CN115739045A - Spherical lithium adsorbent and preparation method and application thereof - Google Patents
Spherical lithium adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN115739045A CN115739045A CN202211423871.5A CN202211423871A CN115739045A CN 115739045 A CN115739045 A CN 115739045A CN 202211423871 A CN202211423871 A CN 202211423871A CN 115739045 A CN115739045 A CN 115739045A
- Authority
- CN
- China
- Prior art keywords
- lithium
- adsorbent
- lithium adsorbent
- spherical
- inorganic
- Prior art date
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- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 173
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 239000003463 adsorbent Substances 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000010410 layer Substances 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 238000000605 extraction Methods 0.000 claims abstract description 16
- 239000012792 core layer Substances 0.000 claims abstract description 15
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 14
- 229920000768 polyamine Polymers 0.000 claims abstract description 13
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 11
- 239000004952 Polyamide Substances 0.000 claims abstract description 7
- 229920002647 polyamide Polymers 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 27
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 21
- 238000001723 curing Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 16
- 239000011164 primary particle Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000012267 brine Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
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- 239000011734 sodium Substances 0.000 claims description 9
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
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- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 7
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- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 6
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
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- 239000003431 cross linking reagent Substances 0.000 claims description 6
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- 239000000463 material Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012798 spherical particle Substances 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- XESUCHPMWXMNRV-UHFFFAOYSA-M sodium;2-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=C XESUCHPMWXMNRV-UHFFFAOYSA-M 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- JGPIKFZCMVIHJN-UHFFFAOYSA-N ethenyl 3-pyridin-2-ylprop-2-enoate Chemical group C=COC(=O)C=CC1=CC=CC=N1 JGPIKFZCMVIHJN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229940080350 sodium stearate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 239000011787 zinc oxide 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 provides a spherical lithium adsorbent and a preparation method and application thereof. The interior of the spherical lithium adsorbent is of a cross-linked network structure doped with the inorganic lithium adsorbent, and the appearance of the spherical lithium adsorbent is spherical; the cross-linked network structure in the lithium ion battery consists of an inner core layer and an outer shell layer which are double cross-linked layers, wherein the outer shell layer is cross-linked polyamide doped with an inorganic lithium adsorbent, and the inner core layer is a cross-linked hydrophilic polymer doped with the inorganic lithium adsorbent; the cross-linked polyamide is prepared from polyamine monomers and acyl chloride through polycondensation, and the cross-linked hydrophilic polymer is prepared from hydrophilic monomers through free radical polymerization. The preparation process is simple and environment-friendly, and the prepared lithium adsorbent has the advantages of stable structure, good hydrophilicity, large lithium ion adsorption capacity, low running friction loss, high adsorption speed and low dissolution loss, and can be widely used for extraction and recycling of liquid lithium resources.
Description
Technical Field
The invention belongs to the technical field of lithium adsorbents, and particularly relates to a spherical lithium adsorbent suitable for extracting lithium from lithium-containing solutions such as salt lake brine, underground brine, seawater and battery recovery solutions and a preparation method thereof.
Background
Through the development of the lithium industry for many years, products of the lithium industry are all over the aspect of modern society, and the lithium industry is widely applied to the fields of medicines, polymers, new materials, new energy sources and the like. With the rapid development of downstream industries, the market demand for lithium products is rapidly increasing. In recent years, the extraction of lithium from salt lakes has become one of the important ways to obtain lithium resources.
The extraction method of lithium from salt lake is divided into calcination leaching method, solar cell method, precipitation method, extraction method, membrane method and adsorption method, the former four methods are traditional lithium extraction method, the process is relatively mature, but the short plate is also very prominent. For example, the calcining leaching method has large energy consumption and high cost; the precipitation method has long airing period and low efficiency; the solar pond method is only suitable for salt lakes with extremely low magnesium-lithium ratio, and the capacity is greatly influenced by weather; extraction equipment is susceptible to corrosion by the extractant and the extractant is susceptible to loss. The whole membrane method and the adsorption method are emerging technologies of the current salt lake lithium extraction industry, the two methods have the advantages of simple process and small pollution, but the whole membrane method has the defects of high membrane consumption and easy membrane pollution, and further increases the comprehensive cost of lithium extraction; the adsorption method is to extract lithium ions from brine by two steps of adsorption and elution by adopting a specific adsorbent, and has high technical difficulty and difficulty in preparation of a lithium adsorbent (a lithium-enriched material), but the adsorption method is the most competitive method in the lithium extraction method of brine with high magnesium/sodium-lithium ratio.
The difficulty of extracting lithium by an adsorption method lies in the preparation and forming of lithium adsorbents, and the active ingredients of the existing lithium adsorbents such as aluminum adsorbents, manganese adsorbents and titanium adsorbents are inorganic powder, so that the defects of poor permeability and high dissolution loss exist when the lithium adsorbents are directly used, and the inorganic adsorbents need to be granulated. Common forming methods include granulation, film making, and foaming (or porous material loading), wherein granulation is generally divided into physical blending and chemical reaction granulation. The physical blending granulation is a process of uniformly mixing an inorganic adsorbent and an inert binder and then molding. Uniformly mixing resin such as polyvinyl chloride, polyvinylidene fluoride and the like with an inorganic adsorbent, and then granulating (CN 113996274A); the chemical reaction granulation is a process of uniformly mixing an inorganic adsorbent and an active binder, and then carrying out reaction and solidification. Mixing binder such as epoxy resin and phenolic resin with inorganic adsorbent, granulating, reacting, shaping (CN 112871127A), or crushing (CN 108435142B).
