Methods for regenerating li and ni from a solution

Patent metadata

Field	Value
Publication number	US-2024011123-A1
Application number	US-202118039881-A
Country	US
Kind code	A1
Filing date	Nov 4, 2021
Priority date	Dec 1, 2020
Publication date	Jan 11, 2024
Grant date	—

Abstract

Disclosed herein are methods of recycling elements, such as, e.g., lithium and/or nickel, from a solution, such as, e.g., methods of recovering reusable lithium and nickel from a waste stream produced by the delithiation of a lithium nickel oxide material.

First claim

1 . A process for isolating lithium and/or nickel comprising:
(A) delithiating a lithium nickel oxide (LNO) material in the presence of a mineral acid and a hypochlorite salt to produce a delithiated nickel oxide (DLNO) material and a waste stream, wherein the waste stream comprises a chloride ion, a lithium ion, and a nickel ion; and (B1) precipitating Ni(OH) 2 from the waste stream to produce a lithium rich solution.

2 . The process according to claim 1 , wherein the hypochlorite salt is selected from calcium hypochlorite salts, lithium hypochlorite salts, and sodium hypochlorite salts.

3 . The process according to claim 1 , further comprising treating the waste stream by solvent extraction in the presence of input LiOH, input NaOH, or a combination thereof

4 . (canceled)

5 . A process for isolating lithium and/or nickel comprising:
(A) delithiating a lithium nickel oxide (LNO) material in the presence of HCl and a hypochlorite salt to produce a delithiated nickel oxide (DLNO) material and a waste stream, wherein the waste stream comprises a chloride ion, a lithium ion, and a nickel ion; and (B2) treating the waste stream by solvent extraction in the presence of input LiOH, input NaOH, or a combination thereof to produce a lithium rich solution.

6 . The process according to claim 1 , wherein the lithium rich solution comprises one or more multivalent ions.

7 . (canceled)

8 . The process according to claim 1 , further comprising:
(D1) subjecting the lithium rich solution to ion exchange to remove at least some multivalent ions other than Li + and produce a LiCl stream.

9 . The process according to claim 8 , wherein:
the hypochlorite salt is chosen from calcium hypochlorite salts and sodium hypochlorite salts; and step (D1) further comprises: subjecting the lithium rich solution to solvent extraction in the presence of input HCl to remove at least some multivalent ions to produce the LiCl stream; separating Na from the LiCl stream using solvent extraction to produce a NaCl stream; and optionally concentrating the LiCl stream.

10 . The process according to claim 9 , further comprising subjecting at least a portion of the NaCl stream to electrolysis to produce NaOH, a H 2 gas, and a Cl 2 gas, and optionally further comprising any of (1) subjecting at least a portion of the H 2 gas to an HCl burner to produce HCl, or (2) reacting at least a portion of the Cl 2 gas with Ca(OH) 2 or NaOH to produce calcium hypochlorite or sodium hypochlorite.

11 . (canceled)

12 . (canceled)

13 . The process according to claim 1 , wherein:
the hypochlorite salt is a lithium hypochlorite salt; and the process further comprises:
(D2) converting the lithium rich solution to a Li 2 CO 3 stream

wherein step (D2) optionally comprises:
treating the lithium rich solution with soda ash to produce the Li 2 CO 3 stream.

14 . (canceled)

15 . The process according to claim 8 , further comprising:
(E) isolating LiOH from the LiCl stream, wherein the isolated LiOH is optionally in a liquid form, a crystalline form, or both, and optionally reacting at least a portion of the isolated LiOH with a Cl 2 gas to produce lithium hypochlorite or crystallizing LiOH monohydrate from at least a portion of the isolated LiOH.

16 .- 19 . (canceled)

20 . The process according to claim 15 , wherein step (E) comprises:
(F) subjecting the LiCl stream to electrolysis to produce a LiOH liquid, a H 2 gas, and a Cl 2 gas; and (G) precipitating LiOH monohydrate from the LiOH liquid, and optionally, subjecting at least a portion of the H 2 gas to an HCl burner in the presence of at least a portion of the Cl 2 gas to produce HCl, or reacting at least a portion of the Cl 2 gas with Ca(OH) 2 to produce calcium hypochlorite, or reacting at least a portion of the LiOH liquid with at least a portion of the Cl 2 gas to produce lithium hypochlorite.

