CN110975795A - Synthesis method of lithium extraction adsorbent - Google Patents
Synthesis method of lithium extraction adsorbent Download PDFInfo
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- CN110975795A CN110975795A CN201911323242.3A CN201911323242A CN110975795A CN 110975795 A CN110975795 A CN 110975795A CN 201911323242 A CN201911323242 A CN 201911323242A CN 110975795 A CN110975795 A CN 110975795A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- 239000003463 adsorbent Substances 0.000 title claims abstract description 35
- 238000001308 synthesis method Methods 0.000 title claims abstract description 23
- 238000000605 extraction Methods 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910003890 H2TiO3 Inorganic materials 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 235000010338 boric acid Nutrition 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- AXMOZGKEVIBBCF-UHFFFAOYSA-M lithium;propanoate Chemical compound [Li+].CCC([O-])=O AXMOZGKEVIBBCF-UHFFFAOYSA-M 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Polymers [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 229910010252 TiO3 Inorganic materials 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 12
- 239000012267 brine Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000010828 elution Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000013535 sea water Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000010532 solid phase synthesis reaction Methods 0.000 description 6
- 238000005554 pickling Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910007052 Li—Ti—O Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- NYAVNTYRFWSLQL-UHFFFAOYSA-N lithium oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[Ti+4] NYAVNTYRFWSLQL-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- Environmental & Geological Engineering (AREA)
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- Metallurgy (AREA)
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- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a synthesis method of a lithium extraction adsorbent, which comprises the steps of dissolving a lithium source in a solvent containing a certain amount of additives, adding a titanium source into the solvent to uniformly mix the lithium source and the solvent to form a solid-liquid mixed state, performing drying treatment to assist synthesis, drying the raw materials quickly, mixing the raw materials fully, and calcining the raw materials to obtain a lithium ion sieve precursor Li with uniformly distributed particle sizes2TiO3(ii) a Precursor Li2TiO3Metatitanic acid type lithium ion sieve H obtained after acid elution of lithium2TiO3Has obvious adsorption effect. The invention is simple and easy to implement, and the lithium ion sieve H2TiO3The method is mainly used for extracting lithium from water bodies such as salt lake brine, oil field brine, seawater and the like, and has great potential in the aspect of liquid lithium extraction.
Description
Technical Field
The invention relates to the technical field of adsorption materials, and particularly relates to a synthesis method of a lithium extraction adsorbent.
Background
Lithium is closely related to human life, and lithium is an alkali metal with the smallest atomic radius and is also the lightest metal known at present. It is known as an energy material and strategic resource and has a wide range of applications in many areas like glass, ceramics, pharmaceuticals, aerospace vehicles, nuclear industry and the best known lithium battery industry. Especially, in recent years, the demand for lithium resources has been increasing.
The total amount of lithium resources in China is the fourth world and accounts for about 13.21% of the total amount of lithium stored in the world. However, over 79% of the lithium resources in China exist in salt lake brine and oil field underground brine in a liquid state. The ore lithium resource is gradually reduced along with the exploitation, and the demand of lithium at present and in the future is far from being met. Therefore, one focuses on the extraction of lithium resources from liquids. However, the content of magnesium in the salt lake brine in China is high, when the ratio of magnesium to lithium reaches 20, lithium is defined as difficult to extract, and the ratio of magnesium to lithium in some salt lakes in China is even as high as 500.
There are many methods for extracting lithium from liquids, such as evaporative crystallization, coprecipitation, solvent extraction, etc. The evaporation crystallization and the coprecipitation are only suitable for low lithium-magnesium ratio, and a large amount of organic solvent is needed for solvent extraction, so that the method not only causes harm to the environment, but also has an erosion effect on equipment, and is difficult to industrialize. The ion exchange adsorption has the advantages of high selectivity, economy, environmental protection, regeneration and cyclic utilization and the like, and has wide prospect in the aspect of liquid lithium extraction.
The lithium ion sieve type adsorbent mainly comprises manganese system and titanium system. Manganese-based lithium ion sieves were the earliest studied and are the most studied lithium ion adsorbents, but the dissolution loss of manganese makes them difficult to recycle. The metatitanic acid type lithium ion sieve adsorbent has more researches in recent years due to the advantages of stable structure, large theoretical adsorption capacity and the like. However, they are relatively late to study and are currently still under the exploratory stage of synthesis.
