Methods for recovering metals from metal-containing materials

Patent metadata

Field	Value
Publication number	US-12049683-B2
Application number	US-201917287258-A
Country	US
Kind code	B2
Filing date	Oct 22, 2019
Priority date	Oct 23, 2018
Publication date	Jul 30, 2024
Grant date	Jul 30, 2024

Abstract

Methods for recovering metals from metal-containing materials are provided. The metal-containing material comprises either Co and Li (e.g., an electrode material from a spent lithium ion battery) or Fe and Al (e.g., bauxite). The metal-containing material is exposed to a leaching solution comprising ammonium hydrogen oxalate, oxalic acid, or both, to provide a solid composed of either cobalt oxalate or iron oxalate, and a solution of either lithium oxalate or aluminum oxalate. The solid is processed to provide either cobalt oxide or iron oxide; the solution is processed to provide either a lithium precipitate or an aluminum precipitate, and a filtrate comprising an oxalate; and the filtrate comprising the oxalate is processed to recover ammonium hydrogen oxalate, oxalic acid, or both. The method further comprises repeating the digestion step with the recovered ammonium hydrogen oxalate, the recovered oxalic acid, or both.

First claim

What is claimed is:

1. A method for recovering metals from an electrode material, method comprising:
(a) exposing an electrode material comprising Co and Li, to a leaching solution comprising ammonium hydrogen oxalate, wherein the leaching solution is substantially free of oxalic acid, to provide a solid composed of cobalt oxalate and a solution of lithium oxalate;
(b) processing the solid to recover cobalt;
(c) processing the solution to provide a lithium precipitate and a filtrate comprising an oxalate;
(d) processing the filtrate comprising the oxalate to recover ammonium hydrogen oxalate; and
(e) repeating step (a) with the recovered ammonium hydrogen oxalate.

2. The method of claim 1 , wherein the leaching solution consists of water, the ammonium hydrogen oxalate, and optionally, a reducing agent or an oxidizing agent.

3. The method of claim 1 , wherein the filtrate comprises potassium oxalate and step (d) comprises exposing the filtrate to an ion exchange resin to exchange potassium ions for hydrogen ions.

4. The method of claim 1 , wherein the filtrate comprises diammonium oxalate and step (d) comprises exposing the filtrate to an ion exchange resin to exchange ammonium ions for hydrogen ions to provide recovered ammonium hydrogen oxalate; and step (d) further comprises exposing the ion exchange resin to sulfuric acid to provide a solution of diammonium sulfate; and subjecting the solution of diammonium sulfate to crystallization and deammoniation to provide recovered ammonia.

5. The method of claim 1 , wherein step (b) recovers the cobalt as a cobalt oxide product.

6. The method of claim 5 , wherein the leaching solution further comprises hydrogen peroxide.

7. The method of claim 5 , wherein step (c) comprises adding a salt to the solution of lithium oxalate to induce the precipitation.

8. The method of claim 7 , wherein the salt is a potassium salt.

9. The method of claim 5 , wherein the leaching solution consists of water, the ammonium hydrogen oxalate, and optionally, a reducing agent or an oxidizing agent.

10. The method of claim 5 , wherein the filtrate comprises potassium oxalate and step (d) comprises exposing the filtrate to an ion exchange resin to exchange potassium ions for hydrogen ions.

11. The method of claim 5 , wherein the filtrate comprises diammonium oxalate; step (d) comprises exposing the filtrate to an ion exchange resin to exchange ammonium ions for hydrogen ions to provide recovered ammonium hydrogen oxalate; and step (d) further comprises exposing the ion exchange resin to sulfuric acid to provide a solution of diammonium sulfate; and subjecting the solution of diammonium sulfate to crystallization and deammoniation to provide recovered ammonia.

12. The method of claim 1 , wherein the processing of the solid in step (b) comprises exposing the solid to a base to induce hydrolysis of the solid to recover the cobalt and to provide a second filtrate.

13. The method of claim 12 , wherein the base is provided by the filtrate comprising the oxalate from step (c).

14. The method of claim 1 , wherein step (a) is carried out under inert conditions.

15. The method of claim 14 , wherein the leaching solution consists of water and the ammonium hydrogen oxalate.

16. The method of claim 1 , wherein step (a) is carried out under reductive conditions.

17. The method of claim 16 , wherein the leaching solution consists of water, the ammonium hydrogen oxalate, and a reducing agent.

Assignees

• Univ Kansas

Inventors

• Shiflett Mark Brandon
• Corbin David Richard
• Verma Ankit

Classifications

• B09B3/70

  Chemical treatment, e.g. pH adjustment or oxidation (involving an extraction step B09B3/80) · CPC title

• H01M10/54

  Reclaiming serviceable parts of waste accumulators · CPC title

• C22B26/12

  Obtaining lithium · CPC title

• C22B7/007

  by acid leaching · CPC title

• Y02W30/84

  Recycling of batteries or fuel cells · CPC title