IP Library Granted Patent US 9,233,863
Granted Patent B2
US 9,233,863 · App. 13/432,987 · Granted Jan 12, 2016

Rare earth removal of hydrated and hydroxyl species

Inventors: Robert Cable (Las Vegas, NV); Carl Hassler (Gig Harbor, WA); John Burba (Parker, CO)
Assignee: Molycorp Minerals, LLC
C02F1/72C02F1/281C02F1/66C02F1/705C02F2001/007C02F2101/103C02F2101/20C02F2303/16Y02W10/37
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Quick Facts
Patent No.
US 9,233,863
App. No.
13/432,987
Granted
Jan 12, 2016
Kind
B2
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 (89)

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(H 2 O) 6 n , M(H 2 O) 5 OH (n-1) , M(OH) (n-1) , M(H 2 O) 4 (OH) 2 (n-2) , M(OH) 2 (n-2) , M(H 2 O) 3 (OH) 3 (n-3) , M(OH) 3 (n-3) , M(H 2 O) 2 (OH) 4 (n-4) , M(OH) 4 (n-4) , M(H 2 O)(OH) 5 (n-5) , M(OH) 5 (n-5) , M(OH) 6 (n-6) , M(H 2 O) 5 CO 3 (n-2) , MCO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , M(CO 3 ) 2 (n-4) , M(H 2 O) 3 (CO 3 ) 3 (n-6) , M(CO 3 ) 3 (n-6) , M(H 2 O) 2 (CO 3 ) 4 (n-8) , M(CO 3 ) 4 (n-8) , M(H 2 O)(CO 3 ) 5 (n-10) , M(CO 3 ) 5 (n-10) , M(CO 3 ) 6 (n- 12) , M(H 2 O) 4 n , M(H 2 O) 3 OH (n-1) , M(H 2 O) 2 (OH) 2 (n-2) , and M(H 2 O)(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(H 2 O) 6 n , Pb(H 2 O) 5 OH (n-1) , Pb(H 2 O) 4 (OH) 2 (n-2) m, Pb(H 2 O) 3 (OH) 3 (n-3) , Pb(H 2 O) 2 (OH) 4 (n-4) , Pb(H 2 O)(OH) 5 (n-5) , Pb(H 2 O) 5 CO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , Pb(H 2 O) 3 (CO 3 ) 3 (n-6) , Pb(H 2 O) 2 (CO 3 ) 4 (n-8) , Pb(H 2 O)(CO 3 ) 5 (n-10) , Pb(H 2 O ) 4 n , Pb(H 2 O) 3 OH (n-1) , Pb(H 2 O) 2 (OH) 2 (n-2) , P(H 2 O)(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(H 2 O) 6 n , Pb(H 2 O) 5 OH (n-1) , Pb(OH) (n-1) , Pb(H 2 O) 4 (OH) 2 (n-2) , Pb(OH) 2 (n-2) , Pb(H 2 O) 3 (OH) 3 (n-3) , Pb(OH) 3 (n-3) , Pb(H 2 O) 2 (OH) 4 (n-4) , Pb(OH) 4 (n-4) , Pb(H 2 O)(OH) 5 (n-5) , Pb(OH) 5 (n-5) , Pb(OH) 6 (n-6) , Pb(H 2 O) 5 CO 3 (n-2) , PbCO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , Pb(CO 3 ) 2 (n-4) , Pb(H 2 O) 3 (CO 3 ) 3 (n-6) , Pb(CO 3 ) 3 (n-6) , Pb(H 2 O) 2 (CO 3 ) 4 (n-8) , Pb(CO 3 ) 4 (n-8) , Pb(H 2 O)(CO 3 ) 5 (n-10) , Pb(CO 3 ) 5 (n-10) , Pb(CO 3 ) 6 (n-12) , Pb(H 2 O) 4 n , Pb(H 2 O) 3 OH (n-1) , Pb(H 2 O) 2 (OH) 2 (n-2) , and P(H 2 O)(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(H 2 O) 5 CO 3 (n-2) , PbCO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , Pb(CO 3 ) 2 (n-4) , Pb(H 2 O) 3 (CO 3 ) 3 (n-6) , Pb(CO 3 ) 3 (n-6) , Pb(H 2 O) 2 (CO 3 ) 4 (n-8) , Pb(CO 3 ) 4 (n-8) , Pb(H 2 O)(CO 3 ) 5 (n-10) and Pb(CO 3 ) 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(H 2 O) 5 OH (n-1) , Pb(OH) (n-1) , Pb(H 2 O) 4 (OH) 2 (n-2) , Pb(OH) 2 (n-2) , Pb(H 2 O ) 3 (OH) 3 (n-3) , Pb(OH) 3 (n-3) , Pb(H 2 O) 2 (OH) 4 (n-4) , Pb(OH) 4 (n-4) , Pb(H 2 O)(OH) 5 (n-5) , Pb(OH) 5 (n-5) , Pb(OH) 6 (n-6) , Pb(H 2 O) 3 OH (n-1) , Pb(H 2 O) 2 (OH) 2 (n-2) , and P(H 2 O)(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, CeO 2 , 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(H 2 O) 6 n , M(H 2 O) 5 OH (n-1) , M(OH) (n-1) , M(OH 2 O) 4 (OH) 2 (n-2) , M(OH) 2 (n-2) , M(H 2 O) 3 (OH) 3 (n-3) , M(OH) 3 (n-3) , M(H 2 O) 2 (OH) 4 (n-4) , M(OH) 4 (n-4) , M(H 2 O)(OH) 5 (n-5) , M(OH) 5 (n-5) , M(OH) 6 (n-6) , M(H 2 O) 5 CO 3 (n-2) , MCO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , M(CO 3 ) 2 (n-4) , M(H 2 O) 3 (CO 3 ) 3 (n-6) , M(CO 3 ) 3 (n-6) , M(H 2 O) 2 (CO 3 ) 4 (n-2) , M(CO) 4 (n-8) , M(H 2 O)(CO 3 ) 5 (n-10) , M(CO 3 ) 5 (n-10) , M(CO 3 ) 6 (n-12) , M(H 2 O) 4 n , M(OH 2 O) 3 OH (n-1) , M(OH 2 O) 2 (OH) 2 (n-2) , M(OH 2 O)(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(H 2 O) 6 n , Pb(H 2 O) 5 OH (n-1) , Pb(OH) (n-1) , Pb(H 2 O) 4 (OH) 2 (n-2) , Pb(OH) 2 (n-2) , Pb(H 2 O) 3 (OH) 3 (n-3) , Pb(OH) 3 (n-3) , Pb(H 2 O) 2 (OH) 4 (n-4) , Pb(OH) 4 (n-4) , Pb(H 2 O)(OH) 5 (n-5) , Pb(OH) 5 (n-5) , Pb(OH) 6 (n-6) , Pb(H 2 O) 5 CO 3 (n-2) , PbCO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , Pb(CO 3 ) 2 (n-4) , Pb(H 2 O) 3 (CO 3 ) 3 (n-6) , Pb(CO 3 ) 3 (n-6) , Pb(H 2 O) 2 (CO 3 ) 4 (n-8) , Pb(CO 3 ) 4 (n-8) , Pb(H 2 O)(CO 3 ) 5 (n-10) , Pb(CO 3 ) 5 (n-10) , Pb(CO 3 ) 6 (n-12) , Pb(H 2 O) 4 n , Pb(H 2 O) 3 OH (n-1) , Pb(H 2 O) 2 (OH) 2 (n-2) , and P(H 2 O)(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(H 2 O) 5 OH (n-1) , M(OH) (n-1) , M(H 2 O) 4 (OH) 2 (n-2) , M(OH) 2 (n-2) , M(H 2 O) 3 (OH) 3 (n-3) , M(OH) 3 (n-3) , M(H 2 O) 2 (OH) 4 (n-4) , M(OH) 4 (n-4) , M(H 2 O)(OH) 5 (n-5) , M(OH) 5 (n-5) , M(OH) 6 (n-6) , M(H 2 O) 3 OH (n-1) , M(H 2 O) 2 (OH) 2 (n-2) , and M(H 2 O)(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(H 2 O) 5 CO 3 (n-2) , MCO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , M(CO 3 ) 2 (n-4) , M(H 2 O) 3 (CO 3 ) 3 (n-6) , M(CO 3 ) 3 (n-6) , M(H 2 O) 2 (CO 3 ) 4 (n-8) , M(CO 3 ) 4 (n-8) , M(H 2 O)(CO 3 ) 5 (n-10) , M(CO 3 ) 5 (n-10) , and M(CO 3 ) 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(H 2 O) 6 n , M(H 2 O) 5 OH (n-1) , M( 2 O) 4 (OH) 2 (n-2) , M(H 2 O) 3 (OH) 3 (n-3) , M(H 2 O) 2 (OH) 4 (n-4) , M(H 2 O)(OH) 5 (n-5) , M(H 2 O) 5 CO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , M(H 2 O) 3 (CO 3 ) 3 (n-6) , M(H 2 O) 2 (CO 3 ) 4 (n-8) , M(H 2 O)(CO 3 ) 5 (n-10) , M(H 2 O) 4 n , M(H 2 O) 3 (n-1) , M(H 2 O) 2 (OH) 2 (n-2) , and M(H 2 O)(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(H 2 O) 5 CO 3 (n-2) , PbCO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , Pb(CO 3 ) 2 (n-4) , Pb(H 2 O) 3 (CO 3 ) 3 (n-6) , Pb(CO 3 ) 3 (n-6) , Pb(H 2 O) 2 (CO 3 ) 4 (n-8) , Pb(CO 3 ) 4 (n-8) , Pb(H 2 O)(CO 3 ) 5 (n-10) , Pb(CO 3 ) 5 (n-10) , and Pb(CO 3 ) 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(H 2 O) 6 n , Pb(H 2 O) 5 OH (n-1) , Pb(OH) (n-1) , Pb(H 2 O) 4 (OH) 2 (n-2) , Pb(OH) 2 (n-2) , Pb(H 2 O) 3 (OH) 3 (n-3) , Pb(OH) 3 (n-3) , Pb(H 2 O) 2 (OH) 4 (n-4) , Pb(OH) 4 (n-4) , Pb(H 2 O)(OH) 5 (n-5) , Pb(OH) 5 (n-5) , Pb(OH) 6 (n-6) , Pb(H 2 O) 5 CO 3 (n-2) , PbCO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , Pb(CO 3 ) 2 (n-4) , Pb(H 2 O) 3 (CO 3 ) 3 (n-6) , Pb(CO 3 ) 3 (n-6) , Pb(H 2 O) 2 (CO 3 ) 4 (n-8) , Pb(CO 3 ) 4 (n-8) , Pb(H 2 O)(CO 3 ) 5 (n-10) , Pb(CO 3 ) 5 (n-10) , Pb(CO 3 ) 6 (n-12) , Pb(H 2 O) 4 n , Pb(H 2 O) 3 OH (n-1) , Pb(H 2 O) 2 (OH) 2 (n-2) , and P(H 2 O)(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(H 2 O) 5 CO 3 (n-2) , PbCO 3 (n-2) , M(H 2 O) 4 (CO 3 ) 2 (n-4) , Pb(CO 3 ) 2 (n-4) , Pb(H 2 O) 3 (CO 3 ) 3 (n-6) , Pb(CO 3 ) 3 (n-6) Pb(H 2 O) 2 (CO 3 ) 4 (n-8) , Pb(CO 3 ) 4 (n-8) , Pb(H 2 O)(CO 3 ) 5 (n-10) , Pb(CO 3 ) 5 (n-10) , and Pb(CO 3 ) 6 (n-12) ,

