Lithium extraction composite for recovery of lithium from brines, and process of using said composition

Patent metadata

Field	Value
Publication number	US-2019275473-A1
Application number	US-201916296943-A
Country	US
Kind code	A1
Filing date	Mar 8, 2019
Priority date	Mar 8, 2018
Publication date	Sep 12, 2019
Grant date	—

Abstract

A lithium extraction composite comprising: (i) a porous support and (ii) particles of a lithium-selective sorbent material coated on at least one surface of the support, wherein the support has a planar membrane, fiber (or rod), or tubular shape. A method for extracting and recovering a lithium salt from an aqueous solution by use of the above-described composition is also described, the method comprising (a) flowing the aqueous source solution through a first zone or over a first surface of the lithium extraction composite to result in selective lithium intercalation in the lithium-selective sorbent material in the first zone or first surface; and (b) simultaneously recovering lithium salt extracted in step (a) from said lithium-selective sorbent material by flowing an aqueous stripping solution through a second zone or over a second surface of the lithium extraction composite in which lithium ions from the first zone or first surface diffuse.

First claim

What is claimed is:

1 . A lithium extraction composite comprising (i) a porous support and (ii) particles of a lithium-selective sorbent material coated on at least one surface of the support, wherein said support has a planar membrane, fiber, or tubular shape.

2 . The lithium extraction composite of claim 1 , wherein said support is a polymer that has a melting point of at least 80° C.

3 . The lithium extraction composite of claim 1 , wherein said support has a melting point of at least 100° C.

4 . The lithium extraction composite of claim 2 , wherein said polymer is selected from the group consisting of polyimide, polyether ether ketone (PEEK), polybenzimidazole, ionomers, polysiloxanes, vinyl-addition polymers, polyurethanes, polyesters, polycarbonates, polyamides, polyethyleneimine (PEI), and copolymers, mixtures, and composites thereof.

5 . The lithium extraction composite of claim 1 , wherein said support has an inorganic composition.

6 . The lithium extraction composite of claim 5 , wherein said inorganic support has a metal oxide, metal carbide, metal nitride, or metal boride composition.

7 . The lithium extraction composite of claim 5 , wherein said inorganic support has an elemental carbon composition.

8 . The lithium extraction composite of claim 1 , wherein said lithium-selective sorbent material is selected from spinel-type lithium nickel cobalt manganese oxides (NCMs), lithium nickel cobalt aluminum oxides (NCAs), lithium manganese oxides (LMOs), spinel-type lithium titanium oxides (LTOs), and lithium aluminum layered double hydroxide chloride (LiCl.2Al(OH) 3 ).

9 . The lithium extraction composite of claim 1 , wherein said lithium-selective sorbent material is a framework structure comprising LiX and M(OH) z units, wherein X is at least one anionic species selected from halide, nitrate, sulfate, carbonate, and bicarbonate; M is at least one oxophilic transition metal atom, and/or at least one oxophilic main group metal atom selected from aluminum, gallium, indium, silicon, germanium, and tin; and z is independently 2, 3, or 4, depending on the metal atom M; provided that, if M is exclusively aluminum, then the framework structure further includes M′(OH) z units, either in the same framework structure comprising LiX and M(OH) Z units or in a separate framework structure comprising LiX and M′(OH) Z units, wherein M′ is at least one oxophilic transition metal atom and/or at least one oxophilic main group metal atom selected from gallium, indium, silicon, germanium, and tin.

10 . The lithium extraction composite of claim 9 , wherein said at least one anionic species X is selected from halide atoms.

11 . The lithium extraction composite of claim 9 , wherein said composition is represented by the following chemical formula:
LiX:M1 x-y M2 y (OH) 3 .n H 2 O  (1)

wherein X is at least one anionic species selected from halide, nitrate, sulfate, carbonate, and bicarbonate; M1 is at least one oxophilic main group metal atom selected from aluminum, gallium, and indium; and M2 is at least one oxophilic transition metal atom, and/or at least one oxophilic main group metal atom selected from aluminum, gallium, indium, silicon, germanium, and tin, provided that M1 and M2 are different; x is at least 1 and up to 1.5; y is at least 0.1× and less than x; n is ≤4, and the species Li, X, M1, and M2 in Formula (1) are within a framework structure.