The granulated adsorbent can generally solve or reduce the problem of dissolution loss, but because part of the adhesive has poor hydrophilicity, the active sites of the inorganic adsorbent cannot fully exert the adsorption effect due to coating, or the formed particles are irregular, and the friction loss during column filling operation is large, so the adsorption capacity is greatly reduced.
Disclosure of Invention
The invention aims to provide a spherical lithium adsorbent and a preparation method thereof, and aims to solve the problems that in the prior granulation technology, the adsorbent column packing operation loss is large and the adsorption capacity is greatly reduced due to hydrophobic binder or irregular formed particles. The spherical lithium adsorbent prepared by the invention has the advantages of regular appearance and appearance, stable structure and large lithium ion adsorption capacity, can be widely applied to lithium extraction in lithium-containing solutions such as salt lake brine, underground brine, seawater, battery recovery solution and the like, and has wide application prospect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a spherical lithium adsorbent, wherein the interior of the spherical lithium adsorbent is of a cross-linked network structure doped with an inorganic lithium adsorbent, and the appearance of the spherical lithium adsorbent is spherical;
the cross-linked network structure in the shell is composed of an inner core layer and an outer shell layer, the outer shell layer is cross-linked polyamide doped with an inorganic lithium adsorbent, and the inner core layer is a cross-linked hydrophilic polymer doped with the inorganic lithium adsorbent;
the cross-linked polyamide doped with the inorganic lithium adsorbent is prepared by performing polycondensation on a polyamine monomer and acyl chloride mixed with an inorganic lithium adsorbent precursor, and the cross-linked hydrophilic polymer doped with the inorganic lithium adsorbent is prepared by performing free radical polymerization on a hydrophilic monomer mixed with the inorganic lithium adsorbent precursor.
In the invention, the inorganic lithium adsorbent is a material having specific adsorption on lithium ions and is generated from an inorganic lithium adsorbent precursor through a delithiation operation, and the delithiation method is a routine operation in the field, for example, lithium can be eluted through an eluent;
the describedThe inorganic adsorbent precursor is selected from LiCl.2Al (OH) 3 .nH 2 O、LiMn 2 O 4 、Li 1.6 Mn 1.6 O 4 、Li 1.33 Mn 1.67 O 4 、Li 2 TiO 3 、Li 4 Ti 5 O 12 One or more of (a);
the particle size of the inorganic adsorbent precursor is 0.1-100 μm, preferably 1-60 μm.
In the invention, the shell layer is cross-linked polyamide doped with inorganic lithium adsorbent, and is prepared by performing polycondensation reaction on polyamino monomer and acyl chloride and mixing inorganic lithium adsorbent precursors in a polycondensation reaction system, wherein the polycondensation reaction method is a known process in the prior art, and specific steps can be determined according to actual needs by a person skilled in the art with the aid of the prior art, and are not specifically limited;
wherein the polyamine monomer is selected from one or more of nitrogen heterocyclic, aromatic and aliphatic polyamine monomers, and is preferably melamine, piperazine, m-phenylenediamine, o-phenylenediamine,P-phenylenediamine,One or more of ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine, more preferably melamine, piperazine, m-phenylenediamine, o-phenylenediamine, poly (ethylene-co-ethyleneimine),P-phenylenediamineOne or more of;
wherein, the acyl chloride is selected from one or more of trimesoyl chloride, isophthaloyl dichloride and terephthaloyl dichloride.
In the invention, the inner core layer is a cross-linked hydrophilic polymer doped with an inorganic lithium adsorbent, and is prepared by carrying out free radical polymerization reaction on a hydrophilic monomer and mixing an inorganic lithium adsorbent precursor in a polymerization reaction system, wherein the free radical polymerization reaction method is a process known in the prior art, and specific steps can be determined by a person skilled in the art according to actual needs by means of the prior art, and are not specifically limited;
the hydrophilic monomer is slightly water soluble or water soluble monomer, and is selected from one or more of vinyl, acrylonitrile, acrylic acid (salt or ester) and acrylamide hydrophilic monomers, preferably one or more of sodium p-vinylbenzene sulfonate, sodium vinylsulfonate, 2-acrylamido-2-methylpropanesulfonic acid (sodium) acrylonitrile, (sodium (meth) acrylate), (methyl (meth) acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol methacrylate, vinylpyridine, vinylpyrrolidone, acrylamide, methacrylamide, N-methylolacrylamide, N-dimethylacrylamide and N-isopropylacrylamide, more preferably one or more of sodium vinylbenzene sulfonate, (sodium (meth) acrylate), (methyl (meth) acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinylpyridine, vinylpyrrolidone, acrylamide and N-methylolacrylamide.
In the present invention, the content of the inorganic lithium adsorbent doped in the spherical lithium adsorbent is 30 to 85wt%, preferably 50 to 80wt%.
