CN117654443B - Lithium adsorbent and preparation method thereof - Google Patents
Lithium adsorbent and preparation method thereof Download PDFInfo
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- CN117654443B CN117654443B CN202410141401.2A CN202410141401A CN117654443B CN 117654443 B CN117654443 B CN 117654443B CN 202410141401 A CN202410141401 A CN 202410141401A CN 117654443 B CN117654443 B CN 117654443B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 67
- 239000003463 adsorbent Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 13
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 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 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 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
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229940118662 aluminum carbonate Drugs 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 25
- -1 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt Chemical class 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 238000003780 insertion Methods 0.000 abstract description 3
- 230000037431 insertion Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 229910000616 Ferromanganese Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000012267 brine Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000004321 preservation Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of solid adsorbents, and discloses a lithium adsorbent and a preparation method thereof. The invention provides a preparation method of a lithium adsorbent, which comprises the following steps: preparing a first mixed solution containing aluminum salt, lithium salt and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt; preparing a second mixed solution of manganese salt, ferric salt and sodium borohydride; preparing alkali liquor; sequentially adding the second mixed solution and the alkali liquor into the first mixed solution under the stirring state, separating solids, drying and crushing to obtain powder; and bonding the powder to obtain the lithium adsorbent. The invention solves the technical problem of lower effective insertion amount of lithium salt in the aluminum-based lithium adsorbent, can reduce the consumption of adhesive and comprehensively improves the adsorption performance of the aluminum-based lithium adsorbent.
Description
Technical Field
The invention belongs to the technical field of solid adsorbents, and discloses a lithium adsorbent and a preparation method thereof.
Background
Lithium and its compounds have been widely used in the fields of electronics, metallurgy, chemical industry, medicine, nuclear energy, aerospace, energy, etc., and extraction of lithium resources from salt lake brine is currently the most dominant acquisition route. The method for extracting lithium from salt lake brine mainly comprises a precipitation method, an ion exchange adsorption method, a carbonization method, a calcination leaching method, a salting-out method, a solvent adsorption method and the like. The adsorption method has the advantages of continuous operation, high enrichment ratio, high yield, simple equipment, low cost, safe operation and the like, and is widely applied. The adsorption method for extracting lithium utilizes the special adsorption performance of the adsorbent to lithium to achieve the purpose of extracting lithium, and the key point is to find a proper adsorbent.
The aluminum-based adsorbent is convenient to prepare, high in selectivity, good in stability and long in service life, and is a lithium adsorbent with very promising development prospect. The aluminum-based lithium extraction adsorbent has a relatively stable layered structure, and when in use, lithium salt inserted in the synthesis process is removed to form octahedral holes which are negatively charged and matched with Li + in size, so that the lithium extraction adsorbent has the capability of selectively adsorbing Li +. For example, CN106975436a discloses a preparation method of a lithium adsorbent and a lithium adsorbent, which are prepared by mixing an aluminum chloride solution with a lithium compound, adding a sodium hydroxide solution to react to generate licl.2.2-2.8 al (OH) 3·2.7~3.9H2 O, and then adding an adhesive and liquid chlorine to realize mixed granulation. However, in the method, as the active body is generated in the reaction process, the concentration of lithium in the liquid phase is continuously reduced, so that the driving force of inserting lithium salt into amorphous aluminum hydroxide is continuously reduced along with the progress of the reaction, and the effective insertion amount of the lithium salt is lower; on the other hand, the adsorbent is in powder form, has poor fluidity and permeability in the adsorption process, and if the adsorbent is to be applied in production, the powder adsorbent must be granulated, and organic binders and the like in the granulation process can block the pore channels of the adsorbent, so that the adsorption capacity of the adsorbent is greatly reduced.
Disclosure of Invention
The invention aims to improve the adsorption performance of an aluminum-based lithium extraction adsorbent.
In order to solve the technical problems, the present invention provides a lithium adsorbent and a preparation method thereof to meet the needs in the art.