The metatitanic acid type lithium ion sieve may be prepared by hydrothermal synthesis, sol-gel method, solid phase method, etc. Wherein, the hydrothermal synthesis method has complex synthesis and high cost and is difficult to realize industrialization. The sol-gel method is influenced by more preparation parameters, has low repetition rate, and has the problems of long synthesis period, high cost and the like. Compared with the high-temperature solid-phase method, the method has obvious advantages, and the synthesis process is simple and easy to industrialize. In patent CN101944600A, a lithium source and a titanium source are mixed by ball milling, and then a lithium ion sieve precursor Li is prepared by adopting a high-temperature solid-phase roasting method2TiO3The dissolution loss of the obtained lithium ion sieve is less than 1 percent, and the adsorption capacity is more than 14 mg/g; in the patent CN101157476A, self-made one-dimensional nano titanium dioxide is mixed with a lithium source and calcined to obtain a Li-Ti-O ternary oxide, and the Li-Ti-O ternary oxide is treated by an inorganic acid to obtain a titanium dioxide lithium ion sieve with better selectivity; yan Schwann et al uses rutile titanium dioxide as titanium source, and is synthesized by high-temp. solid-phase method, and its adsorption capacity is 29.15mg/g (Yan Schwann, Huangshihua. granular titanium dioxide exchanger development and lithium extraction from bittern]Ion exchange and adsorption, 1994, (3): 219-; respectively using TiO for face brightness and the like2With Li2CO3Lithium ion sieves were synthesized by solid phase reaction for lithium and titanium sources and found to have a concentration of 5g/L of Li in LiOH and LiCl configurations+Research on preparation of novel lithium adsorbent with adsorption capacity of 32.29mg/g in solution [ J]Inorganic salt industry, 2014, 46(2): 38). The solid phase method has the defects that the mass transfer of the solid phase reaction is difficult to control, the complete and uniform mixing is difficult to ensure, and the contact state of reactants and whether the reaction process is sufficient or not or the particle size range of the product is overlarge are influenced by the mixing mode, the calcination temperature, the calcination time and the like of the reactants.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a synthesis method of a lithium extraction adsorbent, which is characterized in that a lithium source is dissolved in a solvent containing a certain amount of additives, then a titanium source is added to form a solid-liquid mixed state, slurry is dried, and the obtained precursor powder is regular in calcined morphology and uniform in particle size, so that the problems that solid-phase reaction mass transfer is difficult to control and complete and uniform mixing is difficult to ensure in solid-phase synthesis can be effectively solved.
The technical scheme is as follows: the invention relates to a synthesis method of a lithium extraction adsorbent, which comprises the following steps: adding the additive A into the solvent B, adding the lithium source C into the solvent B, dissolving the lithium source C, and stirring the mixture according to the proportion of Li: the molar ratio of Ti elements is 1.6-2.8: 1 adding a titanium source D, mixing to form slurry, continuously stirring for 0.5-48 h, and then drying the slurry to obtain solid powder; calcining the obtained solid powder to prepare lithium ion sieve adsorbent precursor Li2TiO3Precursor Li2TiO3Acid washing and lithium removing are carried out for 0.15-72H at the temperature of 20-90 ℃ to obtain metatitanic acid type lithium ion sieve adsorbent H2TiO3。
Further, the additive A is one or a combination of more than two of sodium hexametaphosphate, polyethylene glycol, ethyl cellulose, terpineol, a silane coupling agent, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and polyacrylate.
Further, the mass content of the additive A is 0-20%.
Further, the solvent B is one or a combination of more than two of water, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, acetone, butanol, ethyl acetate, cyclohexane and n-octane.
Further, the lithium source C is one or the combination of more than two of lithium hydroxide, lithium sulfate, lithium chloride, lithium acetate, lithium propionate, lithium nitrate, lithium hydroxide monohydrate, lithium acetate dihydrate and lithium oxalate.
Further, the titanium source D is one or the combination of more than two of anatase type titanium dioxide, rutile type titanium dioxide and brookite type titanium dioxide; the liquid-solid ratio of the solvent B to the titanium source D is 10-200 mL/g.
Further, the drying treatment mode is spray drying, airflow drying, flash evaporation drying or vacuum conduction drying.
Further, in the calcining process, the temperature is raised to 550-950 ℃ at the temperature rise rate of 1-10 ℃/min, and the temperature is kept for 1-72 hours.
Further, the acid used for acid elution of lithium is one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, hypochlorous acid, malonic acid, formic acid, acetic acid, propionic acid, citric acid and boric acid.
Further, the concentration of acid in the acid-eluted lithium is 0.01-1 mol/L, and the using amount of the acid is 0.5-50 g/L.
