Method for manufacturing lithium hydroxide and lithium carbonate, and device therefor

Patent metadata

Field	Value
Publication number	US-10759671-B2
Application number	US-201615570400-A
Country	US
Kind code	B2
Filing date	Apr 29, 2016
Priority date	Apr 30, 2015
Publication date	Sep 1, 2020
Grant date	Sep 1, 2020

Abstract

The present invention relates to a method for manufacturing lithium hydroxide and lithium carbonate, and a device therefor. The present invention provides a method for manufacturing lithium hydroxide, comprising: a step of dissolving lithium phosphate in an acid; a step of preparing a monovalent ion selective-type electrodialysis device disposed in the order of a cathode cell containing a cathode separator, a monovalent anion selective-type dialysis membrane for selectively permeating a monovalent anion, a monovalent cation selective-type dialysis membrane for selectively permeating a monovalent cation, and an anode cell containing an anode separator, injecting the lithium phosphate dissolved in the acid between the anode separator of the anode cell and the monovalent cation selective-type dialysis membrane, and between the cathode separator of the cathode cell and the monovalent anion selective-type dialysis membrane, respectively, and injecting water between the monovalent cation selective-type dialysis membrane and the monovalent anion selective-type dialysis membrane; a step of obtaining an aqueous lithium chloride solution, and at the same time, obtaining a phosphoric acid aqueous solution formed as a byproduct, by applying an electric current to the monovalent ion selective-type electrodialysis device; and a step of converting the obtained aqueous lithium chloride solution into an aqueous lithium hydroxide solution.

First claim

The invention claimed is:

1. A method for manufacturing lithium hydroxide, comprising
a step of dissolving lithium phosphate in a hydrochloric acid;
a step of preparing a monovalent ion selective-type electrodialysis device disposed in the order of a cathode cell containing a cathode separator, a monovalent anion selective-type dialysis membrane for selectively permeating a monovalent anion, a monovalent cation selective-type dialysis membrane for selectively permeating a monovalent cation, and an anode cell containing an anode separator;
a step of injecting the lithium phosphate dissolved in the hydrochloric acid between the anode separator of the anode cell and the monovalent cation selective-type dialysis membrane, and between the cathode separator of the cathode cell and the monovalent anion selective-type dialysis membrane, respectively;
a step of injecting water between the monovalent cation selective-type dialysis membrane and the monovalent anion selective-type dialysis membrane;
a step of obtaining an aqueous lithium chloride solution, and at the same time, obtaining a phosphoric acid aqueous solution formed as a byproduct, by applying an electric current to the monovalent ion selective-type electrodialysis device; and
a step of converting the obtained aqueous lithium chloride solution into an aqueous lithium hydroxide solution.

2. The method for manufacturing lithium hydroxide of claim 1 , wherein the step of converting the obtained aqueous lithium chloride solution into an aqueous lithium hydroxide solution includes
a step of preparing a bipolar electrodialysis device disposed in the order of an anode cell containing an anode; a first bipolar membrane; an anion selective-type dialysis membrane; a cation selective-type dialysis membrane, a second bipolar membrane; and a cathode cell containing a cathode;
a step of injecting the aqueous lithium chloride solution between the cation selective-type dialysis membrane and the anion selective-type dialysis membrane;
a step of injecting water between the first bipolar membrane and the anion selective-type dialysis membrane and between the second bipolar membrane and the cation selective-type dialysis membrane, respectively; and
a step of obtaining an aqueous lithium hydroxide solution and at the same time, obtaining an aqueous hydrochloric acid solution formed as a byproduct by applying an electric current to the bipolar electrodialysis device.

3. The method for manufacturing lithium hydroxide of claim 2 , wherein the lithium phosphate is prepared by a method including: a step of preparing a lithium-containing solution; and
a step of injecting a solution comprising phosphoric acid to the lithium-containing solution to precipitate a dissolved lithium as lithium phosphate.

4. The method for manufacturing lithium hydroxide of claim 3 , wherein the aqueous phosphoric acid solution obtained by the monovalent ion selective-type electrodialysis device is used as the solution comprising phosphoric acid in the step of injecting a solution comprising phosphoric acid to the lithium-containing solution to precipitate a dissolved lithium as lithium phosphate.

5. The method for manufacturing lithium hydroxide of claim 4 , wherein the aqueous hydrochloric acid solution obtained by the bipolar electrodialysis device is used as a part of or a whole of the hydrochloric acid in the step of dissolving lithium phosphate in a hydrochloric acid.

