# US 12,599,893 B2 · Spherical lithium adsorbent as well as preparation method and use thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,599,893 B2 - Document ID: US12599893B2 - Status: Granted - Kind: B2 - Application number: 18/846,285 - Filed: 2022-11-04 - Published: 2025-04-03 - Granted: 2026-04-14 - Earliest claimed: 2022-11-04 - Assignees: Qinghai Institute of Salt Lakes, Chinese Academy of Sciences - Applicants: Qinghai Institute of Salt Lakes, Chinese Academy of Sciences - Inventors: Min Wang; Xiaofei Lv; Huaiyou Wang - Web page: https://patentgrep.com/patent/US12599893B2 ## CPC - B01J 20/3064: {Addition of pore forming agents, e.g. pore inducing or porogenic agents} - B01J 20/04: comprising compounds of alkali metals, alkaline earth metals or magnesium - B01J 20/041: {Oxides or hydroxides} - B01J 20/06: comprising oxides or hydroxides of metals not provided for in group B01J20/04 - B01J 20/08: comprising aluminium oxide or hydroxide; comprising bauxite - B01J 20/20: comprising free carbon; comprising carbon obtained by carbonising processes - B01J 20/28004: {Sorbent size or size distribution, e.g. particle size} - B01J 20/28019: {Spherical, ellipsoidal or cylindrical} - B01J 20/30: Processes for preparing, regenerating, or reactivating - B01J 20/3028: {Granulating, agglomerating or aggregating} - B01J 20/3042: {Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent} - B01J 20/3071: {Washing or leaching} - B01J 20/3078: {Thermal treatment, e.g. calcining or pyrolizing} - B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078} - B01J 20/3236: {containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts} - B05D 1/02: performed by spraying - C01D 15/00: Lithium compounds - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) - C01D: COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides C01B17/22; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia and cyanogen, containing nitrogen and other non-metals C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; phosphides C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20) ## Abstract A spherical lithium adsorbent, as well as a preparation method and use thereof are provided. The preparation method includes: dry mixing an adsorbent and a forming agent followed by evenly mixing with a first solvent to form a mixed solution, and adding a thickening and pore forming agent to obtain a mixed system; spraying out the mixed system from a nozzle of a spray device and receiving sprayed drips using a second solvent that is incompatible with the forming agent as a receiving solvent so that the drips become particles to obtain a spherical adsorbent with good performance and even granularity. Spray granulation is performed utilizing airflow so that the particles have a larger specific area and are more suitable for industrial absorption column filling. Furthermore, adsorbent powders in the particles are tightly wrapped and difficult to fall off during cyclic use. ## Claims ### Claim 1 A preparation method of a spherical lithium adsorbent, comprising: dry mixing an adsorbent and a forming agent followed by evenly mixing with a first solvent to form a mixed solution, and adding a thickening and pore forming agent to obtain a mixed system; and spraying out the mixed system from a nozzle of a spray device and receiving sprayed drips using a second solvent as a receiving solvent so that a solid-phase spherical lithium adsorbent is obtained via a phase conversion, wherein a particle size of the spherical lithium adsorbent is in a range from 100 μm to 1000 μm, and wherein the adsorbent is one or more selected from the group consisting of a lithium titanium ion sieve, an aluminum based adsorbent, a lithium manganese ion sieve, graphite powders, and a graphene oxide; the forming agent is one or more selected from the group consisting of polyvinyl chloride, polyethersulfone, polyvinyl acetate, polyformaldehyde, polyamide, polysulfone, and polyimide; and the thickening and pore forming agent is one or more selected from the group consisting of hydroxyethyl cellulose, carboxymethyl cellulose, polyethylene glycol, and sodium alginate. ### Claim 2 (depends on 1) The preparation method according to claim 1, wherein the aluminum based adsorbent is one or more selected from the group consisting of LiCl·2Al(OH)3·nH2O and LiAl2(OH)6Cl·nH2O; and/or a weight ratio of the adsorbent to the forming agent is 1:1-9:1. ### Claim 3 (depends on 1) The preparation method according to claim 1, wherein the first solvent comprises a combination of any one or more than two of N-methylpyrrolidone, N,N-dimethylformamide, N, N-dimethylacetamide, and tetrahydrofuran; and/or, the forming agent accounts for 6%-40% by a weight of the first solvent. ### Claim 4 (depends on 1) The preparation method according to claim 1, comprising: dissolving the thickening and pore forming agent into a third solvent and then adding an obtained mixture into the mixed solution, stirring and ultrasonically treating to obtain the mixed system; and/or, a mass ratio of the thickening and pore forming agent to the forming agent being 6:100-1:3. ### Claim 5 (depends on 4) The preparation method according to claim 4, wherein the