Has the advantages that:
(1) the lithium source is dissolved into a solvent containing a certain amount of additive and is mixed with the titanium source to form slurry, so that the lithium source and the titanium source form a solid-liquid mixed state, and the phenomenon that solid particles are difficult to mix uniformly in a solid-phase synthesis method is effectively improved;
(2) the slurry is dried, so that the raw materials are quickly dried and uniformly mixed, the particle size of the lithium ion sieve precursor obtained by calcining the obtained solid powder is uniform, and the agglomeration phenomenon in the synthesis process is remarkably reduced; metatitanic acid type lithium ion sieve H obtained after acid elution of lithium2TiO3The adsorption capacity is large, the selectivity is high, and the structure is stable;
(3) metatitanic acid type lithium ion sieve H prepared by the invention2TiO3The preparation process is simple, the operation and control are easy, and the large-scale production is easy to realize.
Drawings
FIG. 1 shows the adsorbent precursor Li of metatitanic acid type lithium ion sieve prepared in example 12TiO3And lithium ion sieve adsorbent H2TiO3X-ray diffraction patterns of (a);
FIG. 2 shows the adsorbent precursor Li of metatitanic acid type lithium ion sieve prepared in example 12TiO3And lithium ion sieve adsorbent H2TiO3An FTIR spectrum of (a);
FIG. 3 shows the adsorbent precursor Li of metatitanic acid type lithium ion sieve prepared in example 12TiO3And lithium ion sieve adsorbent H2TiO3SEM image of (d).
Detailed Description
The invention is further described below with reference to the following figures and examples:
the instrument comprises the following steps: XRD: MiniFlex600 japan, scan range: 5-80 °, step size 0.02, scanning speed: 10 degrees/min, the scanning voltage is 40kV, and the current is 15 mA; FTIR: nicolet8700 nyoko corporation, usa; SEM: s4800, hitachi, japan; ICP-OES: optima 7000DV, Perkin-Elmer, USA.
Example 1
1. 6.1835g of lithium hydroxide monohydrate is dissolved in 100ml of aqueous solution containing 5 percent of hexadecyl trimethyl ammonium bromide, 4.0338g (the molar ratio of Li to Ti is 2.80:1) of anatase titanium dioxide is added into the aqueous solution under the stirring state, the stirring is continued for 24 hours, and the obtained slurry is subjected to spray drying under the stirring state at the feeding rate of 5ml/min and the spraying temperature of 120 ℃ to obtain solid powder;
2. heating the obtained solid powder to 700 ℃ at a speed of 5 ℃/min in a muffle furnace, and calcining for 72h to obtain a metatitanic acid type lithium ion sieve precursor Li2TiO3；
3. Mixing the precursor Li2TiO3Adding the powder into 0.3mol/L hydrochloric acid solution (solid-to-liquid ratio is 6g/L), magnetically stirring at 50 deg.C for 6H to remove lithium, filtering, washing, and drying to obtain metatitanic acid type lithium ion sieve adsorbent H2TiO3；
4. Adding the ionic sieve into a solution with the pH of 10 and the lithium concentration of 500mg/L, and magnetically stirring at 35 ℃ for 12 hours, wherein the adsorption capacity is 37 mg/g;
5. precursor Li2TiO3The XRD pattern of (A) is shown in figure 1, the FTIR pattern is shown in a in figure 2, and the SEM pattern is shown in a, b in figure 3; ion sieve H2TiO3The XRD pattern of (A) is shown in fig. 1 b, the FTIR pattern is shown in fig. 2 b, and the SEM pattern is shown in fig. 3 c, d. It can be seen from FIG. 1 that the crystal structure of the powder was changed slightly before and after the acid-washing for lithium removal, because the hydrogen ions were ion-exchanged with the lithium ions in the crystal, replacing the lithium ions in the crystal. From the precursor Li of FIG. 22TiO3And ion sieve H2TiO3The FTIR spectrum of (5) shows H after acid washing2TiO3At 3489cm-1Has a narrow peak of+/Li+Exchange-related OH stretching vibrations not involved in interactions with other oxygen-hydrogen groups, 3134cm-1And 1632cm-1Adsorbed water having a broad peak of hydrogen bondingStretching and bending vibration of the OH group. As can be seen from FIG. 3, Li before pickling2TiO3The surface of the pickling solution is rough after pickling, obvious pickling traces are formed, the appearance before pickling is still maintained, and the phenomenon of structural collapse is avoided.
