Rare earth removal of hydrated and hydroxyl species

• US 9,233,863 B2
• Filed: 03/28/2012
• Issued: 01/12/2016
• Est. Priority Date: 04/13/2011
• Status: Active Grant

• Current Assignee: Secure Natural Resources LLC (MP Materials Corp.)
• Original Assignee: Molycorp Minerals LLC (Oaktree Capital Management LP)
• Inventors: Cable, Robert, Hassler, Carl, Burba, John
• Primary Examiner(s): Savage, Matthew O
• Application Number:
  US13/432,987
• Publication Number:
  US 20120261345A1
• Time in Patent Office: 1,385 Days
• Field of Search: 210/660, 210/665, 210/669, 210/688, 210/912, 210/683, 210/684
• US Class Current: 1/1
• CPC Class Codes: C02F 1/281 using inorganic sorbents
• CPC Class Codes: C02F 1/66 by neutralisation; pH adjustment for degassing C02F1/20; using ion-exchange C02F1/42; for flocculation or precipitation of suspended impurities C02F1/52; for removing dissolved compounds C02F1/58
• CPC Class Codes: C02F 1/705 Reduction by metals
• CPC Class Codes: C02F 1/72 by oxidation C02F1/4672 takes precedence
• CPC Class Codes: C02F 2001/007 Processes including a sedimentation step
• CPC Class Codes: C02F 2101/103 Arsenic compounds
• CPC Class Codes: C02F 2101/20 Heavy metals or heavy metal compounds
• CPC Class Codes: C02F 2303/16 Regeneration of sorbents, filters
• CPC Class Codes: Y02W 10/37 using solar energy

Abstract

This disclosure relates generally to methods and rare earth-containing additives for removing target materials in the form of hydroxides, carbonates, hydrates, or oxyhydroxyls from, a typically aqueous, liquid medium.

Claims

1. A method, comprising:

contacting, in an aqueous liquid medium, a rare earth-containing additive with one or more of a metal or metalloid hydroxide, carbonate, and hydrate to remove the one or more of the metal or metalloid hydroxide, carbonate, and hydrate from the aqueous liquid medium.

2. The method of claim 1, wherein the metal or metalloid has an atomic number selected from the group consisting of 5, 13, 22-33, 40-52, 56, 72-84, and 88-94 and the one or more of the metal or metalloid hydroxide, carbonate, and hydrate is selected from the group consisting of:

M(H₂O)₆ⁿ, M(H₂O)₅OH^(n-1), M(OH)^(n-1), M(H₂O)₄(OH)₂^(n-2), M(OH)₂^(n-2), M(H₂O)₃(OH)₃^(n-3), M(OH)₃^(n-3), M(H₂O)₂(OH)₄^(n-4), M(OH)₄^(n-4), M(H₂O)(OH)₅^(n-5), M(OH)₅^(n-5), M(OH)₆^(n-6), M(H₂O)₅CO₃^(n-2), MCO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), M(CO₃)₂^(n-4), M(H₂O)₃(CO₃)₃^(n-6), M(CO₃)₃^(n-6), M(H₂O)₂(CO₃)₄^(n-8), M(CO₃)₄^(n-8), M(H₂O)(CO₃)₅^(n-10), M(CO₃)₅^(n-10), M(CO₃)₆<sup>(n-

     12)</sup>, M(H₂O)₄ⁿ, M(H₂O)₃OH^(n-1), M(H₂O)₂(OH)₂^(n-2), and M(H₂O)(OH)₃^(n-3),

wherein “

M”

is the metal or metalloid,

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of “

M”

.

3. The method of claim 2, wherein the aqueous liquid medium has an Eh and pH sufficient to render the one or more of a metal or metalloid hydroxide, carbonate, and hydrate as a primary species of M.

4. The method of claim 1, wherein the rare earth-containing additive is in the form of cerium (IV) and/or cerium (III) and wherein M is lead.

5. The method of claim 1, wherein metal or metalloid is in the form of a hydroxide.

6. The method of claim 1, wherein metal of metalloid is in the form of a carbonate.

7. The method of claim 1, wherein metal or metalloid is in the form a metal or metalloid hydrate.

8. The method of claim 1, wherein the metal or metalloid is one or more of boron, vanadium, chromium, cadmium, antimony, lead, and bismuth.

