Lithium extraction with coated ion exchange particles

Abstract

The present invention relates to the extraction of lithium from liquid resources such as natural and synthetic brines, leachate solutions from minerals, and recycled products.

1 - 42 . (canceled) 
     
     
         43 . A porous structure comprising:
 a) ion exchange particles, wherein the ion exchange particles comprise an ion exchange material; and   b) a structural support;   wherein the ion exchange particles are embedded in, adhered to, or otherwise supported by the structural support to form the porous structure;   wherein the ion exchange material comprises an oxide, the oxide comprising Li 4 Mn 5 O 12 , Li 4 Ti 5 O 12 , Li 2 TiO 3 , Li 2 MnO 3 , Li 2 SnO 3 , LiMn 2 O 4 , Li 1.6 Mn 1.6 O 4 , LiAlO 2 , LiCuO 2 , LiTiO 2 , Li 4 TiO 4 , Li 7 Ti 11 O 24 , Li 3 VO 4 , Li 2 Si 3 O 7 , SnO 2 —xSb 2 O 5 —yH 2 O, TiO 2 —xSb 2 O 5 —yH 2 O, solid solutions thereof, or combinations thereof, wherein x is from 0.1-10; and y is from 0.1-10;   wherein the structural support comprises a polymer, an oxide, a phosphate, or combinations thereof, and   wherein the porous structure comprises pores with diameters ranging from more than 1 μm to less than 100 μm.   
     
     
         44 . The porous structure of  claim 43 , wherein the structural support comprises a polymer. 
     
     
         45 . The porous structure of  claim 43 , wherein the mass ratio of the structural support to the ion exchange particles is from 5:1 to 1:20. 
     
     
         46 . The porous structure of  claim 43 , wherein the structural support comprises polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, a chloro-polymer, a fluoro-polymer, a fluoro-chloro-polymer, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, a sulfonated polymer, a carboxylated polymer, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (Nafion®), copolymers thereof, or combinations thereof. 
     
     
         47 . The porous structure of  claim 43 , wherein the structural support comprises polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, sulfonated polytetrafluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, polyacrylonitrile, perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (Nafion®), copolymers thereof, or combinations thereof. 
     
     
         48 . The porous structure of  claim 43 , wherein the structural support comprises polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, copolymers thereof, or combinations thereof. 
     
     
         49 . The porous structure of  claim 43 , wherein the structural support comprises an oxide. 
     
     
         50 . The porous structure of  claim 49 , wherein the oxide is selected from titanium dioxide, zirconium dioxide, silicon dioxide, solution solutions thereof, or combinations thereof. 
     
     
         51 . The porous structure of  claim 43 , wherein the ion exchange material comprises Li 2 SnO 3 , Li 2 MnO 3 , Li 2 TiO 3 , Li 4 Ti 5 O 12 , Li 4 Mn 5 O 12 , Li 1.6 Mn 1.6 O 4 , solid solutions thereof, or combinations thereof. 
     
     
         52 . The porous structure of  claim 43 , wherein the ion exchange material comprises Li 4 Mn 5 O 12 , Li 2 MnO 3 , LiMn 2 O 4 , Li 1.6 Mn 1.6 O 4 , solid solutions thereof, or combinations thereof. 
     
     
         53 . The porous structure of  claim 43 , wherein the ion exchange material comprises Li 4 Ti 5 O 12 , Li 2 TiO 3 , LiTiO 2 , Li 4 TiO 4 , Li 7 Ti 11 O 24 , solid solutions thereof, or combinations thereof. 
     
     
         54 . The porous structure of  claim 43 , wherein the ion exchange particles are coated ion exchange particles, wherein the coated ion exchange particles comprise the ion exchange material and a coating material, and wherein the coating material comprises i) an oxide different from the oxide of the ion exchange material, ii) a polymer, or iii) any combinations thereof. 
     
     
         55 . The porous structure of  claim 54 , wherein the coating material comprises TiO 2 , ZrO 2 , MoO 2 , SnO 2 , Nb 2 O 5 , Ta 2 O 5 , Li 2 TiO 3 , SiO 2 , Li 2 ZrO 3 , Li 2 MoO 3 , LiNbO 3 , LiTaO 3 , ZrSiO 4 , solid solutions thereof, or combinations thereof. 
     
     
         56 . The porous structure of  claim 54 , wherein the coating material comprises TiO 2 , ZrO 2 , SiO 2 , solid solutions thereof, or combinations thereof. 
     
     
         57 . The porous structure of  claim 54 , wherein the coating material comprises a polymer. 
     
     
         58 . The porous structure of  claim 54 , wherein the coating material comprises polyvinylidene difluoride, polyvinyl chloride, a fluoro-polymer, a chloro-polymer, a fluoro-chloro-polymer, or combinations thereof. 
     
     
         59 . The porous structure of  claim 54 , wherein the coating material comprises polyvinylidene difluoride, polyvinyl chloride, or combinations thereof. 
     
     
         60 . The porous structure of  claim 54 , wherein the ion exchange material comprises Li 2 SnO 3 , Li 2 MnO 3 , Li 2 TiO 3 , Li 4 Ti 5 O 12 , Li 4 Mn 5 O 12 , Li 1.6 Mn 1.6 O 4 , solid solutions thereof, or combinations thereof. 
     
     
         61 . The porous structure of  claim 54 , wherein the ion exchange material comprises Li 4 Mn 5 O 12 , Li 2 MnO 3 , LiMn 2 O 4 , Li 1.6 Mn 1.6 O 4 , solid solutions thereof, or combinations thereof. 
     
     
         62 . The porous structure of  claim 54 , wherein the ion exchange material comprises Li 4 Ti 5 O 12 , Li 2 TiO 3 , LiTiO 2 , Li 4 TiO 4 , Li 7 Ti 11 O 24 , solid solutions thereof, or combinations thereof. 
     
     
         63 . The porous structure of  claim 43 , wherein the porous structure forms a porous membrane, a porous bead, a dense membrane, a dense bead, a scaffold, a woven membrane, a wound membrane, a spiral wound membrane, or combinations thereof. 
     
     
         64 . The porous structure of  claim 43 , wherein the porous structure forms a porous membrane, a porous bead, or combinations thereof. 
     
     
         65 . A method of extracting lithium from a liquid resource, comprising:
 a) contacting a coated ion exchange particle with the liquid resource to produce a lithiated coated ion exchange particle, wherein the coated ion exchange particle comprises an uncoated ion exchange particle and a coating material; and   b) treating the lithiated coated ion exchange particle with an acid solution to produce a salt solution comprising lithium ions;   wherein the uncoated ion exchange particle comprises an ion exchange material that comprises an oxide,   wherein the oxide further comprises:
 (i) lithium, and 
 (ii) manganese or titanium; 
   wherein the coating material comprises an oxide different from the oxide of the ion exchange material, a polymer, or combinations thereof; and   wherein the uncoated ion exchange particle has a diameter that is more than about 100 nm and that is less than about 100 μm.