Example 2
1. 8.2440g of lithium acetate dihydrate is dissolved in 80ml of absolute ethyl alcohol, 4.0338g of rutile type titanium dioxide (the molar ratio of Li to Ti is 1.60:1) is added into the anhydrous ethyl alcohol under the stirring state, the stirring is continued for 0.5h, and the obtained slurry is subjected to flash evaporation and drying under the stirring state at the feeding rate of 3ml/min and the air inlet temperature of 110 ℃ to obtain solid powder;
2. heating the obtained solid powder in a muffle furnace at 1 ℃/min to 550 ℃ to calcine for 12h to obtain a metatitanic acid type lithium ion sieve precursor Li2TiO3；
3. Mixing the precursor Li2TiO3Adding the powder into 0.01mol/L hydrochloric acid solution (solid-to-liquid ratio is 0.5g/L), magnetically stirring at 90 deg.C for 8H to remove lithium, filtering, washing, and drying to obtain metatitanic acid type lithium ion sieve adsorbent H2TiO3；
4. The ionic sieve was added to a solution of pH 11 and lithium concentration 1g/L, and the mixture was magnetically stirred at 55 ℃ for 12 hours, giving an adsorbed amount of 39 mg/g.
Example 3
1. 4.4794g of lithium chloride is dissolved in 800ml of aqueous solution containing 20 percent of polyvinylpyrrolidone, 4.0338g of rutile type titanium dioxide (the molar ratio of Li to Ti is 2.05:1) is added into the aqueous solution under the stirring state, the stirring is continued for 48 hours, and the obtained slurry is heated by steam under the stirring state at the feeding rate of 20ml/min, the vacuum degree of 60kPa and the shaft rotating speed of 10rpm for vacuum drying to obtain solid powder;
2. heating the obtained powder in a muffle furnace at 5 ℃/min to 800 ℃ for calcining for 9h to obtain a metatitanic acid type lithium ion sieve precursor Li2TiO3；
3. Mixing the precursor Li2TiO3Adding the powder into 1mol/L nitric acid solution (solid-to-liquid ratio is 50g/L), magnetically stirring at 45 deg.C for 0.15h to remove lithium, filtering, washing,drying to obtain metatitanic acid type lithium ion sieve adsorbent H2TiO3；
4. The ionic sieve is added into a solution with pH of 10 and lithium concentration of 200mg/L, and the solution is magnetically stirred for 12 hours at 35 ℃ and the adsorption capacity is 33 mg/g.
Example 4
1. 4.6030g of lithium chloride is dissolved in 40ml (70%) of ethylene glycol solution, 2.0169g of rutile type titanium dioxide and anatase type titanium dioxide (the molar ratio of Li to Ti is 2.15:1) are respectively added into the solution under the stirring state, the stirring is continued for 10 hours, and the obtained slurry is subjected to air flow drying under the stirring state at the feeding rate of 1ml/min and the air flow temperature of 120 ℃ to obtain solid powder;
2. heating the obtained solid powder to 950 ℃ at the speed of 10 ℃/min in a muffle furnace, and calcining for 1h to obtain a metatitanic acid type lithium ion sieve precursor Li2TiO3；
3. Mixing Li2TiO3Adding the powder into 0.05mol/L hydrochloric acid solution (solid-to-liquid ratio is 2g/L), magnetically stirring at 20 deg.C for 72H to remove lithium, filtering, washing, and drying to obtain metatitanic acid type lithium ion sieve adsorbent H2TiO3；
4. Weighing 1g of lithium ion sieve adsorbent H2TiO3Adding 1L of a solution containing Li+，Na+，K+,Ca2+，Mg2+The adsorption results of the lithium ion sieve on each metal ion are shown in Table 1, wherein the lithium ion sieve is magnetically stirred for 24 hours at the temperature of 35 ℃.
TABLE 1H2TiO3Adsorption selectivity of
Claims (10)
1. A synthesis method of a lithium extraction adsorbent is characterized in that the synthesis process comprises the following steps: adding the additive A into the solvent B, adding the lithium source C into the solvent B, dissolving the lithium source C, and stirring the mixture according to the proportion of Li: the molar ratio of Ti elements is 1.6-2.8: 1 adding a titanium source D, mixing to form slurry, continuously stirring for 0.5-48 h, and then drying the slurry to obtain solid powder(ii) a Calcining the obtained solid powder to prepare lithium ion sieve adsorbent precursor Li2TiO3Precursor Li2TiO3Acid washing and lithium removing are carried out for 0.15-72H at the temperature of 20-90 ℃ to obtain metatitanic acid type lithium ion sieve adsorbent H2TiO3。
2. The synthesis method of the lithium extraction adsorbent according to claim 1, wherein the synthesis method comprises the following steps: the additive A is one or the combination of more than two of sodium hexametaphosphate, polyethylene glycol, ethyl cellulose, terpineol, a silane coupling agent, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and polyacrylate.