In the invention, the particle size of the spherical lithium adsorbent is 0.5-5mm, and the thickness of the shell layer is 0.5-10 μm.
In the invention, the spherical lithium adsorbent is spherical, the uniform particle size coefficient is less than or equal to 1.4, the density is 1.0-1.4g/mL, and the specific surface area is more than or equal to 40m 2 G, pore diameter of 4.0-50nm, pore volume of 0.1-0.5cm 3 /g。
The invention also provides a preparation method of the spherical lithium adsorbent, which comprises the following steps:
(1) Uniformly mixing an inorganic lithium adsorbent precursor, a hydrophilic monomer, a cross-linking agent, an initiator, a polyamine monomer, an auxiliary agent and water to obtain a water phase;
(2) Dropwise adding the water phase into a mixed solution of acyl chloride and an organic solvent A to form spherical particles, and then carrying out a curing reaction to obtain primary particles;
(3) Adding the primary particles into an organic solvent B, stirring, heating, curing, washing and drying to obtain a spherical lithium adsorbent precursor;
(4) And (3) eluting lithium from the spherical lithium adsorbent precursor by using an eluent to obtain the spherical lithium adsorbent.
In the step (1), the prepared water phase comprises the following components in percentage by mass: 20-60%, preferably 30-60% of inorganic lithium adsorbent precursor; 2-15% of hydrophilic monomer, preferably 2-10%; 5-15% of a cross-linking agent, preferably 10-15%; initiator 0.1-2%, preferably 0.5-1.5%; polyamine monomer 2-5%, preferably 2-3%; 0.1 to 3 percent of auxiliary agent, preferably 1 to 3 percent; the balance of water.
In step (1) of the present invention, the inorganic lithium adsorbent precursor powder is a material having specific adsorption to lithium ions, and is selected from licl.2al (OH) 3 .nH 2 O、LiMn 2 O 4 、Li 1.6 Mn 1.6 O 4 、Li 1.33 Mn 1.67 O 4 、Li 2 TiO 3 、Li 4 Ti 5 O 12 One or more of; the particle size of the inorganic adsorbent precursor is 0.1-100 μm, preferably 1-60 μm.
In step (1) of the present invention, the hydrophilic monomer is a slightly water-soluble or water-soluble monomer selected from one or more of hydrophilic monomers of vinyl type, acrylonitrile type, acrylic acid (salt or ester) type, and acrylamide type, preferably one or more of sodium p-vinylbenzene sulfonate, sodium vinylsulfonate, 2-acrylamido-2-methylpropanesulfonic acid (sodium), acrylonitrile, (sodium (meth) acrylate, (meth) acrylic acid methyl ester, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol methacrylate, vinylpyridine, vinylpyrrolidone, acrylamide, methacrylamide, N-methylolacrylamide, N-dimethylacrylamide, and N-isopropylacrylamide, more preferably one or more of sodium vinylbenzene sulfonate, (meth) acrylic acid (sodium), (meth) acrylic acid methyl ester, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinylpyridine, vinylpyrrolidone, acrylamide, and N-methylolacrylamide.
In step (1) of the present invention, the crosslinking agent is selected from N, N-Methylene bisacrylamideTrimethylolpropane diallyl ether, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, preferably N, N-Methylene bisacrylamideTrimethylolpropane diallyl ether and diethylene glycol dipropylene glycolOne or more of alkenoic acid esters.
In step (1) of the present invention, the initiator is selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide, cumene hydroperoxide, ammonium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride,azo bis Cyanovaleric acidAnd azodiisopropyl imidazoline, preferably one or more of azodiisobutyronitrile, dibenzoyl peroxide, ammonium persulfate and potassium persulfate.
In step (1) of the present invention, the polyamine monomer is one or more selected from the group consisting of azacyclo-type, aromatic-type and aliphatic-type polyamine monomers, preferably melamine, piperazine, m-phenylenediamine, o-phenylenediamine,P-phenylenediamine,One or more selected from ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine, more preferably melamine, piperazine, m-phenylenediamine, o-phenylenediamine, poly (ethylene-co-propylene-diamine),P-phenylenediamineOne or more of (a).
In step (1) of the present invention, the auxiliary agent is one or more selected from polyvinyl alcohol, sodium stearate, sodium dodecylbenzenesulfonate and sodium dodecylsulfate.
In step (2) of the present invention, the acid chloride is mixed with the organic solvent a, wherein the concentration of the acid chloride is 1 to 5wt%, preferably 1 to 3wt%;
the acyl chloride is selected from one or more of trimesoyl chloride, isophthaloyl dichloride and terephthaloyl dichloride;
the organic solvent A is selected from one or more of C6-C20 cyclic, normal and isoparaffin, preferably one or more of C6-C10 cyclic, normal and isoparaffin; more preferably one or more of n-hexane, n-heptane, n-octane, n-nonane and n-decane.
In step (2) of the present invention, the mass ratio of the mixed solution of the acid chloride and the organic solvent a to the aqueous phase is 1 to 10, preferably 2.