9. The method of claim 1, wherein, before the contacting of the aqueous liquid medium with the rare earth-containing additive, the contacting step comprises the sub-step of:

introducing, to the aqueous liquid medium, an agent to convert a metal or metalloid to a primary species, wherein the agent is selected from the group consisting of an oxidizing agent, a reducing agent, a base and/or base equivalent and a acid and/or acid equivalent, wherein the primary species is in the form of the one or more of the metal or metalloid hydroxide, carbonate, and hydrate.

10. The method of claim 1, wherein the rare earth-containing additive is selected from the group consisting of water soluble and water insoluble rare earth-containing additives.

11. The method of claim 1, wherein the lead hydrate is selected from the group consisting of:

Pb(H₂O)₆ⁿ, Pb(H₂O)₅OH^(n-1), Pb(H₂O)₄(OH)₂^(n-2)m, Pb(H₂O)₃(OH)₃^(n-3), Pb(H₂O)₂(OH)₄^(n-4), Pb(H₂O)(OH)₅^(n-5), Pb(H₂O)₅CO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), Pb(H₂O)₃(CO₃)₃^(n-6), Pb(H₂O)₂(CO₃)₄^(n-8), Pb(H₂O)(CO₃)₅^(n-10), Pb(H₂O )₄ⁿ, Pb(H₂O)₃OH_(n-1), Pb(H₂O)₂(OH)₂^(n-2), P(H₂O)(OH)₃^(n-3),

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of Pb.

12. A method, comprising:

contacting, in an aqueous liquid medium, a rare earth-containing additive with one or more of a lead hydroxide, lead carbonate, and lead hydrate to remove the one or more of the hydroxide, lead carbonate, and lead hydrate from the aqueous liquid medium.

13. The method of claim 12, wherein the one or more of the lead hydroxide, lead carbonate, and lead hydrate is selected from the group consisting of:

Pb(H₂O)₆ⁿ, Pb(H₂O)₅OH^(n-1), Pb(OH)^(n-1), Pb(H₂O)₄(OH)₂^(n-2), Pb(OH)₂^(n-2), Pb(H₂O)₃(OH)₃^(n-3), Pb(OH)₃^(n-3), Pb(H₂O)₂(OH)₄^(n-4), Pb(OH)₄^(n-4), Pb(H₂O)(OH)₅^(n-5), Pb(OH)₅^(n-5), Pb(OH)₆^(n-6), Pb(H₂O)₅CO₃^(n-2), PbCO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), Pb(CO₃)₂^(n-4), Pb(H₂O)₃(CO₃)₃^(n-6), Pb(CO₃)₃^(n-6), Pb(H₂O)₂(CO₃)₄^(n-8), Pb(CO₃)₄^(n-8), Pb(H₂O)(CO₃)₅^(n-10), Pb(CO₃)₅^(n-10), Pb(CO₃)₆^(n-12), Pb(H₂O)₄ⁿ, Pb(H₂O)₃OH^(n-1), Pb(H₂O)₂(OH)₂^(n-2), and P(H₂O)(OH)₃^(n-3),

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of Pb.

14. The method of claim 13, wherein the aqueous liquid medium has an Eh and pH sufficient to render the one or more of the metal or metalloid hydroxide, carbonate, and hydrate as primary species.

15. The method of claim 12, wherein the one or more of the lead hydroxide, lead carbonate, and lead hydrate is selected from the group consisting of:

Pb(H₂O)₅CO₃^(n-2), PbCO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), Pb(CO₃)₂^(n-4), Pb(H₂O)₃(CO₃)₃^(n-6), Pb(CO₃)₃^(n-6), Pb(H₂O)₂(CO₃)₄^(n-8), Pb(CO₃)₄^(n-8), Pb(H₂O)(CO₃)₅^(n-10) and Pb(CO₃)₆^(n-12),

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of Pb.

16. The method of claim 12, wherein the rare earth-containing additive is in the form of cerium (IV) and/or cerium (III).

