Process for producing crystallized metal sulfates

• US 10,995,014 B1
• Filed: 10/09/2020
• Issued: 05/04/2021
• Est. Priority Date: 07/10/2020
• Status: Active Grant

• Current Assignee: Hatch Limited (Hatchcos Holdings Limited), Northvolt AB
• Original Assignee: Northvolt AB
• Inventors: Fraser, Robert John, Stamatiou, Evangelos, Machado, Mark Joseph, von Schroeter, Henry Christian Immo, Alemrajabi, Mahmood
• Primary Examiner(s): Johnson, Edward M
• Application Number:
  US17/066,769
• Time in Patent Office: 207 Days
• Field of Search: 423 52
• CPC Class Codes: C01D 15/06 Sulfates; Sulfites
• CPC Class Codes: C01D 5/02 Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
• CPC Class Codes: C01G 1/10 Sulfates
• CPC Class Codes: C01G 45/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/10 Sulfates
• CPC Class Codes: C01G 51/04 Oxides; Hydroxides
• CPC Class Codes: C01G 51/10 Sulfates
• CPC Class Codes: C01G 53/04 Oxides; Hydroxides
• CPC Class Codes: C01G 53/10 Sulfates
• CPC Class Codes: C01G 9/02 Oxides; Hydroxides
• CPC Class Codes: C01G 9/08 Sulfides
• CPC Class Codes: C22B 23/0415 with acids or salt solutions except ammonium salts solutions
• CPC Class Codes: C22B 26/12 Obtaining lithium
• CPC Class Codes: C22B 3/08 Sulfuric acid , other sulfurated acids or salts thereof
• CPC Class Codes: C22B 3/1633 with oximes
• CPC Class Codes: C22B 3/42 by ion-exchange extraction
• CPC Class Codes: C22B 47/0054 leaching processes
• CPC Class Codes: C22B 7/007 by acid leaching
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/54 : Reclaiming serviceable parts of waste accumulators
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02P 10/20 : Recycling
• CPC Class Codes: Y02W 30/84 : Recycling of batteries or fuel cells

Abstract

A process for generating a metal sulfate that involves crystallizing a metal sulfate from an aqueous solution to form a crystallized metal sulfate in a mother liquor with uncrystallized metal sulfate remaining in the mother liquor; separating the crystallized metal sulfate from the mother liquor; basifying a portion of the mother liquor to convert the uncrystallized metal sulfate to a basic metal salt; and using the basic metal salt upstream of crystallizing the metal sulfate. So crystallized, the generated metal sulfate may be battery-grade or electroplating-grade.

Claims

1. A process for generating a metal sulfate, the process comprising:

crystallizing a metal sulfate from an aqueous solution to form a crystallized metal sulfate in a mother liquor, the mother liquor comprising an uncrystallized metal sulfate;

separating the crystallized metal sulfate from the mother liquor;

basifying a portion of the mother liquor to convert the uncrystallized metal sulfate to a basic metal salt; and

using the basic metal salt upstream of crystallizing the metal sulfate.

2. The process of claim 1, wherein using the basic metal salt upstream comprises converting the basic metal salt back to the uncrystallized metal sulfate.

3. The process of claim 2, wherein converting the basic metal salt back to the uncrystallized metal sulfate comprises using the basic metal salt as a first neutralizing agent to neutralize acid upstream of crystallizing the metal sulfate.

4. The process of claim 3, wherein basifying the portion of the mother liquor to convert the uncrystallized metal sulfate to the basic metal salt further comprises:

bleeding the mother liquor and controlling the bleed rate to produce an amount of the basic metal salt that is at least approximately equivalent to an amount of the acid to be neutralized upstream of crystallizing the metal sulfate.

5. The process of claim 3, wherein using the basic metal salt as the first neutralizing agent comprises using the basic metal salt as the first neutralizing agent in one or more of a leaching stage and a refining stage.