In the step (2) of the invention, when the water phase is dripped into the mixed solution of acyl chloride and organic solvent A, the dripping speed is 0.2-3 seconds per drop, preferably 0.5-1.5 seconds per drop;
during the dropwise addition, the temperature of the mixed solution of the acid chloride and the organic solvent A is 20 to 40 ℃, preferably 25 to 40 ℃.
In the step (2), the curing reaction is carried out at the reaction temperature of 20-40 ℃, preferably 25-40 ℃; the reaction time is 0.5-10min, preferably 2-10min.
In step (2) of the present invention, the primary particles have a particle size of 0.5 to 5mm, preferably 0.5 to 3mm; the uniform coefficient of the granularity is less than or equal to 1.40.
In step (3) of the present invention, the organic solvent B is selected from one or more of C6-C20 cyclic, normal, and isoparaffin, preferably one or more of C6-C10 cyclic, normal, and isoparaffin; more preferably one or more of n-hexane, n-heptane, n-octane, n-nonane and n-decane;
the organic solvent B and the organic solvent A may be the same or different, and preferably, both are the same.
In step (3) of the present invention, the mass ratio of the organic solvent B to the primary particles is 1.
In the step (3) of the invention, the heating and curing are carried out, wherein the curing temperature is 50-90 ℃, and preferably 65-90 ℃; the curing time is 2-20h, preferably 8-15h.
In step (3) of the present invention, the stirring, washing (preferably ethanol washing), drying and the like are conventional operations in the art, and the present invention is not particularly required.
In the step (4) of the invention, the eluent is selected from water (such as deionized water) or dilute acid solution with the hydrogen ion concentration of 0.1-1 mol/L;
wherein the dilute acid solution is selected from one or more of hydrochloric acid, nitric acid and sulfuric acid;
the dosage of the eluent is 20-100mL/g of adsorbent precursor.
In the step (4) of the invention, the temperature of the lithium-removing solution is 15-70 ℃, preferably 15-50 ℃; the time is 0.5-24h, preferably 2-10h.
The spherical lithium adsorbent is suitable for the field of lithium extraction of a solution system containing lithium ions, and is particularly suitable for the field of lithium extraction of lithium-containing aqueous solutions such as salt lake brine, underground brine, seawater, battery recovery solution and the like with the lithium ion concentration of 20-2000 ppm.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) In the preparation process of the spherical lithium adsorbent, a large amount of organic solvent which is difficult to recover and treat is avoided, and the used oil phase can be repeatedly used, so that the production cost is effectively reduced;
2) The spherical lithium adsorbent prepared by the composite granulation method has the advantages of regular appearance and appearance, stable structure, good hydrophilicity, large lithium ion adsorption capacity, high adsorption speed and low solvent loss, can effectively reduce the friction loss of packed operation of the granular adsorbent while solving the problem of large loss of the direct use of inorganic lithium adsorbent powder, reduces the annual supplement amount, and can be widely used for extraction and recycling of liquid lithium resources.
Detailed Description
For better understanding of the technical aspects of the present invention, the following specific examples are given for the purpose of illustrating the contents of the present invention, and suitable substitutions and modifications are within the scope of the present invention without departing from the spirit of the present invention.
The main raw materials used in the examples and comparative examples of the present invention were obtained from the following sources, and other raw materials and reagents were obtained from ordinary commercial sources unless otherwise specified:
inorganic lithium adsorbent precursor LiCl.2Al (OH) 3 .H 2 O reference prepared by the method disclosed in aluminum hydroxide as selective solvent of lithium salts from crystals and technical solvents;
Li 1.6 Mn 1.6 O 4 the preparation method is disclosed in the reference of preparation of the high manganese-lithium ratio adsorption material and research on lithium adsorption performance;
Li 2 TiO 3 purchased from Shanghai Aladdin Biotechnology Ltd.
Example 1
Preparing a spherical lithium adsorbent, comprising the following steps:
(1) Preparation of a water phase: 50g of LiCl having a particle size of 20 μm were weighed.2Al(OH) 3 .H 2 O, 2g of sodium vinylbenzenesulfonate, 10g of NMethylene bisacrylamide、0.5 ammonium persulfate、2g piperazine2g of sodium dodecyl benzene sulfonate and 33.5g of deionized water, and stirring, dissolving and dispersing into uniform slurry to obtain a water phase.
(2) Preparing a mixed solution of isophthaloyl dichloride and n-hexane: weighing 2g of isophthaloyl dichloride and 198g of n-hexane, stirring, dissolving and heating to 25 ℃ to obtain a mixed solution.
Slowly dripping 100g of the prepared water phase into 200g of mixed solution of isophthaloyl dichloride and n-hexane at the speed of 0.5 second/drop to form spherical particles, then carrying out curing reaction for 1min at 25 ℃, and filtering to obtain primary particles with the particle size of 0.5-1.5mm, wherein the uniformity coefficient of the particle size is 1.20.
(3) Transferring 98g of primary particles into 200g of n-decane, heating to 80 ℃ under stirring for curing reaction for 10h, washing with ethanol, and drying to obtain the spherical lithium adsorbent precursor.
(4) Weighing 20g of spherical lithium adsorbent precursor, adding 800mL of deionized water, and heating to 40 ℃ to remove lithium for 4h to obtain the spherical lithium adsorbent.