In one aspect, the present invention relates to a method for preparing a lithium adsorbent, comprising: preparing a first mixed solution containing 1-2 mol/L aluminum salt, 3-5 mol/L lithium salt and 0.3-0.5 mol/L1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt; preparing a second mixed solution of 0.2-0.4 mol/L manganese salt, 0.5-0.8 mol/L ferric salt and 2-4 mol/L sodium borohydride; preparing 2-4 mol/L alkali liquor; sequentially adding the second mixed solution and the alkali liquor into the first mixed solution under the stirring state, filtering and separating solids, and drying and crushing to obtain powder; mixing the powder, the adhesive and the solvent, and drying, crushing and taking particles with the particle size of 0.5-2.0 mm after extrusion molding to prepare the lithium adsorbent; the ratio of the first mixed solution to the second mixed solution to the alkali liquor is 10:1-3:8-10 in terms of volume ratio; the adhesive is polystyrene, epoxy resin, polymethyl methacrylate, polyvinyl chloride or perchloroethylene; the solvent is liquid chlorine, N-dimethylformamide, ethyl acetate, dichloromethane, dichloroethane, acetone or toluene.
Further, in the preparation method of the lithium adsorbent provided by the invention, the lithium salt is lithium chloride, lithium bromide, lithium carbonate, lithium nitrate or lithium sulfate;
The aluminum salt is aluminum chloride, aluminum bromide, aluminum carbonate, aluminum nitrate, aluminum sulfate or aluminum potassium sulfate dodecahydrate;
the manganese salt is manganese sulfate or manganese dichloride;
The ferric salt is ferric sulfate or ferric trichloride;
The alkali contained in the alkali liquor is lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water or urea.
In the preparation method of the lithium adsorbent, the first mixed solution is heated to 30-50 ℃ under the stirring state, the second mixed solution is added, the alkali liquor is added after 30-60 min, stirring and heat preservation are stopped after 1-3 h, and suction filtration is performed to obtain solid.
Further, in the preparation method of the lithium adsorbent provided by the invention, the stirring speed is 400-800 rpm.
Further, in the preparation method of the lithium adsorbent provided by the invention, the mass ratio of the powder to the binder to the solvent is 100:3-5:10-30.
In another aspect, the present invention relates to a lithium adsorbent prepared by the above-described method for preparing a lithium adsorbent.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects or advantages:
The invention provides a preparation method of a lithium adsorbent, firstly, by adding ionic liquid 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, li + can be pushed to enter octahedral cavity positions of lamellar Al (OH) 3 preferentially due to size matching, and an inorganic ion sieve with a void structure with more binding sites can be obtained under the same lithium salt consumption, so that the adsorption capacity of the lithium adsorbent is improved; secondly, manganese oxide is added, and the characteristic of a layered structure is presented by the octahedral joint connection mode, so that the adsorption capacity of the lithium adsorbent is improved; thirdly, the addition of the iron oxide endows the material with certain magnetism, greatly reduces the use of the adhesive, better improves the adsorption quantity of the lithium adsorbent and is also beneficial to the magnetic attraction separation of the material; and fourthly, the trace nano zero-valent iron and the nano zero-valent manganese can be mutually mixed and piled up, so that the specific surface area and the stability of the adsorbent can be effectively improved.
Detailed Description
The following describes the technical aspects of the present invention with reference to examples, but the present invention is not limited to the following examples.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1: this example provides a process for preparing a lithium adsorbent.
Step 1: adding pure water, aluminum chloride, lithium chloride and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt into a beaker to prepare a first mixed solution of 1mol/L aluminum chloride, 3mol/L lithium chloride and 0.3 mol/L1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, transferring the first mixed solution into a three-neck flask with a mechanical stirring and thermometer, keeping stirring at 400rpm, and heating to 30 ℃ for heat preservation.
Step 2: preparing MnSO 4·H2 O and Fe 2（SO4）3·6H2 O into solutions with proper concentrations respectively with pure water, and then mixing to obtain a ferromanganese mixed solution; and pumping the sodium borohydride solution by a constant flow pump, adding the sodium borohydride solution into the ferromanganese mixed solution until the pumping is completed, and continuing the reaction for 30min to obtain a second mixed solution of 0.2mol/L MnSO 4·H2O,0.5mol/L Fe2（SO4）3·6H2 O and 2mol/L sodium borohydride.
Step 3: adding the second mixed solution prepared in the step 2 into the three-neck flask of the first mixed solution filled in the step 1, maintaining the temperature and the stirring rotation speed, adding 2mol/L lithium hydroxide after 30min, continuously maintaining the temperature and the stirring rotation speed, stopping stirring and preserving heat after 1h, and carrying out suction filtration on the reaction mixture to obtain the wet active body.