6. The process of claim 1, wherein basifying the portion of the mother liquor comprises using a second neutralizing agent to convert the uncrystallized metal sulfate to the basic metal salt.

7. The process of claim 6, wherein the second neutralizing agent is sodium hydroxide, and the sodium hydroxide is converted to sodium sulfate when converting the uncrystallized metal sulfate to the basic metal salt.

8. The process of any claim 1, further comprising crystallizing the uncrystallized metal sulfate.

9. The process of claim 1, wherein crystallizing the metal sulfate further comprises bleeding the mother liquor and controlling the bleed rate to selectively inhibit crystallizing an impurity when crystallizing the metal sulfate.

10. The process of claim 1, wherein crystallizing the metal sulfate further comprises controlling an amount of free water in the crystallizer, by one or more of controlling the rate of water evaporation from the crystallizer, and controlling the addition of water to the crystallizer, to selectively inhibit crystallizing an impurity when crystallizing the metal sulfate.

11. The process of claim 9, wherein the impurity comprises lithium, sodium, potassium, or magnesium.

12. The process of claim 1, further comprising isolating the basic metal salt from the mother liquor.

13. The process of claim 12, wherein isolating the basic metal salt comprises using a one-stage or two-stage precipitation circuit and selectively precipitating the basic metal salt.

14. The process of claim 1, wherein the metal sulfate is any one or combination of nickel sulfate, cobalt sulfate, or manganese sulfate.

15. The process of claim 1, wherein the basic metal salt comprises a metal hydroxide.

16. The process of claim 15, wherein the metal hydroxide comprises any one or a combination of nickel hydroxide, cobalt hydroxide, or manganese hydroxide.

17. The process of claim 14, wherein crystallizing the metal sulfate comprises selectively crystallizing any one or more of the nickel sulfate, manganese sulfate, and cobalt sulfate from the aqueous solution.

18. The process of claim 1, further comprising leaching a feedstock to form the aqueous solution comprising the metal sulfate, wherein:

the feedstock comprises material derived from recycled lithium ion batteries or lithium ion battery manufacturing scrap;

the crystallized metal sulfate comprises nickel sulfate, cobalt sulfate, and manganese sulfate;

the basic metal salt comprises nickel hydroxide, cobalt hydroxide and manganese hydroxide; and

crystallizing the metal sulfate further comprises bleeding the mother liquor and controlling the bleed rate to selectively inhibit crystallizing a lithium impurity when crystallizing the metal sulfate.

19. The process of claim 18, wherein crystallizing the metal sulfate is performed at a pH level in a range of <

0-5.

20. The process of claim 19, wherein the pH level is in the range of 1.5-2.5.

21. The process of claim 18, wherein basifying the portion of the mother liquor comprises adding a base that comprises a hydroxide of an alkali metal or alkaline earth metal.

22. The process of claim 21, wherein adding the base increases pH to a level in a range of 7.5-10.

23. The process of claim 18, wherein crystallizing the metal sulfate comprises adding sulfuric acid to the aqueous solution.

24. The process of claim 18, wherein crystallizing the metal sulfate comprises evaporating an amount of water from the aqueous solution that is less than the amount of water to be evaporated to reach a saturation point for the lithium impurity and/or a sodium impurity.

25. The process of claim 18, wherein basifying the portion of the mother liquor to convert the uncrystallized metal sulfate to the basic metal salt further comprises removing the basic metal salt from the mother liquor and forming a cake of the basic metal salt.

26. The process of claim 25, wherein using the basic metal salt upstream comprises using a first part of the cake when leaching the feedstock.

27. The process of claim 26, wherein the first part is 0-40% by weight of the cake.

28. The process of claim 25, wherein using the basic metal salt upstream comprises using a second part of the cake in refining stage.

29. The process of claim 28, wherein the second part is 60-100% by weight of the cake.

30. The process of claim 18, wherein the feedstock comprises by weight at least 50% recycled lithium ion battery materials and/or lithium ion battery manufacturing scrap.