The spherical lithium adsorbent prepared in this example is spherical in appearance, and includes an inner core layer and an outer shell layer, the outer shell layer is crosslinked aliphatic polyamide doped with an inorganic lithium adsorbent, the inner core layer is a sodium vinylbenzenesulfonate-acrylamide co-crosslinked hydrophilic polymer doped with an inorganic lithium adsorbent, the doping amount of the inorganic lithium adsorbent in the spherical lithium adsorbent is 78wt%, and the following characteristic parameters are as in table 1 below:
TABLE 1
Example 2
Preparing a spherical lithium adsorbent, comprising the following steps:
(1) Preparation of a water phase: 40g of Li having a particle size of 15 μm were weighed 1.6 Mn 1.6 O 4 5g of hydroxyethyl methacrylate, 15g of triethylene glycol diacrylate,1g of azobisisobutyronitrile、3g of p-phenylenediamine1g of dodecyl sulfuric acidSodium and 35g of deionized water are stirred, dissolved and dispersed into uniform slurry to obtain a water phase.
(2) Preparing a mixed solution of trimesoyl chloride and n-heptane: 3g of trimesoyl chloride and 197g of n-heptane are weighed, dissolved by stirring and heated to 30 ℃ to obtain a mixed solution.
Slowly dripping 100g of the prepared water phase into a mixed solution of 200g of trimesoyl chloride and n-heptane at the speed of 0.8 s/drop to form spherical particles, then carrying out curing reaction at 30 ℃ for 3min, and filtering to obtain primary particles with the particle size of 1-2mm, wherein the uniform coefficient of particle size is 1.11.
(3) Transferring 95g of primary particles into 240g of n-heptane, heating to 85 ℃ under stirring for curing reaction for 12h, washing with ethanol, and drying to obtain the spherical lithium adsorbent precursor.
(4) Weighing 20g of spherical lithium adsorbent precursor, adding the spherical lithium adsorbent precursor into 800mL of dilute hydrochloric acid with the concentration of 0.4mol/L, and heating to 40 ℃ to remove lithium for 2h to obtain the spherical lithium adsorbent.
The spherical lithium adsorbent prepared in this example is spherical in appearance, and includes an inner core layer and an outer shell layer, the outer shell layer is crosslinked aromatic polyamide doped with the inorganic lithium adsorbent, the inner core layer is crosslinked acrylate hydrophilic polymer doped with the inorganic lithium adsorbent, the doping amount of the inorganic lithium adsorbent in the spherical lithium adsorbent is 63wt%, and the following characteristic parameters are as follows:
TABLE 2
Example 3
Preparing a spherical lithium adsorbent, comprising the following steps:
(1) Preparing a water phase: 60g of Li having a particle size of 1 μm were weighed 2 TiO 3 8g of vinylpyridine, 10g of dipropylene glycol diacrylate,1gPotassium persulfate,4g of diethylenetriamine3g of sodium dodecyl sulfate and 14g of deionized water, and stirring, dissolving and dispersing into uniform slurry to obtain a water phase.
(2) Preparing a mixed solution of terephthaloyl chloride and n-nonane: weighing 10g of terephthaloyl chloride and 490g of n-nonane, stirring, dissolving and heating to 40 ℃ to obtain a mixed solution.
Slowly dripping 100g of the prepared water phase into 500g of mixed solution of terephthaloyl chloride and n-nonane at the speed of 1.5 s/drop to form spherical particles, then carrying out curing reaction at 40 ℃ for 5min, and filtering to obtain primary particles with the particle size of 0.8-1.5mm, wherein the uniform coefficient of the particle size is 1.14.
(3) And transferring 96g of primary particles into 300g of n-nonane, heating to 90 ℃ under stirring for curing reaction for 8h, washing with ethanol, and drying to obtain the spherical lithium adsorbent precursor.
(4) Weighing 20g of spherical lithium adsorbent precursor, adding the spherical lithium adsorbent precursor into 800mL of dilute hydrochloric acid with the concentration of 0.4mol/L, and removing lithium for 2h at 40 ℃ to obtain the spherical lithium adsorbent.
The spherical lithium adsorbent prepared in this example is spherical in appearance, and includes an inner core layer and an outer shell layer, the outer shell layer is crosslinked aliphatic polyamide doped with inorganic lithium adsorbent, the inner core layer is vinyl pyridine-acrylate co-crosslinked hydrophilic polymer doped with inorganic lithium adsorbent, the doping amount of the inorganic lithium adsorbent in the spherical lithium adsorbent is 72wt%, and the following characteristic parameters are as follows in table 3:
TABLE 3
Example 4
Preparing a spherical lithium adsorbent, comprising the following steps:
(1) Preparation of a water phase: 60g of Li having a particle size of 1 μm were weighed 2 TiO 3 5g of methyl methacrylate, 5g of diethylene glycol diacrylate,2gAzodiisobutyl amidine hydrochloride,5g of m-phenylenediamine2g of sodium dodecyl sulfate and 21g of deionized water, and stirring, dissolving and dispersing into uniform slurry to obtain a water phase.