17. The method of claim 16, wherein the rare earth-containing additive further comprises lanthanum.

18. The method of claim 12, wherein the one or more of the lead hydroxide, is selected from the group consisting of:

Pb(H₂O)₅OH^(n-1), Pb(OH)^(n-1), Pb(H₂O)₄(OH)₂^(n-2), Pb(OH)₂^(n-2), Pb(H₂O )₃(OH)₃^(n-3), Pb(OH)₃^(n-3), Pb(H₂O)₂(OH)₄^(n-4), Pb(OH)₄^(n-4), Pb(H₂O)(OH)₅^(n-5), Pb(OH)₅^(n-5), Pb(OH)₆^(n-6), Pb(H₂O)₃OH^(n-1), Pb(H₂O)₂(OH)₂^(n-2), and P(H₂O)(OH)₃^(n-3),

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of Pb.

19. The method of claim 12, wherein, before the contacting of the aqueous liquid medium with the rare earth-containing additive, the contacting step comprises the sub-step of:

introducing, to the aqueous liquid medium, an agent to convert lead to a primary species, wherein the agent is selected from the group consisting of an oxidizing agent, a reducing agent, a base and/or base equivalent and a acid and/or acid equivalent, wherein the primary species is in the form of the one or more of lead hydroxide, lead carbonate, and lead hydrate.

20. A method, comprising:

contacting, in an aqueous liquid medium, a rare earth-containing additive comprising cerium (IV) oxide, CeO₂, with one or more of a metal or metalloid hydroxide, carbonate, and hydrate to remove the one or more of the metal or metalloid hydroxide, carbonate, and hydrate from the aqueous liquid medium.

21. The method of claim 20, wherein the metal or metalloid has an atomic number selected from the group consisting of 5, 13, 22-33, 40-52, 56, 72-84, and 88-94 and the one or more of the metal or metalloid hydroxide, carbonate, and hydrate is selected from the group consisting of:

M(H₂O)₆ⁿ, M(H₂O)₅OH^(n-1), M(OH)^(n-1), M(OH₂O)₄(OH)₂^(n-2), M(OH)₂^(n-2), M(H₂O)₃(OH)₃^(n-3), M(OH)₃^(n-3), M(H₂O)₂(OH)₄^(n-4), M(OH)₄^(n-4), M(H₂O)(OH)₅^(n-5), M(OH)₅^(n-5), M(OH)₆^(n-6), M(H₂O)₅CO₃^(n-2), MCO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), M(CO₃)₂^(n-4), M(H₂O)₃(CO₃)₃^(n-6), M(CO₃)₃^(n-6), M(H₂O)₂(CO₃)₄^(n-2), M(CO)₄^(n-8), M(H₂O)(CO₃)₅^(n-10), M(CO₃)₅^(n-10), M(CO₃)₆^(n-12), M(H₂O)₄ⁿ, M(OH₂O)₃OH^(n-1), M(OH₂O)₂(OH)₂^(n-2), M(OH₂O)(OH)₃^(n-3),

wherein “

M”

is the metal or metalloid,

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of “

M”

.

22. The method of claim 20, wherein the metal is lead and the one or more of the metal hydroxide, metal carbonate, and metal hydrate is selected from the group consisting of:

Pb(H₂O)₆ⁿ, Pb(H₂O)₅OH^(n-1), Pb(OH)^(n-1), Pb(H₂O)₄(OH)₂^(n-2), Pb(OH)₂^(n-2), Pb(H₂O)₃(OH)₃^(n-3), Pb(OH)₃^(n-3), Pb(H₂O)₂(OH)₄^(n-4), Pb(OH)₄^(n-4), Pb(H₂O)(OH)₅^(n-5), Pb(OH)₅^(n-5), Pb(OH)₆^(n-6), Pb(H₂O)₅CO₃^(n-2), PbCO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), Pb(CO₃)₂^(n-4), Pb(H₂O)₃(CO₃)₃^(n-6), Pb(CO₃)₃^(n-6), Pb(H₂O)₂(CO₃)₄^(n-8), Pb(CO₃)₄^(n-8), Pb(H₂O)(CO₃)₅^(n-10), Pb(CO₃)₅^(n-10), Pb(CO₃)₆^(n-12), Pb(H₂O)₄ⁿ, Pb(H₂O)₃OH^(n-1), Pb(H₂O)₂(OH)₂^(n-2), and P(H₂O)(OH)₃^(n-3),

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of Pb.