wherein “n” is a real number ≦8, and

wherein “n” represents a charge or oxidation state of Pb.

Assignments (5)
SHORT FORM PATENT SECURITY AGREEMENT Recorded Sep 5, 2025
From: MP MINE OPERATIONS LLC; SECURE NATURAL RESOURCES LLC
To: JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT
Reel/Frame 072818/0718 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE'S ADDRESS PREVIOUSLY RECORDED ON REEL 038340 FRAME 0265. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded May 3, 2016
From: MOLYCORP MINERALS, LLC; PP IV MOUNTAIN PASS II, INC.; PP IV MOUNTAIN PASS INC.; RCF IV SPEEDWAGON INC.
To: SECURE NATURAL RESOURCES LLC
Reel/Frame 038596/0138 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 21, 2016
From: MOLYCORP MINERALS, LLC; PP IV MOUNTAIN PASS II, INC.; PP IV MOUNTAIN PASS INC.; RCF IV SPEEDWAGON INC.
To: SECURE NATURAL RESOURCES LLC
Reel/Frame 038340/0265 →
SECURITY AGREEMENT Recorded Jun 11, 2012
From: MOLYCORP MINERALS, LLC
To: WELLS FARGO BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 028355/0440 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 11, 2012
From: HASSLER, CARL; BURBA, JOHN; CABLE, ROBERT
To: MOLYCORP MINERALS, LLC
Reel/Frame 028025/0524 →
Continuity (15)
Continuation In Part 13356581 · Jan 23, 2012
Provisional Application 61474902 · Apr 13, 2011
Provisional Application 61475155 · Apr 13, 2011
Provisional Application 61539780 · Sep 27, 2011
Provisional Application 61546803 · Oct 13, 2011
Provisional Application 61614427 · Mar 22, 2012
Provisional Application 61476667 · Apr 18, 2011
Provisional Application 61558887 · Nov 11, 2011
Provisional Application 61564132 · Nov 28, 2011
Provisional Application 61614418 · Mar 22, 2012
Provisional Application 61613883 · Mar 21, 2012
Provisional Application 61613857 · Mar 21, 2012
Provisional Application 61538634 · Sep 23, 2011
Provisional Application 61553809 · Oct 31, 2011
Related Publication 20120261345A1 · Oct 18, 2012