Step 4: vacuum drying the wet active body obtained in step3 at 65deg.C for 16 hr, and conveying to impact mill pulverizing device by air flow conveyor until the dry active body is pulverized to particle size below 100Obtaining powder.
Step 5: and (3) adding 100g of the powder prepared in the step (4) into a conical double-screw mixer, adding 3g of polyvinyl chloride and 10g of dichloroethane into the conical double-screw mixer, fully and uniformly mixing, extruding the mixture into a strip with the cross section diameter of 4.0mm, standing the mixture at room temperature for 1 hour, drying the mixture at 60 ℃ for 2 hours, and crushing the mixture to obtain particles with the particle size of 0.5-2.0 mm, thus obtaining the lithium adsorbent.
In the steps, the ratio of the first mixed solution to the second mixed solution to the alkali liquor is 10:1:8 by volume ratio.
It should be noted that in step 2, as the sodium borohydride solution is added, mnSO 4·H2 O and Fe 2（SO4）3·6H2 O in the second mixed solution have reacted and reduced, and the concentration of each component in the second mixed solution is only convenient for calculating the specific amount of each component.
Example 2: this example provides a process for preparing a lithium adsorbent.
Step 1: adding pure water, aluminum sulfate, lithium sulfate and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt into a beaker to prepare a first mixed solution of 1.5mol/L aluminum sulfate, 4mol/L lithium sulfate and 0.4 mol/L1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, transferring the first mixed solution into a three-neck flask with a mechanical stirring and thermometer, keeping stirring at 600rpm, and heating to 45 ℃ for heat preservation.
Step 2: preparing MnSO 4·H2 O and Fe 2（SO4）3·6H2 O into solutions with proper concentrations respectively with pure water, and then mixing to obtain a ferromanganese mixed solution; and pumping the sodium borohydride solution by a constant flow pump, adding the sodium borohydride solution into the ferromanganese mixed solution until the pumping is completed, and continuing the reaction for 30min to obtain a second mixed solution of 0.3mol/L MnSO 4·H2O,0.6mol/L Fe2（SO4）3·6H2 O and 3mol/L sodium borohydride.
Step 3: adding the second mixed solution prepared in the step 2 into the three-neck flask of the first mixed solution filled in the step 1, maintaining the temperature and the stirring rotation speed, adding 3mol/L sodium hydroxide after 45min, continuously maintaining the temperature and the stirring rotation speed, stopping stirring and preserving heat after 2h, and carrying out suction filtration on the reaction mixture to obtain the wet active body.
Step 4: vacuum drying the wet active body obtained in step3 at 65deg.C for 16 hr, and conveying to impact mill pulverizing device by air flow conveyor until the dry active body is pulverized to particle size below 100Obtaining powder.
Step 5: adding 100g of the powder prepared in the step 4 into a conical double-screw mixer, adding 4g of perchloroethylene and 20g of liquid chlorine into the conical double-screw mixer, fully and uniformly mixing, extruding the mixture into strips with the cross section diameter of 4.0mm, standing for 1 hour at room temperature, drying at 60 ℃ for 2 hours, and crushing to obtain particles with the particle size of 0.5-2.0 mm, thus obtaining the lithium adsorbent.
In the steps, the ratio of the first mixed solution to the second mixed solution to the alkali liquor is 10:2:9 by volume ratio.
Example 3: this example provides a process for preparing a lithium adsorbent.
Step 1: adding pure water, aluminum bromide, lithium bromide and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt into a beaker to prepare a first mixed solution of 2mol/L aluminum sulfate, 5mol/L lithium sulfate and 0.5 mol/L1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, transferring the first mixed solution into a three-neck flask with a mechanical stirring and thermometer, keeping stirring at 800rpm, and heating to 50 ℃ for heat preservation.
Step 2: respectively preparing manganese dichloride and ferric trichloride into solutions with proper concentrations with pure water, and then mixing to obtain a ferromanganese mixed solution; and (3) extracting the sodium borohydride solution by a constant flow pump, adding the sodium borohydride solution into the ferromanganese mixed solution until extraction is completed, and continuing the reaction for 30min to obtain a second mixed solution of 0.4mol/L manganese dichloride, 0.8mol/L ferric trichloride and 4mol/L sodium borohydride.