(2) Preparing a mixed solution of terephthaloyl chloride and isooctane: 9g of terephthaloyl chloride and 291g of isooctane are weighed, stirred, dissolved and heated to 40 ℃ to obtain a mixed solution.
Slowly dripping 100g of the prepared water phase into a mixed solution of terephthaloyl chloride and isooctane at the speed of 3.0 s/drop to form spherical particles, then carrying out curing reaction for 10min at the temperature of 40 ℃, and filtering to obtain primary particles with the particle size of 1.5-3.0mm, wherein the uniform coefficient of the particle size is 1.10.
(3) And transferring 96g of primary particles into 200g of isooctane, heating to 85 ℃ under stirring for curing reaction for 15 hours, washing with ethanol, and drying to obtain the spherical lithium adsorbent precursor.
(4) Weighing 20g of the precursor of the spherical lithium adsorbent, adding the precursor into 800mL of dilute hydrochloric acid with the concentration of 0.4mol/L, and removing lithium for 2h at 40 ℃ to obtain the spherical lithium adsorbent.
The spherical lithium adsorbent prepared in this example is spherical in appearance, and includes an inner core layer and an outer shell layer, the outer shell layer is a crosslinked aromatic polyamide doped with an inorganic lithium adsorbent, the inner core layer is a crosslinked acrylate hydrophilic polymer doped with the inorganic lithium adsorbent, and the doping amount of the inorganic lithium adsorbent in the spherical lithium adsorbent is 78wt%, and the following characteristic parameters are as follows in table 4:
TABLE 4
Comparative example 1
6g of polyvinyl chloride having a polymerization degree of 1000 was weighed at room temperature and dissolved in 66mL of NMP, and 20g of LiCl.2Al (OH) having a particle size of 20 μm was added 3 .H 2 And (3) uniformly stirring the precursor O, dripping the precursor O into 400mL of deionized water by using a dropper, and washing and drying to obtain the spherical lithium adsorbent precursor.
Weighing 20g of spherical lithium adsorbent precursor, adding into 800mL of deionized water, and heating to 40 ℃ to remove lithium for 4h to obtain the spherical lithium adsorbent.
The spherical lithium adsorbent prepared by the comparative example is spherical in appearance, and polyvinyl chloride doped with the inorganic lithium adsorbent is arranged inside, and the characteristic parameters are as follows in the following table 5:
TABLE 5
Comparative example 2
70g of Li having a particle size of 15 μm 2 TiO 3 Uniformly mixing the precursor powder with 10g of zinc oxide and 20g of active carbon; adding 30g of EVA emulsion with solid content of 50% into the mixture powder, adding 5mL of water, kneading into dough, extruding and cutting into granules to prepare columnar lithium adsorbent precursor particles with the diameter of 2mm and the length of 1-3mm, and drying at 80 ℃ for 2h; weighing 20g of the dried precursor, adding the precursor into 800mL of dilute hydrochloric acid with the concentration of 0.4mol/L, and removing lithium for 2h at 40 ℃ to obtain the columnar lithium adsorbent.
The lithium adsorbent prepared by the comparative example is a columnar ethylene-vinyl acetate copolymer with the interior doped with the inorganic lithium adsorbent, and the characteristic parameters are as follows in the following table 6:
TABLE 6
The main performance test methods adopted in the examples and comparative examples of the present invention are:
adsorption capacity: adding m into adsorbent m after lithium removal 1 Lithium concentration of C 0 Adsorbing the brine for 20 hours at the rotating speed of 150rpm at room temperature by oscillation, and measuring the lithium concentration C of the supernatant a Then, the adsorption amount (mg/g) = (C) 0 -C a )*m 1 /m/1000。
Adsorption equilibrium time: and (3) taking the supernatant every 1h during adsorption to measure the lithium ion concentration of the supernatant until the time t is required when the lithium concentration is unchanged.
Desorption rate: collecting all the solutions, and measuring their total mass m 2 And lithium ion concentration C d Resolution = C d *m 2 /[(C 0 -C a )*m 1 ]*100％。
The dissolution loss rate: filtering the adsorbent through a 0.5mm filter screen after adsorption is finished every time, collecting and drying fragments, wherein the dissolution loss rate = the total mass m of the fragments after 20 cumulative cycles r Mass m of adsorbent before adsorption 0 *100％。
Lithium extraction application of the adsorbents prepared in examples and comparative examples:
using a zankie halide, the main metal ion component of whichComprises the following steps: na (Na) + Concentration 3% K + Concentration 1% Li + The concentration of Mg is 1000Mg/kg 2+ The concentration was 20mg/kg.