third solvent comprises a combination of any one or more than two of ethanol, cyclohexanol and isopropanol; and/or, the thickening and pore forming agent accounts for 3%-10% by a weight of dry mixed powders; and/or, the thickening and pore forming agent accounts for 10%-80% by a weight of the third solvent. ### Claim 6 (depends on 1) The preparation method according to claim 1, wherein the second solvent comprises a combination of any one or two of alcohol and water; wherein the alcohol comprises a combination of any one or more than two of methanol, n-propanol, isopropanol, and ethanol, and the water is deionized water; and wherein a volume ratio of the alcohol to the water is 30:70-90:10. ### Claim 7 (depends on 1) The preparation method according to claim 1, comprising: extracting the mixed system using an extraction device to be input into a first inlet of the spray device, and introducing a gas into a second inlet; and spraying out the mixed system via the nozzle of the spray device, allowing the sprayed drips to fall in the second solvent based on the second solvent as the receiving solvent, so as to obtain the solid-phase spherical lithium adsorbent via the phase conversion. ### Claim 8 (depends on 7) The preparation method according to claim 7, wherein a ratio of a liquid extraction speed of the extraction device to an airflow speed of the gas is 1:2-5:1; and/or, the gas comprises a combination of any one or more than two of air, carbon dioxide, nitrogen, and argon. ### Claim 9 A spherical lithium adsorbent, wherein a particle size of the spherical lithium adsorbent is in a range from 100 μm to 1000 μm, and wherein a preparation method of the spherical lithium adsorbent comprises: dry mixing an adsorbent and a forming agent followed by evenly mixing with a first solvent to form a mixed solution, and adding a thickening and pore forming agent to obtain a mixed system; extracting the mixed system using an extraction device to be input into a first inlet of the spray device, and introducing a gas into a second inlet; and spraying out the mixed system from a nozzle of a spray device and receiving sprayed drips using a second solvent as a receiving solvent so that a solid-phase spherical lithium adsorbent is obtained via a phase conversion; wherein the adsorbent is one or more selected from the group consisting of a lithium titanium ion sieve, an aluminum based adsorbent, a lithium manganese ion sieve, graphite powders, and a graphene oxide; the forming agent is one or more selected from the group consisting of polyvinyl chloride, polyethersulfone, polyvinyl acetate, polyformaldehyde, polyamide, polysulfone, and polyimide; and the thickening and pore forming agent is one or more selected from the group consisting of hydroxyethyl cellulose, carboxymethyl cellulose, polyethylene glycol, and sodium alginate. ### Claim 10 (depends on 9) Use of the spherical lithium adsorbent according to claim 9 in a field of an absorption column filling. ### Claim 11 (depends on 9) The spherical lithium adsorbent according to claim 9, wherein the aluminum based adsorbent is one or more selected from the group consisting of LiCl·2Al(OH)3·nH2O and LiAl2(OH)6Cl·nH2O; and a weight ratio of the adsorbent to the forming agent is 1:1-9:1. ### Claim 12 (depends on 9) The spherical lithium adsorbent according to claim 9, wherein in the preparation method, the first solvent comprises a combination of any one or more than two of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and tetrahydrofuran; and/or, the forming agent accounts for 6%-40% by a weight of the first solvent. ### Claim 13 (depends on 9) The spherical lithium adsorbent according to claim 9, wherein the preparation method comprises: dissolving the thickening and pore forming agent into a third solvent and then adding an obtained mixture into the mixed solution, stirring and ultrasonically treating to obtain the mixed system; and, a mass ratio of the thickening and pore forming agent to the forming agent being 6:100-1:3. ### Claim 14 (depends on 13) The spherical lithium adsorbent according to claim 13, wherein in the preparation method, the third solvent comprises a combination of any one or more than two of ethanol, cyclohexanol and isopropanol; and/or, the thickening and pore forming agent accounts for 3%-10% by a weight of dry mixed powders; and/or, the thickening and pore forming agent accounts for 10%-80% by a weight of the third solvent. ### Claim 15 (depends on 9) The spherical lithium adsorbent according to claim 9, wherein in the preparation method, the second solvent comprises a combination of any one or two of alcohol and water; wherein the alcohol comprises a combination of any one or more than two of methanol, n-propanol, isopropanol, and ethanol, and the water is deionized water; and wherein a volume ratio of the alcohol to the water is 30:70-90:10. ### Claim 16 (depends on 1) The spherical lithium adsorbent according to claim 1, wherein in the preparation method, a ratio of a liquid extraction speed of the extraction device to an airflow speed of the gas is 1:2-5:1; and the gas comprises a combination of any one or more than two of air, carbon dioxide, nitrogen, and argon.