Step 3: adding the second mixed solution prepared in the step 2 into the three-neck flask of the first mixed solution filled in the step 1, maintaining the temperature and the stirring rotation speed, adding 4mol/L potassium hydroxide after 60min, continuously maintaining the temperature and the stirring rotation speed, stopping stirring and preserving heat after 3h, and carrying out suction filtration on the reaction mixture to obtain the wet active body.
Step 4: vacuum drying the wet active body obtained in step3 at 65deg.C for 16 hr, and conveying to impact mill pulverizing device by air flow conveyor until the dry active body is pulverized to particle size below 100Obtaining powder.
Step 5: and (3) adding 100g of the powder prepared in the step (4) into a conical double-screw mixer, adding 5g of polystyrene and 30g of dichloromethane into the conical double-screw mixer, fully and uniformly mixing, extruding the mixture into strips with the cross section diameter of 4.0mm, standing at room temperature for 1 hour, drying at 60 ℃ for 2 hours, and crushing to obtain particles with the particle size of 0.5-2.0 mm, thus obtaining the lithium adsorbent.
In the steps, the ratio of the first mixed solution to the second mixed solution to the alkali liquor is 10:3:10 by volume ratio.
Comparative example 1: this comparative example is intended to illustrate the effect of the order of addition of the second mixed liquor and the lye on the preparation of the lithium adsorbent.
This comparative example is identical to example 2, except that the alkaline solution is added first and then the second mixed solution is added.
Comparative example 2: this comparative example is intended to illustrate the effect of ionic liquid addition on lithium sorbent preparation.
This comparative example is identical to example 2, except that no 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimine salt was added.
Comparative example 3: this comparative example is intended to illustrate the effect of manganese addition on lithium sorbent preparation.
This comparative example is identical to example 2, except that no manganese salt is added to the second mixed solution.
Comparative example 4: this comparative example is intended to illustrate the effect of iron addition on lithium sorbent preparation.
This comparative example is identical to example 2, except that no iron salt was added to the second mixed liquor.
Comparative example 5: this comparative example is intended to illustrate the effect of the addition of the second mixed liquor on the preparation of the lithium adsorbent.
This comparative example is identical to example 2, except that the second mixed solution is not added.
The pore structure parameters of the detected examples 1 to 3, comparative example 1 and comparative example 5 are shown in Table 1.
TABLE 1 pore Structure parameters of lithium adsorbents
As can be seen from Table 1, compared with the lithium adsorbents prepared in comparative examples 1 and 5, the lithium adsorbent prepared by the method of the present invention has a higher specific surface area and uniform pore diameter of the total pores Rong Heping, and increases the contact area between the lithium adsorbent and brine, so that the lithium adsorbent composite particles are fully contacted with the brine, and the lithium adsorption capacity and adsorption effect are effectively improved.
Loading the lithium adsorbent samples prepared in examples 1-3 and comparative examples 1-5 into a chromatographic column, passing through the column with pure water for activation until the lithium content of the passing column liquid is less than 100mg/L, and performing dynamic adsorption-desorption experiments by using brine (the lithium content is 264.91 ppm) extracted from a salt lake. Adsorption: performing adsorption experiment with liquid-solid ratio of 40, stirring at room temperature of 10Hz for 1 hr, filtering, and collecting filtrate; and (3) desorption: the adsorbent was eluted three times with deionized water at a liquid-to-solid ratio of 50, stirred at 20Hz at room temperature for 1 hour each time, and dried at 80 ℃. The first, 10 th and 100 th Li adsorption amounts were tested, and the test results are shown in table 2.