5g of the lithium adsorbent prepared in comparative examples 1-2 and examples 1-4 above was added to 200g of the above Zaubje bittern, and the mixture was subjected to shaking adsorption at 150rpm for 20 hours, and then the adsorbent was filtered off through a filter having a pore size of 0.5mm, and after washing with clean water, the elution was performed under the above-mentioned delithiation conditions according to the corresponding comparative examples and examples preparation methods, respectively, followed by repeating the above adsorption and desorption. After each adsorption, sampling and testing are carried out, the adsorption capacity, the adsorption equilibrium time, the desorption rate and the dissolution loss rate are respectively calculated, and the performances of each sample after 20 periods of adsorption-desorption and adsorption-desorption in the first period are respectively shown in tables 7 and 8:
TABLE 7 first cycle adsorption and desorption Performance of the samples
TABLE 8 Performance of each sample after 20 cycles of adsorption and desorption
As can be seen from the above table, the spherical aluminum-based adsorbent prepared in the first cycle example 1 and the spherical manganese/titanium-based lithium adsorbents prepared in examples 2 to 4 are slightly better than the aluminum-based adsorbent prepared in comparative example 1 and the titanium-based lithium adsorbent prepared in comparative example 2 in terms of adsorption amount, average equilibrium time of adsorption and desorption rate, but the spherical aluminum-based lithium adsorbent prepared in example 1 still has an adsorption amount of 5.6mg/g after 20 cycles of adsorption, and the spherical manganese/titanium-based lithium adsorbent prepared in examples 2 to 4 still has an adsorption amount of more than 9.0mg/g after 20 cycles of adsorption (the adsorption amount of the aluminum-based adsorbent is lower than that of the manganese-based adsorbent or the titanium-based adsorbent), and the dissolution loss rate of the aluminum-based lithium adsorbent after 20 cycles is less than or equal to 1.0%; compared with the aluminum adsorbent obtained in the comparative example 1 and the titanium adsorbent obtained in the comparative example 2, the adsorption amount of the aluminum adsorbent is greatly lower than that of the aluminum adsorbent in the examples after long-period operation, the adsorption equilibrium time of the aluminum adsorbent is longer than that of the titanium adsorbent in the examples, and the adsorption loss of the aluminum adsorbent in the comparative example 2 in the 20 periods is up to 20 percent because the sample prepared in the example (1) is spherical, the friction loss is small under the long-time action of brine, the dissolution loss rate is low, and the adsorption amount retention rate is high; (2) The prepared sample has rich space network structure and hydrophilic skeleton, and is favorable for lithium ion diffusion to the inside of the inorganic adsorbent, so that the lithium ion adsorption is facilitated. The results of the above examples show that the spherical lithium adsorbent prepared by the invention has regular appearance and appearance, stable structure and large lithium ion adsorption capacity.
The spherical lithium adsorbent can be widely applied to extracting lithium from lithium-containing solutions such as salt lake brine, underground brine, seawater, battery recovery solution and the like, and has wide application prospect.
Claims (10)
1. The spherical lithium adsorbent is characterized in that the interior of the spherical lithium adsorbent is a cross-linked network structure doped with an inorganic lithium adsorbent, and the appearance of the spherical lithium adsorbent is spherical;
the cross-linked network structure in the shell is composed of an inner core layer and an outer shell layer, the outer shell layer is cross-linked polyamide doped with an inorganic lithium adsorbent, and the inner core layer is a cross-linked hydrophilic polymer doped with the inorganic lithium adsorbent;
the cross-linked polyamide doped with the inorganic lithium adsorbent is prepared by mixing polyamine monomers and acyl chloride with inorganic lithium adsorbent precursors through polycondensation, and the cross-linked hydrophilic polymer doped with the inorganic lithium adsorbent is prepared by mixing hydrophilic monomers with the inorganic lithium adsorbent precursors through free radical polymerization.
2. The spherical lithium adsorbent according to claim 1, wherein the inorganic lithium adsorbent is a material having a specific adsorption effect on lithium ions, and is produced by delithiating an inorganic lithium adsorbent precursor;
the inorganic adsorbent precursor is selected from LiCl.2Al (OH) 3 .nH 2 O、LiMn 2 O 4 、Li 1.6 Mn 1.6 O 4 、Li 1.33 Mn 1.67 O 4 、Li 2 TiO 3 、Li 4 Ti 5 O 12 One or more of;
the particle size of the inorganic adsorbent precursor is 0.1-100 μm, preferably 1-60 μm;
the polyamine monomer is selected from one or more of nitrogen heterocyclic, aromatic and aliphatic polyamine monomers, preferably one or more of melamine, piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine, and more preferably one or more of melamine, piperazine, m-phenylenediamine, o-phenylenediamine and p-phenylenediamine;
the acyl chloride is selected from one or more of trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride;
the hydrophilic monomer is slightly water soluble or water soluble monomer, and is selected from one or more of vinyl, acrylonitrile, acrylic acid (salt or ester) and acrylamide hydrophilic monomers, preferably one or more of sodium p-vinylbenzene sulfonate, sodium vinylsulfonate, 2-acrylamido-2-methylpropanesulfonic acid (sodium), acrylonitrile, (sodium (meth) acrylate), (methyl) acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol methacrylate, vinylpyridine, vinylpyrrolidone, acrylamide, methacrylamide, N-methylolacrylamide, N-dimethylacrylamide and N-isopropylacrylamide, more preferably one or more of sodium vinylbenzene sulfonate, (sodium (meth) acrylate), (methyl) acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinylpyridine, vinylpyrrolidone, acrylamide and N-methylolacrylamide.