23. The method of claim 20, wherein the metal or metalloid has an atomic number selected from the group consisting of 5, 13, 22-33, 40-52, 56, 72-84, and 88-94 and wherein the metal or metalloid hydroxide is selected from the group consisting of:

M(H₂O)₅OH^(n-1), M(OH)^(n-1), M(H₂O)₄(OH)₂^(n-2), M(OH)₂^(n-2), M(H₂O)₃(OH)₃^(n-3), M(OH)₃^(n-3), M(H₂O)₂(OH)₄^(n-4), M(OH)₄^(n-4), M(H₂O)(OH)₅^(n-5), M(OH)₅^(n-5), M(OH)₆^(n-6), M(H₂O)₃OH^(n-1), M(H₂O)₂(OH)₂^(n-2), and M(H₂O)(OH)₃^(n-3),

wherein “

M”

is the metal or metalloid,

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of “

M”

.

24. The method of claim 20, wherein the metal or metalloid has an atomic number selected from the group consisting of 5, 13, 22-33, 40-52, 56, 72-84, and 88-94 and wherein the metal or metalloid carbonate is selected from the group consisting of:

M(H₂O)₅CO₃^(n-2), MCO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), M(CO₃)₂^(n-4), M(H₂O)₃(CO₃)₃^(n-6), M(CO₃)₃^(n-6), M(H₂O)₂(CO₃)₄^(n-8), M(CO₃)₄^(n-8), M(H₂O)(CO₃)₅^(n-10), M(CO₃)₅^(n-10), and M(CO₃)₆^(n-12),

wherein “

M”

is the metal or metalloid,

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of “

M”

.

25. The method of claim 20, wherein the metal or metalloid has an atomic number selected from the group consisting of 5, 13, 22-33, 40-52, 56, 72-84, and 88-94 and wherein the metal or metalloid hydrate is selected from the group consisting of:

M(H₂O)₆ⁿ, M(H₂O)₅OH^(n-1), M(₂O)₄(OH)₂^(n-2), M(H₂O)₃(OH)₃^(n-3), M(H₂O)₂(OH)₄^(n-4), M(H₂O)(OH)₅^(n-5), M(H₂O)₅CO₃^(n-2), M(H₂O)₄(CO³)₂^(n-4), M(H₂O)₃(CO₃)₃^(n-6), M(H₂O)₂(CO₃)₄^(n-8), M(H₂O)(CO₃)₅^(n-10), M(H₂O)₄ⁿ, M(H₂O)₃^(n-1), M(H₂O)₂(OH)₂^(n-2), and M(H₂O)(OH)₃^(n-3),

wherein “

M”

is the metal or metalloid,

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of “

M”

.

26. The method of claim 20, wherein the aqueous liquid medium has an Eh and pH sufficient to render the one or more of a metal or metalloid hydroxide, carbonate, and hydrate as a primary species.

27. The method of claim 20, wherein the rare earth-containing additive further comprises cerium (III).

28. The method of claim 20, wherein the rare earth-containing additive further comprises lanthanum.

29. The method of claim 20, wherein the rare earth-containing additive is in the form of cerium (IV) other than cerium (IV) oxide.

30. The method of claim 20, wherein, before the contacting of the aqueous liquid medium with the rare earth-containing additive, the contacting step comprises the sub-step of:

introducing, to the aqueous liquid medium, an agent to convert the metal or metalloid to a primary species, wherein the agent is selected from the group consisting of an oxidizing agent, a reducing agent, a base and/or base equivalent and a acid and/or acid equivalent, wherein the primary species is in the form of the metal or metalloid hydroxide.