6. The method for manufacturing lithium hydroxide of claim 3 , wherein after the step of obtaining an aqueous lithium hydroxide solution and at the same time, obtaining a aqueous hydrochloric acid solution formed as a byproduct by applying an electric current to the bipolar electrodialysis device,
the method further includes a step of concentrating the aqueous lithium hydroxide solution to crystallize it; and
a step of drying the crystallized lithium hydroxide to obtain lithium hydroxide in a powder form.

7. The method for manufacturing lithium hydroxide of claim 6 , wherein in the step of preparing a lithium-containing solution,
the lithium-containing solution is selected from a solution extracting lithium dissolved in the ocean, a solution generated in a process of recycling a wasted lithium battery, a lithium mineral-leaching solution, a brine, a lithium-containing hot spring water, a lithium-containing underground water, a lithium-containing bittern, and a combination thereof.

8. The method for manufacturing lithium hydroxide of claim 7 , wherein before the step of injecting a solution comprising phosphoric acid to the lithium-containing solution to precipitate dissolved lithium as lithium phosphate,
the method further includes a step of removing a divalent ion impurity in the lithium-containing solution.

9. The method for manufacturing lithium hydroxide of claim 8 , wherein the step of removing a divalent ion impurity in the lithium-containing solution includes
a step of removing a calcium ion and a magnesium ion by injecting a compound selected from sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ), calcium hydroxide (Ca(OH) 2 ), sodium sulfate (Na 2 SO 4 ), and a combination thereof to the lithium-containing solution.

10. The method for manufacturing lithium hydroxide of claim 2 , wherein in the step of preparing a monovalent ion selective-type electrodialysis device disposed in the order of a cathode cell containing a cathode separator, a monovalent anion selective-type dialysis membrane for selectively permeating a monovalent anion, a monovalent cation selective-type dialysis membrane for selectively permeating a monovalent cation, and an anode cell containing an anode separator, injecting the lithium phosphate dissolved in the acid between the anode separator of the anode cell and the monovalent cation selective-type dialysis membrane, and between the cathode separator of the cathode cell and the monovalent anion selective-type dialysis membrane, respectively, and injecting water between the monovalent cation selective-type dialysis membrane and the monovalent anion selective-type dialysis membrane,
the cathode cell and the anode cell include an electrode solution selected from lithium sulfate (Li 2 SO 4 ), lithium hydroxide (LiOH), lithium dihydrogen phosphate (LiH 2 PO 4 ), phosphoric acid (H 3 PO 4 ), and a combination thereof, respectively.

11. The method for manufacturing lithium hydroxide of claim 10 , wherein electrical conductivity of the electrode solution is 10 to 100 ms/cm.

12. The method for manufacturing lithium hydroxide of claim 2 , wherein the step of obtaining an aqueous lithium chloride solution, and at the same time, obtaining a phosphoric acid aqueous solution formed as a byproduct, by applying an electric current to the monovalent ion selective-type electrodialysis device comprises:
a step of permeating lithium ions in the lithium phosphate dissolved in the acid through the monovalent cation selective-type dialysis membrane to be transferred in a direction to the cathode; and
a step of permeating the chlorine ion in the lithium phosphate dissolved in the acid through the monovalent anion selective-type dialysis membrane to be transferred in a direction to the anode,
wherein the transferred lithium ion and the transferred chlorine ion are gathered between the monovalent cation selective-type dialysis membrane and the monovalent anion selective-type dialysis membrane to provide the aqueous lithium chloride solution, and
phosphate ion in the lithium phosphate dissolved in the acid remaining behind is gathered between the anode separator of the anode cell and the monovalent cation selective-type dialysis membrane and between the cathode separator of the cath

Assignees

• Res Inst Ind Science & Tech

Inventors

• Park Sung Kook
• Park Kwang Seok
• Lee Sang Gil
• Jung Woo Chul
• Kim Ki Young
• Lee Hyun Woo

Classifications

• B01D2311/25

  Recirculation, recycling or bypass, e.g. recirculation of concentrate into the feed · CPC title

• C01D15/08 Primary

  Carbonates; Bicarbonates · CPC title

• B01J19/08

  Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor (application of shock waves B01J3/08) · CPC title

• B01D61/46

  Apparatus therefor · CPC title

• B01D61/445

  with bipolar membranes; Water splitting · CPC title