3. The spherical lithium sorbent according to claim 1 or 2, wherein the spherical lithium sorbent is internally doped with an inorganic lithium sorbent in an amount of 30 to 85wt%, preferably 50 to 80wt%;
the particle size of the spherical lithium adsorbent is 0.5-5mm, and the thickness of the shell layer is 0.5-10 μm;
the spherical lithium adsorbent is spherical, the particle size uniformity coefficient is less than or equal to 1.4, the density is 1.0-1.4g/mL, and the specific surface area is more than or equal to 40m 2 Per g, the aperture is 4.0-50nm, and the pore volume is 0.1-0.5cm 3 /g。
4. A method for preparing a spherical lithium adsorbent according to any one of claims 1 to 3, comprising the steps of:
(1) Uniformly mixing an inorganic lithium adsorbent precursor, a hydrophilic monomer, a cross-linking agent, an initiator, a polyamine monomer, an auxiliary agent and water to obtain a water phase;
(2) Dropwise adding the water phase into a mixed solution of acyl chloride and an organic solvent A to form spherical particles, and then carrying out a curing reaction to obtain primary particles;
(3) Adding the primary particles into an organic solvent B, stirring, heating, curing, washing and drying to obtain a spherical lithium adsorbent precursor;
(4) And (3) eluting lithium from the spherical lithium adsorbent precursor by using an eluent to obtain the spherical lithium adsorbent.
5. The preparation method according to claim 4, wherein in the step (1), the aqueous phase comprises the following components in percentage by mass: 20-60%, preferably 30-60% of inorganic lithium adsorbent precursor; 2-15%, preferably 2-10% of hydrophilic monomer; 5-15% of a cross-linking agent, preferably 10-15%; initiator 0.1-2%, preferably 0.5-1.5%; polyamine monomer 2-5%, preferably 2-3%; 0.1 to 3 percent of auxiliary agent, preferably 1 to 3 percent; the balance of water.
6. The production method according to claim 4 or 5, wherein in the step (1), the crosslinking agent is selected from one or more of N, N-methylene bisacrylamide, trimethylolpropane diallyl ether, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, preferably one or more of N, N-methylene bisacrylamide, trimethylolpropane diallyl ether, diethylene glycol diacrylate;
the initiator is one or more selected from azobisisobutyronitrile, dibenzoyl peroxide, cumene hydroperoxide, ammonium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisdiisopropylimidazoline, and preferably one or more selected from azobisisobutyronitrile, dibenzoyl peroxide, ammonium persulfate and potassium persulfate;
the auxiliary agent is selected from one or more of polyvinyl alcohol, sodium stearate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
7. The production method according to any one of claims 4 to 6, wherein, in the step (2), the acid chloride is mixed with the organic solvent A, wherein the concentration of the acid chloride is 1 to 5wt%, preferably 1 to 3wt%;
the acyl chloride is selected from one or more of trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride;
the organic solvent A is selected from one or more of C6-C20 cyclic, normal and isoparaffin, preferably one or more of C6-C10 cyclic, normal and isoparaffin; more preferably one or more of n-hexane, n-heptane, n-octane, n-nonane and n-decane;
the mass ratio of the mixed solution of the acyl chloride and the organic solvent A to the water phase is 1-10, preferably 2;
when the water phase is dripped into the mixed solution of acyl chloride and the organic solvent A, the dripping speed is 0.2-3 seconds per drop, preferably 0.5-1.5 seconds per drop;
in the dropping process, the temperature of the mixed solution of acyl chloride and the organic solvent A is 20-40 ℃, preferably 25-40 ℃;
the curing reaction is carried out at the reaction temperature of 20-40 ℃, preferably 25-40 ℃; the reaction time is 0.5-10min, preferably 2-10min;
the primary particles have a particle size of 0.5-5mm, preferably 0.5-3mm; the coefficient of particle size uniformity is less than or equal to 1.40.
8. The process according to any one of claims 4 to 7, wherein in step (3), the organic solvent B is selected from one or more C6-C20 cyclic, normal, and isoparaffins, preferably one or more C6-C10 cyclic, normal, and isoparaffins; more preferably one or more of n-hexane, n-heptane, n-octane, n-nonane and n-decane;
the mass ratio of the organic solvent B to the primary particles is 1;
the heating curing is carried out, wherein the curing temperature is 50-90 ℃, and preferably 65-90 ℃; the curing time is 2-20h, preferably 8-15h.
9. The process according to any one of claims 4 to 8, wherein in the step (4), the eluent is selected from water or a dilute acid solution having a hydrogen ion concentration of 0.1 to 1 mol/L;
wherein the dilute acid solution is selected from one or more of hydrochloric acid, nitric acid and sulfuric acid;
the dosage of the eluent is 20-100mL/g adsorbent precursor;
the temperature of the clean lithium is 15-70 ℃, preferably 15-50 ℃; the time is 0.5-24h, preferably 2-10h.
10. The spherical lithium adsorbent of any one of claims 1 to 3 or the spherical lithium adsorbent prepared by the preparation method of any one of claims 4 to 9 is applied to the field of lithium extraction of lithium ion-containing solution systems, and is particularly suitable for lithium extraction of salt lake brine, underground brine, seawater and battery recovery solutions with lithium ion concentration of 20 to 2000 ppm.
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