELLE ENERGY ALLIANCE, LLC
Reel/Frame 046170/0045 →
NUNC PRO TUNC ASSIGNMENT Recorded Jan 18, 2018
From: BAEK, DONNA L.; FOX, ROBERT V.; LISTER, TEDD E.
To: BATTELLE ENERGY ALLIANCE, LLC
Reel/Frame 044657/0826 →
NUNC PRO TUNC ASSIGNMENT Recorded Jan 10, 2018
From: BAEK, DONNA L.; FOX, ROBERT V.; LISTER, TEDD E.
To: BATTELLE ENERGY ALLIANCE, LLC
Reel/Frame 044584/0696 →
Continuity (1)
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