31. The method of claim 20, wherein, before the contacting of the aqueous liquid medium with the rare earth-containing additive, the contacting step comprises the sub-step of:

introducing, to the aqueous liquid medium, an agent to convert the metal or metalloid to a primary species, wherein the agent is selected from the group consisting of an oxidizing agent, a reducing agent, a base and/or base equivalent and a acid and/or acid equivalent, wherein the primary species is in the form of the metal or metalloid carbonate.

32. The method of claim 20, wherein, before the contacting of the aqueous liquid medium with the rare earth-containing additive, the contacting step comprises the sub-step of:

introducing, to the aqueous liquid medium, an agent to convert the metal or metalloid to a primary species, wherein the agent is selected from the group consisting of an oxidizing agent, a reducing agent, a base and/or base equivalent and a acid and/or acid equivalent, wherein the primary species is in the form of the metal or metalloid hydrate.

33. The method of claim 20, wherein the metal is lead and the one or more of the metal carbonate is selected from the group consisting of:

Pb(H₂O)₅CO₃^(n-2), PbCO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), Pb(CO₃)₂^(n-4), Pb(H₂O)₃(CO₃)₃^(n-6), Pb(CO₃)₃^(n-6), Pb(H₂O)₂(CO₃)₄^(n-8), Pb(CO₃)₄^(n-8), Pb(H₂O)(CO₃)₅^(n-10), Pb(CO₃)₅^(n-10), and Pb(CO₃)₆^(n-12),

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of Pb.

34. The method of claim 20, wherein the metal or metalloid is lead, wherein, before the contacting of the aqueous liquid medium with the rare earth-containing additive, the contacting step comprises the sub-step of:

introducing, to the aqueous liquid medium, an agent to convert lead to a primary species, wherein the agent is selected from the group consisting of an oxidizing agent, a reducing agent, a base and/or base equivalent and a acid and/or acid equivalent, wherein the primary species is selected from the group consisting of;

Pb(H₂O)₆ⁿ, Pb(H₂O)₅OH^(n-1), Pb(OH)^(n-1), Pb(H₂O)₄(OH)₂^(n-2), Pb(OH)₂^(n-2), Pb(H₂O)₃(OH)₃^(n-3), Pb(OH)₃^(n-3), Pb(H₂O)₂(OH)₄^(n-4), Pb(OH)₄^(n-4), Pb(H₂O)(OH)₅^(n-5), Pb(OH)₅^(n-5), Pb(OH)₆^(n-6), Pb(H₂O)₅CO₃^(n-2), PbCO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), Pb(CO₃)₂^(n-4), Pb(H₂O)₃(CO₃)₃^(n-6), Pb(CO₃)₃^(n-6), Pb(H₂O)₂(CO₃)₄^(n-8), Pb(CO₃)₄^(n-8), Pb(H₂O)(CO₃)₅^(n-10), Pb(CO₃)₅^(n-10), Pb(CO₃)₆^(n-12), Pb(H₂O)₄ⁿ, Pb(H₂O)₃OH^(n-1), Pb(H₂O)₂(OH)₂^(n-2), and P(H₂O)(OH)₃^(n-3),

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of Pb.

35. The method of claim 20, wherein the metal or metalloid is lead, wherein, before the contacting of the aqueous liquid medium with the rare earth-containing additive, the contacting step comprises the sub-step of:

introducing, to the aqueous liquid medium, an agent to convert lead to a primary species, wherein the agent is selected from the group consisting of an oxidizing agent, a reducing agent, a base and/or base equivalent and a acid and/or acid equivalent, wherein the primary species is selected from the group consisting of;

Pb(H₂O)₅CO₃^(n-2), PbCO₃^(n-2), M(H₂O)₄(CO₃)₂^(n-4), Pb(CO₃)₂^(n-4), Pb(H₂O)₃(CO₃)₃^(n-6), Pb(CO₃)₃^(n-6)Pb(H₂O)₂(CO₃)₄^(n-8), Pb(CO₃)₄^(n-8), Pb(H₂O)(CO₃)₅^(n-10), Pb(CO₃)₅^(n-10), and Pb(CO₃)₆^(n-12),

wherein “

n”

is a real number ≦

8, and

wherein “

n”

represents a charge or oxidation state of Pb.