# US 11,993,827 B2 · Methods and compositions for recovery of lithium from liquid solutions with nanoparticles > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,993,827 B2 - Document ID: US11993827B2 - Status: Granted - Kind: B2 - Application number: 17/257,811 - Filed: 2019-07-05 - Published: 2021-05-13 - Granted: 2024-05-28 - Earliest claimed: 2018-07-06 - Applicants: Moselle Technologies, LLC - Inventors: Robert L. Albright; Stanley M. Meyer - Web page: https://patentgrep.com/patent/US11993827B2 ## CPC - C22B 26/12: Obtaining lithium - B01J 20/28009: {Magnetic properties} - B01J 20/28069: {Pore volume, e.g. total pore volume, mesopore volume, micropore volume} - B01J 20/3204: {Inorganic carriers, supports or substrates} - B01J 20/3225: {involving a post-treatment of the coated or impregnated product} - B01J 20/3248: {the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such} - B01J 20/327: {Polymers obtained by reactions involving only carbon to carbon unsaturated bonds} - B01J 20/3293: {Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers} - B22F 1/05: Metallic powder characterised by the size or surface area of the particles - B22F 1/102: Metallic powder coated with organic material - C22B 3/22: by physical processes, e.g. by filtration, by magnetic means {, or by thermal decomposition} (treatment or purification of solutions by liquid-liquid extraction C22B3/26) - C22B 3/24: by adsorption on solid substances, e.g. by extraction with solid resins - B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites - B82Y 40/00: Manufacture or treatment of nanostructures - Y02P 10/20: Recycling - C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract The present disclosure relates, according to some embodiments, to a method for recovery of lithium ions from a lithium-ion containing liquid, the method comprising the steps of coating a nanoparticle with a styrene monomer; polymerizing the styrene monomer to form a poly-styrene-coated nanoparticle; attaching a dibenzo-12-crown-4-ether to the polystyrene-coated nanoparticle to form a lithium adsorbing medium; exposing the lithium ion-containing liquid to the lithium adsorbing medium to form a lithium-rich adsorbing medium; and extracting the lithium ion from the lithium-rich adsorbing medium. ## Claims ### Claim 1 A method for recovery of lithium ions from a lithium-ion containing liquid, the method comprising: coating a nanoparticle with a styrene monomer; polymerizing the styrene monomer to form a polystyrene-coated nanoparticle; attaching a crown ether to the polystyrene-coated nanoparticle to form a lithium adsorbing medium; exposing the lithium-ion containing liquid to the lithium adsorbing medium to form a lithium-rich adsorbing medium and a lithium-depleted liquid; and extracting the lithium ion from the lithium-rich adsorbing medium to form an extracted lithium ion and a recycled lithium-adsorbing medium; wherein the nanoparticle includes a ferrous material. ### Claim 2 (depends on 1) The method of claim 1, wherein the nanoparticle has a surface area from about 10 square meters per gram to about 5,000 square meters per gram. ### Claim 3 (depends on 1) The method of claim 1, wherein the nanoparticle has a surface area from about 100 square meters per gram to about 500 square meters per gram. ### Claim 4 (depends on 1) The method of claim 1, further comprising magnetically separating the lithium-rich adsorbing medium from the lithium-depleted liquid. ### Claim 5 (depends on 1) The method of claim 1, wherein the nanoparticle includes a non-magnetic iron. ### Claim 6 (depends on 1) The method of claim 1, wherein extracting the lithium ion from the lithium-rich adsorbing medium includes treating the lithium-rich adsorbing medium with a weak acid. ### Claim 7 (depends on 6) The method of claim 6, wherein the weak acid includes at least one of carbonic acid, acetic acid, phosphoric acid, hydrofluoric acid, oxalic acid, and combinations thereof. ### Claim 8 (depends on 1) The method of claim 1, further comprising separating the extracted lithium ion from the recycled lithium-adsorbing medium. ### Claim 9 (depends on 8) The method according to claim 8, further comprising precipitating the extracted lithium ion to form a precipitated lithium salt, wherein the precipitated lithium salt includes at least one of lithium carbonate, lithium silicate, lithium oxalate, and combinations thereof. ### Claim 10 (depends on 9) The method of claim 9, further comprising drying the precipitated lithium salt to form a dried lithium salt. ### Claim 11 (depends on 10) The method of claim 10, wherein the crown ether includes dibenzo-12-crown-4-ether. ### Claim 12 (depends on 1) The method according to claim 1, wherein the crown ether includes at least one of dibenzo-12-crown-4-ether, diaza-12-crown-4 ether, dibenzo-15-crown-5 ether, diaza-15-crown-5 ether, dibenzo-18-crown-6 ether, and diaza-18-crown-6 ether. ### Claim 13 (depends on 1) The method of claim 1, further comprising separating the lithium-rich adsorbing medium from the lithium-depleted liquid by centrifugation. ### Claim 14 (depends on 1) The method of claim 1, wherein the polystyrene-coated nanoparticle is stable such that exposing the polystyrene-coated nanoparticle to an acidic condition does not degrade the polystyrene-coated nanoparticle. ### Claim 15 (depends on 1) The method of claim 1, wherein the extracting includes exposing the lithium-rich adsorbing medium to a water containing a carbon dioxide. ### Claim 16 (depends on 1) The method of claim 1, wherein the coating includes adding the nanoparticle to a solution containing the styrene monomer. ### Claim 17 (depends on 1) The method of claim 1, wherein: the polymerizing includes adding a free radical initiator to the styrene monomer, and the free radical initiator includes at least one of benzoyl peroxide, di-tert-butyl peroxide, a methyl radical source, a benzoyloxyl radical, methyl ethyl ketone