TABLE 2 Li adsorption quantity (mg/g)
As can be seen from table 1, compared with the lithium adsorbents prepared in comparative examples 1 to 5, the adsorption effect of the lithium adsorbent prepared according to the method of the present invention is significantly improved; and after 10 times and 100 times of recycling, the adsorption quantity of the lithium adsorbent is not obviously reduced, so that the lithium adsorbent has better adsorption stability. As shown in the comparative example, the addition sequence of the second mixed solution and the alkali solution directly influences the combination of the ferro-manganese and the Li X·nAl（OH）3·mH2 O active body, so that the adsorption effect of the lithium adsorbent is obviously reduced; the addition of the ionic liquid enables the insertion of lithium salt into amorphous aluminum hydroxide to have relatively high driving force all the time, and the adsorption effect of the lithium adsorbent is greatly improved; the addition of both manganese and iron improved the adsorption capacity of the lithium adsorbent, and the iron was mainly improved in adsorption stability, as can be seen from comparative examples 4 and 5, the lack of iron added directly resulted in a significant decrease in stability when less binder was used in the present invention.
As described above, the basic principles, main features and advantages of the present invention are better described. The above examples and description are merely illustrative of preferred embodiments of the present invention, and the present invention is not limited to the above examples, and various changes and modifications to the technical solution of the present invention by those skilled in the art should fall within the scope of protection defined by the present invention without departing from the spirit and scope of the present invention.
Claims (4)
1. A method for preparing a lithium adsorbent, comprising: preparing a first mixed solution containing 1-2 mol/L aluminum salt, 3-5 mol/L lithium salt and 0.3-0.5 mol/L1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt;
Preparing a second mixed solution of 0.2-0.4 mol/L manganese salt, 0.5-0.8 mol/L ferric salt and 2-4 mol/L sodium borohydride;
Preparing 2-4 mol/L alkali liquor;
heating the first mixed solution to 30-50 ℃ under stirring, preserving heat, adding the second mixed solution, adding the alkali liquor after 30-60 min, stopping stirring and preserving heat after 1-3 h, performing suction filtration to obtain solid, and drying and crushing to obtain powder;
Mixing the powder, the adhesive and the solvent, and drying, crushing and taking particles with the particle size of 0.5-2.0 mm after extrusion molding to prepare the lithium adsorbent;
the ratio of the first mixed solution to the second mixed solution to the alkali liquor is 10:1-3:8-10 in terms of volume ratio;
the adhesive is polystyrene, epoxy resin, polymethyl methacrylate, polyvinyl chloride or perchloroethylene;
The solvent is liquid chlorine, N-dimethylformamide, ethyl acetate, dichloromethane, dichloroethane, acetone or toluene;
The mass ratio of the powder to the binder to the solvent is 100:3-5:10-30.
2. The method for producing a lithium adsorbent according to claim 1, wherein the lithium salt is lithium chloride, lithium bromide, lithium carbonate, lithium nitrate or lithium sulfate;
The aluminum salt is aluminum chloride, aluminum bromide, aluminum carbonate, aluminum nitrate, aluminum sulfate or aluminum potassium sulfate dodecahydrate;
the manganese salt is manganese sulfate or manganese dichloride;
The ferric salt is ferric sulfate or ferric trichloride;
The alkali contained in the alkali liquor is lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water or urea.
3. The method for producing a lithium adsorbent according to claim 1, wherein the stirring speed is 400 to 800rpm.
4. A lithium adsorbent characterized by being produced by the method for producing a lithium adsorbent according to any one of claims 1 to 3.
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| CN113509912A (en) * | 2020-11-25 | 2021-10-19 | 中国科学院青海盐湖研究所 | Preparation method of lithium ion sieve adsorbent particles for extracting liquid lithium resources |
| CN114570338A (en) * | 2022-01-21 | 2022-06-03 | 广东台泉环保科技有限公司 | Salt lake lithium extraction adsorbent master batch and preparation method thereof |
| WO2022150849A1 (en) * | 2021-01-08 | 2022-07-14 | Global Graphene Group, Inc. | Flame-resistant quasi-solid and solid-state electrolyte for lithium-ion and lithium metal batteries and production method |
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| CN113509912A (en) * | 2020-11-25 | 2021-10-19 | 中国科学院青海盐湖研究所 | Preparation method of lithium ion sieve adsorbent particles for extracting liquid lithium resources |
| WO2022150849A1 (en) * | 2021-01-08 | 2022-07-14 | Global Graphene Group, Inc. | Flame-resistant quasi-solid and solid-state electrolyte for lithium-ion and lithium metal batteries and production method |
| CN114570338A (en) * | 2022-01-21 | 2022-06-03 | 广东台泉环保科技有限公司 | Salt lake lithium extraction adsorbent master batch and preparation method thereof |
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