3. The synthesis method of the lithium extraction adsorbent according to claim 1, wherein the synthesis method comprises the following steps: the mass content of the additive A is 0-20%.
4. The synthesis method of the lithium extraction adsorbent according to claim 1, wherein the synthesis method comprises the following steps: the solvent B is one or the combination of more than two of water, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, acetone, butanol, ethyl acetate, cyclohexane and n-octane.
5. The synthesis method of the lithium extraction adsorbent according to claim 1, wherein the synthesis method comprises the following steps: the lithium source C is one or the combination of more than two of lithium hydroxide, lithium sulfate, lithium chloride, lithium acetate, lithium propionate, lithium nitrate, lithium hydroxide monohydrate, lithium acetate dihydrate and lithium oxalate.
6. The synthesis method of the lithium extraction adsorbent according to claim 1, wherein the synthesis method comprises the following steps: the titanium source D is one or the combination of more than two of anatase titanium dioxide, rutile titanium dioxide and brookite titanium dioxide; the liquid-solid ratio of the solvent B to the titanium source D is 10-200 mL/g.
7. The synthesis method of the lithium extraction adsorbent according to claim 1, wherein the synthesis method comprises the following steps: the drying treatment mode is spray drying, air flow drying, flash evaporation drying or vacuum conduction drying.
8. The synthesis method of the lithium extraction adsorbent according to claim 1, wherein the synthesis method comprises the following steps: in the calcining process, the temperature is raised to 550-950 ℃ at the heating rate of 1-10 ℃/min, and the temperature is kept for 1-72 h.
9. The synthesis method of the lithium extraction adsorbent according to claim 1, wherein the synthesis method comprises the following steps: the acid used for eluting the lithium by the acid is one or the combination of more than two of hydrochloric acid, sulfuric acid, nitric acid, sulfurous acid, hypochlorous acid, malonic acid, formic acid, acetic acid, propionic acid, citric acid and boric acid.
10. The method for synthesizing the lithium extraction adsorbent according to claim 9, wherein the method comprises the following steps: the concentration of acid in the acid-eluted lithium is 0.01-1 mol/L, and the using amount of the acid is 0.5-50 g/L.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101944600A (en) * | 2010-09-16 | 2011-01-12 | 中南大学 | Lithium-titanium oxide type lithium ion sieve absorbent and method for preparing precursor thereof |
| CN102299313A (en) * | 2011-08-10 | 2011-12-28 | 东莞市迈科科技有限公司 | Preparation method of spinel-type lithium titanate |
| KR20170143313A (en) * | 2016-06-21 | 2017-12-29 | 명지대학교 산학협력단 | Method for preparing hto lithium ion adsorbent and lithium ion recovery uses thereof |
| CN109174068A (en) * | 2018-09-07 | 2019-01-11 | 成都理工大学 | A kind of metatitanic acid type lithium adsorbent and preparation method thereof |
| CN109173976A (en) * | 2018-09-07 | 2019-01-11 | 成都理工大学 | It is a kind of to efficiently separate the synthetic method for extracting the metatitanic acid type lithium adsorbent of lithium in brine |
-
2019
- 2019-12-20 CN CN201911323242.3A patent/CN110975795A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101944600A (en) * | 2010-09-16 | 2011-01-12 | 中南大学 | Lithium-titanium oxide type lithium ion sieve absorbent and method for preparing precursor thereof |
| CN102299313A (en) * | 2011-08-10 | 2011-12-28 | 东莞市迈科科技有限公司 | Preparation method of spinel-type lithium titanate |
| KR20170143313A (en) * | 2016-06-21 | 2017-12-29 | 명지대학교 산학협력단 | Method for preparing hto lithium ion adsorbent and lithium ion recovery uses thereof |
| CN109174068A (en) * | 2018-09-07 | 2019-01-11 | 成都理工大学 | A kind of metatitanic acid type lithium adsorbent and preparation method thereof |
| CN109173976A (en) * | 2018-09-07 | 2019-01-11 | 成都理工大学 | It is a kind of to efficiently separate the synthetic method for extracting the metatitanic acid type lithium adsorbent of lithium in brine |
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