12 . A method of extracting and recovering a lithium salt from an aqueous source solution containing said lithium salt, the method comprising:
(a) providing a lithium extraction composite comprising (i) a porous support and (ii) particles of a lithium-selective sorbent material coated on at least one surface of the support, wherein said support has a planar membrane, porous fiber, or tubular shape; (b) flowing the aqueous source solution through a first zone or over a first surface of the lithium extraction composite to result in selective lithium intercalation in the lithium-selective sorbent material in the first zone or first surface; and (c) simultaneously recovering lithium salt extracted in step (b) from said lithium-selective sorbent material by flowing an aqueous stripping solution through a second zone or over a second surface of the lithium extraction composite in which lithium ions from the first zone or first surface diffuse, wherein said aqueous stripping solution contains the lithium salt in a concentration of no more than 50% of the concentration of the lithium salt in the aqueous source solution containing the lithium salt.

13 . The method of claim 12 , wherein said lithium extraction composite is in the shape of a membrane having a first surface and a second surface, and wherein the method comprises:
establishing a first flow containing the aqueous source solution over the first surface; establishing a second flow containing the aqueous stripping solution over the second surface; and recovering lithium from the stripping solution.

14 . The method of claim 13 , wherein the first flow occurs simultaneously with and is co-current with the second flow.

15 . The method of claim 13 , wherein the first flow occurs simultaneously with and is countercurrent to the second flow.

16 . The method of claim 13 , wherein the first flow is applied at a lower hydrostatic pressure than the second flow.

17 . The method of claim 12 , wherein said support is a polymer that has a melting point of at least 80° C.

18 . The method of claim 12 , wherein said support is a polymer that has a melting point of at least 100° C.

19 . The method of claim 17 , wherein said polymer is selected from the group consisting of polyimide, polyether ether ketone (PEEK), polybenzimidazole, ionomers, polysiloxanes, vinyl-addition polymers, polyurethanes, polyesters, polycarbonates, polyamides, polyethyleneimine (PEI), and copolymers, mixtures, and composites thereof.

20 . The method of claim 12 , wherein said support has an inorganic composition.

21 . The method of claim 20 , wherein said inorganic support has a metal oxide, metal carbide, metal nitride, or metal boride composition.

22 . The method of claim 20 , wherein said inorganic support has an elemental carbon composition.

23 . The method of claim 12 , wherein said lithium-selective sorbent material is selected from spinel-type lithium manganese oxides (LMOs), spinel-type lithium titanium oxides (LTOs), and lithium aluminum layered double hydroxide chloride (LiCl.2Al(OH) 3 ).

24 . The method of claim 12 , wherein said lithium-selective sorbent material is a framework structure comprising LiX and M(OH), units, wherein X is at least one anionic species selected from halide, nitrate, sulfate, carbonate, and bicarbonate; M is at least one oxophilic transition metal atom, and/or at least one oxophilic main group metal atom selected from aluminum, gallium, indium, silicon, germanium, and tin; and z is independently 2, 3, or 4, depending on the metal atom M; provided that, if M is exclusively aluminum, then the framework structure further includes M′(OH) z units, either in the same framework structure comprising LiX and M(OH) z units or in a separate framework structure comprising LiX and M′(OH) z units, wherein M′ is at least one oxophilic transition metal atom and/or at least one oxophilic main group metal atom selected from gallium, indium, silicon, germanium, and tin.

25 . The method of claim 24

Assignees

• Ut Battelle Llc
• All American Lithium LLC

Inventors

• Bhave Ramesh R
• Harrison Stephen
• Moyer Bruce A
• Paranthaman M Parans

Classifications

• C02F1/281

  using inorganic sorbents · CPC title

• C02F1/44

  by dialysis, osmosis or reverse osmosis {(general membrane separation processes B01D61/00, membrane modules B01D63/00, electrodialysis C02F1/4693, combination of membrane modules and bioreactors C02F3/1268)} · CPC title

• B01D69/08

  Hollow fibre membranes (manufacture of hollow fibres D01D5/24, D01F1/08) · CPC title

• B01D71/025

  Aluminium oxide · CPC title

• B01D71/34

  Polyvinylidene fluoride · CPC title