peroxide, acetone peroxide, a peroxydisulfate salt, halogen peroxide, an azo compound such as azobisisobutyronitrile, and combinations thereof. ### Claim 18 A lithium adsorbing medium for recovering lithium ions from a lithium-ion containing liquid, the lithium adsorbing medium comprising: a nanoparticle including a ferrous material; a polystyrene coating a surface of the nanoparticle; and a crown ether attached to the polystyrene. ### Claim 19 (depends on 18) The lithium adsorbing medium of claim 18, wherein the ferrous material includes at least one of a magnetic iron, a non-magnetic iron, and combinations thereof. ### Claim 20 (depends on 18) The lithium adsorbing medium of claim 18, wherein the crown ether includes at least one of dibenzo-12-crown-4-ether, diaza-12-crown-4 ether, dibenzo-15-crown-5 ether, diaza-15-crown-5 ether, dibenzo-18-crown-6 ether, and diaza-18-crown-6 ether. ### Claim 21 (depends on 20) The lithium adsorbing medium of claim 20, wherein the crown ether includes dibenzo-12-crown-4-ether. ### Claim 22 (depends on 21) The lithium adsorbing medium of claim 21, further comprising a lithium ion attached to the dibenzo-12-crown-4-ether. ### Claim 23 (depends on 18) The lithium adsorbing medium of claim 18, wherein greater than about 75% of a surface of the nanoparticle is coated with polystyrene. ### Claim 24 (depends on 18) The lithium adsorbing medium of claim 18, wherein greater than about 95% of a surface of the nanoparticle is coated with the polystyrene. ### Claim 25 A method for recovery of lithium ions from a lithium-ion containing liquid, the method comprising: coating a nanoparticle with a styrene monomer; polymerizing the styrene monomer to form a polystyrene-coated nanoparticle; attaching a crown ether to the polystyrene-coated nanoparticle to form a lithium adsorbing medium; exposing the lithium-ion containing liquid to the lithium adsorbing medium to form a lithium-rich adsorbing medium and a lithium-depleted liquid; and extracting the lithium ion from the lithium-rich adsorbing medium to form an extracted lithium ion and a recycled lithium-adsorbing medium; wherein the nanoparticle includes a non-magnetic iron. ### Claim 26 A method for recovery of lithium ions from a lithium-ion containing liquid, the method comprising: coating a nanoparticle with a styrene monomer; polymerizing the styrene monomer to form a polystyrene-coated nanoparticle; attaching a crown ether to the polystyrene-coated nanoparticle to form a lithium adsorbing medium; exposing the lithium-ion containing liquid to the lithium adsorbing medium to form a lithium-rich adsorbing medium and a lithium-depleted liquid; and extracting the lithium ion from the lithium-rich adsorbing medium to form an extracted lithium ion and a recycled lithium-adsorbing medium; wherein extracting the lithium ion from the lithium-rich adsorbing medium includes treating the lithium-rich adsorbing medium with a weak acid. ### Claim 27 A method for recovery of lithium ions from a lithium-ion containing liquid, the method comprising: coating a nanoparticle with a styrene monomer; polymerizing the styrene monomer to form a polystyrene-coated nanoparticle; attaching a crown ether to the polystyrene-coated nanoparticle to form a lithium adsorbing medium; exposing the lithium-ion containing liquid to the lithium adsorbing medium to form a lithium-rich adsorbing medium and a lithium-depleted liquid; extracting the lithium ion from the lithium-rich adsorbing medium to form an extracted lithium ion and a recycled lithium-adsorbing medium; and separating the extracted lithium ion from the recycled lithium-adsorbing medium. ### Claim 28 (depends on 27) The method according to claim 27, further comprising precipitating the extracted lithium ion to form a precipitated lithium salt, wherein the precipitated lithium salt includes at least one of lithium carbonate, lithium silicate, lithium oxalate, and combinations thereof. ### Claim 29 (depends on 28) The method of claim 28, further comprising drying the precipitated lithium salt to form a dried lithium salt. ### Claim 30 (depends on 29) The method of claim 29, wherein the crown ether includes dibenzo-12-crown-4-ether. ### Claim 31 A method for recovery of lithium ions from a lithium-ion containing liquid, the method comprising: coating a nanoparticle with a styrene monomer; polymerizing the styrene monomer to form a polystyrene-coated nanoparticle; attaching a crown ether to the polystyrene-coated nanoparticle to form a lithium adsorbing medium; exposing the lithium-ion containing liquid to the lithium adsorbing medium to form a lithium-rich adsorbing medium and a lithium-depleted liquid; and extracting the lithium ion from the lithium-rich adsorbing medium to form an extracted lithium ion and a recycled lithium-adsorbing medium; wherein the extracting includes exposing the lithium-rich adsorbing medium to a water containing a carbon dioxide. ### Claim 32 A method for recovery of lithium ions from a lithium-ion containing liquid, the method comprising: coating a nanoparticle with a styrene monomer; polymerizing the styrene monomer to form a polystyrene-coated nanoparticle; attaching a crown ether to the polystyrene-coated nanoparticle to form a lithium adsorbing medium; exposing the lithium-ion containing liquid to the lithium adsorbing medium to form a lithium-rich adsorbing medium and a lithium-depleted liquid; and extracting the lithium ion from the lithium-rich adsorbing medium to form an extracted lithium ion and a recycled lithium-adsorbing medium; wherein the polymerizing includes adding a free radical initiator to the styrene monomer; and wherein the free radical initiator includes at least one of benzoyl peroxide, di-tert-butyl peroxide, a methyl radical source, a benzoyloxyl radical, methyl ethyl ketone peroxide, acetone peroxide, a peroxydisulfate salt, halogen peroxide, an azo compound such as azobisisobutyronitrile, and combinations thereof.