21 .- 23 . (canceled)

24 . The process according to claim 15 , wherein step (E) comprises:
separating Li from Na in the LiCl stream using solvent extraction in the presence of input NaOH to produce NaCl; optionally concentrating the LiCl stream to produce a concentrated LiCl stream; and subjecting the LiCl stream or the concentrated LiCl stream to electrolysis to convert the LiCl to a LiOH liquid, a H 2 gas, and a Cl 2 gas.

25 . The process according to claim 24 , further comprising at least one of:
a) precipitating LiOH monohydrate from the LiOH liquid,. b) subjecting at least a portion of the H 2 gas to an HCl burner, optionally in the presence of at least a portion of the Cl 2 gas, to produce HCl, c) reacting at least a portion of the Cl 2 gas with Ca(OH) 2 to produce calcium hypochlorite, or d) subjecting at least a portion of the produced NaCl to electrolysis to produce NaOH.

26 .- 28 . (canceled)

29 . The process according to claim 13 , wherein further comprising a step (E) of:
treating the Li 2 CO 3 stream with calcium hydroxide to produce LiOH and CaCO 3 .

30 The process according to claim 29 , further comprising:
subjecting at least a portion of the LiOH obtained in step (E) to ion exchange; and
crystallizing the ion exchanged LiOH to obtain battery grade lithium hydroxide monohydrate or reacting at least a portion of the ion-exchanged LiOH with Cl 2 gas to produce lithium hypochlorite.

31 . (canceled)

32 . The process according to claim 1 , wherein satisfying at least one of the following:
a) the process is continuous b) a process input is produced during the operation of the process and recycled in the process, c) the mineral acid is HCl, or d) the waste stream has a pH of 2 6.

33 .- 35 . (canceled)

36 . The process according to claim 1 , wherein the LNO material is chosen from LiNi x M y O z materials, wherein:
M is chosen from Ni, Co, Mn, Ti, Zr, Nb, Hf, V, Cr, Sn, Cu, Mo, W, Fe, Si, B, and combinations of any of the foregoing; x is chosen from numbers from 0 to 1.999; y is chosen from numbers from 0 to 1.999; and z is chosen from numbers from 1 to 4.

37 . (canceled)

38 . (canceled)

39 . The process according to claim 36 , wherein the LNO material is chosen from LiNiMO z materials, and is optionally LiNiCoAlO z and LiNiCoAlM′O z materials, wherein M′ is chosen from metals.

40 . (canceled)

41 . The process according to claim 1 , further comprising forming a LNO material using Ni(OH) 2 produced by the process, LiOH monohydrate produced by the process, or both.

42 . A process for isolating lithium and/or nickel comprising:
(A) delithiating a lithium nickel oxide (LNO) material in the presence of a mineral acid and a calcium hypochlorite salt to produce a delithiated nickel oxide (DLNO) material and a waste stream, wherein the waste stream comprises a chloride ion, a lithium ion, and a nickel ion; (B) precipitating Ni(OH) 2 from the waste stream to produce a lithium rich solution; (C) optionally concentrating the lithium rich solution to produce a concentrated lithium rich solution; (D) subjecting the lithium rich solution or the concentrated lithium rich solution to ion exchange to remove at least some multivalent ions other than Li + and produce a LiCl stream; (E) subjecting the LiCl stream to electrolysis to produce a LiO

Assignees

• Basf Corp

Inventors

• Dinn Tinoush
• Mays William C
• Panchula Martin Lawrence
• Von Deak Dieter G

Classifications

• C01G53/01

  Preparation or separation involving a liquid-liquid extraction, an adsorption or an ion-exchange · CPC title

• C01D3/04

  Chlorides · CPC title

• C25B1/02

  Hydrogen or oxygen · CPC title

• H01M6/52

  Reclaiming serviceable parts of waste cells or batteries {, e.g. recycling} · CPC title

• C25B1/34

  Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis · CPC title