Process and method for producing crystallized metal sulfates

Patent metadata

Field	Value
Publication number	US-12054401-B2
Application number	US-202117222264-A
Country	US
Kind code	B2
Filing date	Apr 5, 2021
Priority date	Jul 10, 2020
Publication date	Aug 6, 2024
Grant date	Aug 6, 2024

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.

First claim

What is claimed is:

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; and

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

2. The process of claim 1 , further comprising refining the aqueous solution upstream of crystallizing the metal sulfate.

3. 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; 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.

4. The process of claim 1 , wherein the crystallized metal sulfate is a battery-grade crystallized metal sulfate, or an electroplating-grade crystallized metal sulfate.

5. A process for generating a crystallized metal sulfate, the process comprising:
leaching a feedstock to form a pregnant leach solution, the pregnant leach solution comprising a metal sulfate;
crystallizing the metal sulfate from the pregnant leach 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 as a first neutralizing agent upstream of crystallizing the metal sulfate, converting the basic metal salt back to the uncrystallized metal sulfate;

wherein the crystallized metal sulfate is a battery-grade crystallized metal sulfate.

6. The process of claim 5 , wherein the feedstock comprises any one or combination of mixed hydroxide precipitates, mixed sulfide precipitates, nickel sulfide concentrate, cobalt sulfide concentrate, nickel laterite, nickel matte, ferronickel, material derived from recycled lithium ion batteries or lithium ion battery manufacturing scrap, or spent cathode material.

7. The process of claim 5 , further comprising refining the pregnant leach solution upstream of crystallizing the metal sulfate.

8. The process of claim 7 , wherein refining the pregnant leach solution comprises subjecting the pregnant leach solution to at least one component removal stage to remove one or more impurities or components from the pregnant leach solution.

9. The process of claim 8 , wherein the at least one component removal stage comprises precipitation, atmospheric or pressure leaching, sulfidation, solvent extraction, ion exchange, cementation, or a combination thereof.

10. The process of claim 8 , wherein the impurities comprise sodium, aluminum, iron, copper, zinc, lithium, cobalt, manganese, and combinations thereof; and the components comprise any one or two of nickel, cobalt, and manganese.

11. The process of claim 5 , 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, wherein the second neutralizing agent is any one or combination of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, and magnesium oxide.

12. The process of claim 11 , wherein when 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.

13. The process of claim 12 , further comprising converting the sodium sulfate back to the sodium hydroxide by electrolysis.

14. The process of claim 11 , wherein using the any one or combination of potassium hydroxide, calcium hydroxide, lithium hydroxide, or magnesium oxide as the second neutralizing agent forms any one or combination of potassium sulfate, calcium sulfate, lithium sulfate, or magnesium sulfate as a by-product.

15. The process of claim 5 , further comprising crystallizing the uncrystallized metal sulfate.

16. The process of claim 5 , wherein crystallizing the metal sulfate comprises introducing the pregnant leach solution into a first crystallizer and operating the first crystallizer under conditions to form the crystallized metal sulfate.

17. The process of claim 16 , wherein the conditions to form the crystallized metal sulfate comprise one or more of bleeding the mother liquor from the first crystallizer and controlling the bleed rate, and
controlling an amount of free water in the first crystallizer, to selectively inhibit crystallizing an impurity when crystallizing the metal sulfate.

18. The process of claim 17 , wherein the impurity comprises lithium, sodium, potassium, or magnesium.

19. The process of claim 16 , further comprising:
dissolving the crystallized metal sulfate in an aqueous solution to form an aqueous sulfate solution;
introducing the aqueous sulfate solution into a second crystallizer; and

operating the second crystallizer under conditions to reform the crystallized metal sulfate from the aqueous metal sulfate solution.

20. The process of claim 5 , wherein the metal sulfate is any one or combination of nickel sulfate, cobalt sulfate, or manganese sulfate.

21. The process of claim 20 , wherein crystallizing the metal sulfate comprises selectively crystallizing any one or more of the nickel sulfate, manganese sulfate, and cobalt sulfate from the pregnant leach solution.

22. The process of claim 5 , wherein the basic metal salt comprises a metal hydroxide.

23. The process of claim 22 , wherein the metal hydroxide comprises any one or a combination of nickel hydroxide, cobalt hydroxide, or manganese hydroxide.

24. The process of claim 5 , 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 comprises introducing the pregnant leach solution into a crystallizer and operating the crystallizer under conditions to form the crystallized metal sulfate,
the conditions comprising bleeding the mother liquor from the crystallizer and controlling the bleed rate to selectively inhibit crystallizing a lithium impurity when crystallizing the metal sulfate.

25. The process of claim 24 , wherein crystallizing the metal sulfate is performed at a pH level in a range of 1.5-2.5.

26. The process of claim 24 , wherein basifying the portion of the mother liquor comprises adding a second neutralizing agent that comprises a hydroxide of an alkali metal or alkaline earth metal.

27. The process of claim 26 , wherein adding the second neutralizing agent increases pH to a level in a range of 7.5-9.5.

28. The process of claim 24 , wherein crystallizing the metal sulfate further comprises adding sulfuric acid to the pregnant leach solution.

29. The process of claim 24 , wherein

Assignees

• Hatch Ltd
• Northvolt Ab

Inventors

• Fraser Robert John
• Stamatiou Evangelos
• Machado Mark Joseph
• Von Schroeter Henry Christian Immo
• Alemrajabi Mahmood

Classifications

• H01M10/54

  Reclaiming serviceable parts of waste accumulators · CPC title

• C22B23/0415

  with acids or salt solutions except ammonium salts solutions · CPC title

• C22B7/007

  by acid leaching · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• C22B26/12 Primary

  Obtaining lithium · CPC title