Recovery of nickel and cobalt from black mass

Patent metadata

Field	Value
Publication number	US-12438209-B2
Application number	US-202217815982-A
Country	US
Kind code	B2
Filing date	Jul 29, 2022
Priority date	May 13, 2022
Publication date	Oct 7, 2025
Grant date	Oct 7, 2025

Abstract

The present invention lies in the field of pyrometallurgy and discloses a process and a slag suitable for the recovery of Ni and Co from Li-ion batteries or their waste, particularly from Black Mass.
The slag composition is defined according to:
25%<MnO<70%; Al 2 O 3 +0.5 MnO<45% SiO 2 >5%; Li 2 O>1%; MnO+Li 2 O+Al 2 O 3 +CaO+SiO 2 +FeO+MgO+P 2 O 5 >90%; and, wherein (CaO+2 Li 2 O+0.4 MnO)/SiO 2 ≥2.0.

This composition is particularly adapted to limit or avoid the wear or corrosion of furnaces lined with magnesia-bearing refractory bricks.

First claim

The invention claimed is:

1. Process for the recovery of Ni and Co from Li-ion batteries or their waste, comprising the steps:
providing a furnace lined with magnesia-bearing refractory bricks;
providing a charge comprising slag formers and Li-ion batteries or their waste, wherein the content of Al in the charge is less than 8%; and,
smelting the charge in reducing conditions, thereby obtaining an alloy containing the major part of the Ni and Co, and a Li-containing slag, wherein the slag has a percent composition by weight according to:
25%<MnO<70%;
Al 2 O 3 +0.5 MnO<45%
SiO 2 >5%;
Li 2 O>1%;
MnO+Li 2 O+Al 2 O 3 +CaO+SiO 2 +FeO+MgO+P 2 O 5 >90%; and,
wherein (CaO+2 Li 2 O+0.4 MnO)/SiO 2 ≥2.0.

2. Process according to claim 1 , wherein the content of MnO in the slag is 30% or more.

3. Process according to claim 1 or 2 , wherein the content of Al 2 O 3 in the slag is less than 30%.

4. Process according to claim 1 , wherein Al 2 O 3 +0.5 MnO<30%.

5. Process according to claim 1 , wherein the Li-ion batteries or their waste is Black Mass.

6. Process according to claim 1 , wherein the content of CaO in the slag is 40% or less.

7. Process according to claim 1 , wherein the slag formers contain no CaO.

8. Process according to claim 1 , wherein the content of Li 2 O in the slag is 3% or more.

9. Process according to claim 1 , wherein the content of cobalt oxide in the slag is 0.05%<CoO<1%.

10. Process according to claim 1 , wherein the content of Fe in the slag is 25% or less.

11. Process according to claim 1 , wherein the content of Fe in the charge is 5% or less.

12. Process according to claim 1 , wherein the content of P 2 O 5 in the slag is 0.5%<P 2 O 5 <10%.

13. Process according to claim 1 , wherein the step of smelting the charge is performed at a temperature of at least 1400° C. and at most 300° C. above the liquidus point of the slag, thereby avoiding overheating.

14. Process according to claim 1 , the smelting step comprising the further steps:
sampling the slag;
cooling down the slag sample and assessing its color; and,
in case the slag sample is green, terminating the smelting step; or,
in case the slag sample is not green, proceeding with the smelting step after adjusting the pO 2 -level to achieve more reducing conditions.

15. Process according to claim 1 , wherein the pO 2 -level is adjusted to 10 −7 >pO 2 >10 −12 .

16. Process according to claim 14 , wherein the color of the slag is green.

17. Process according to claim 1 , wherein the furnace is an electric furnace.

18. Li-containing metallurgical slag having a percent composition by weight according to:
25%<MnO<70%;
Al 2 O 3 +0.5 MnO<45%
SiO 2 >5%;
Li 2 O>3%;
MnO+Li 2 O+Al 2 O 3 +CaO+SiO 2 +FeO+MgO+P 2 O 5 >90%; and,
wherein (CaO+2 Li 2 O+0.4 MnO)/SiO 2 ≥2.0.

19. Li-containing metallurgical slag according to claim 18 , wherein the color of the slag is green.

20. Li-containing metallurgical slag according to claim 18 or 19 , wherein the content of MnO in the slag is 30% or more.

21. Li-containing metallurgical slag according to claim 18 , wherein the content of Al 2 O 3 in the slag is less than 30%.

22. Li-containing metallurgical slag according to claim 18 , wherein the content of CaO in the slag is 40% or less.

23. Li-containing metallurgical slag according to claim 18 , wherein the content of Fe in the slag is 25% or less.

24. Slag former in a pyrometallurgical recycling process comprising the Li-containing metallurgical slag according to claim 18 .

25. The process according to claim 1 , wherein the slag former comprises a Li-containing metallurgical slag having a percent composition by weight according to:
25%<MnO<70%;
Al 2 O 3 +0.5 MnO<45%
SiO 2 >5%;
Li 2 O>3%;
MnO+Li 2 O+Al 2 O 3 +CaO+SiO 2 +FeO+MgO+P 2 O 5 >90%; and,
wherein (CaO+2 Li 2 O+0.4 MnO)/SiO2≥2.0.

26. Li-containing metallurgical slag according to claim 18 , wherein the slag further contains cobalt.

Assignees

• Umicore Nv

Inventors

• Yagi Ryohei
• Scheunis Lennart

Classifications

• Y02W30/84

  Recycling of batteries or fuel cells · CPC title

• C22B1/005

  Preliminary treatment of scrap (C22B1/02 - C22B1/26 take precedence) · CPC title

• H01M10/0525

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

• C22B7/004 Primary

  separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing) · CPC title

• C22B23/028

  separation of nickel from cobalt · CPC title