CN111229183A - Preparation method of crown ether functionalized porous multi-cavity microsphere adsorbent and application of adsorbent in lithium ion adsorption - Google Patents
Preparation method of crown ether functionalized porous multi-cavity microsphere adsorbent and application of adsorbent in lithium ion adsorption Download PDFInfo
- Publication number
- CN111229183A CN111229183A CN202010060930.1A CN202010060930A CN111229183A CN 111229183 A CN111229183 A CN 111229183A CN 202010060930 A CN202010060930 A CN 202010060930A CN 111229183 A CN111229183 A CN 111229183A
- Authority
- CN
- China
- Prior art keywords
- crown ether
- porous multi
- preparation
- gma
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 46
- 150000003983 crown ethers Chemical class 0.000 title claims abstract description 43
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 39
- 239000004005 microsphere Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 13
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 53
- ZMXDDKWLCZADIW-UHFFFAOYSA-N Vilsmeier-Haack reagent Natural products CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- -1 2-aminoethyl benzo-12-crown-4 Chemical compound 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 2
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000003995 emulsifying agent Substances 0.000 abstract description 3
- 238000000265 homogenisation Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
- 238000004945 emulsification Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002156 adsorbate Substances 0.000 description 4
- 230000002860 competitive effect Effects 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PVDDBYSFGBWICV-UHFFFAOYSA-N 1,4,8,11-tetraoxacyclotetradecane Chemical compound C1COCCOCCCOCCOC1 PVDDBYSFGBWICV-UHFFFAOYSA-N 0.000 description 1
- CRWZWBQWZASLBK-UHFFFAOYSA-N 1,4,8,12-tetraoxacyclopentadecane Chemical compound C1COCCCOCCOCCCOC1 CRWZWBQWZASLBK-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of chemical separation functional materials, and relates to a preparation method of a crown ether functionalized porous multi-cavity microsphere adsorbent. The invention utilizes hydrogen bond between polystyrene-poly-tetraethyl pyridine and trifluoroacetic acid to construct amphiphilic supermolecular emulsifier, water-in-oil-in-water (W/O/W) double emulsion obtained by one-step homogenization method is introduced into oil phase with monomer glycidyl methacrylate of epoxy group, and crosslinking is carried outEthylene glycol dimethacrylate and 2-hydroxy-2-methyl-1-phenyl-1-acetone as an agent are initiated by ultraviolet light to prepare the porous multi-cavity microsphere, and then the synthesized interface is post-modified by 2-aminoethylbenzo-12-crown-4 to prepare the functionalized porous multi-cavity microsphere. The crown ether functionalized porous multi-cavity microsphere adsorbent prepared by the invention is rich in porous structure, has excellent chemical and mechanical mass transfer dynamic performance and good acid-base response performance, and can be used as an adsorbent for Li+Has specific adsorption capacity.
Description
Technical Field
The invention belongs to the technical field of chemical separation functional materials, and relates to a preparation method of a crown ether functionalized porous multi-cavity microsphere adsorbent and application of the adsorbent to lithium ion adsorption.
Background
Lithium (lithonium) plays an irreplaceable role in the modern industrial fields of batteries, ceramics, lubricants, medicines, etc. due to its unique properties, and has an important commercial value. In view of the rapid increase in global lithium consumption, the subject of extracting lithium from waste batteries or salt lakes is attracting much attention. It is known that most of the lithium resources in nature are mainly present in salt lakes in america and asia as important strategic resources. How to extract lithium ions (Li) from salt lake by using economical, efficient and environment-friendly method+) Is one of the hot research subjects in the technical fields of chemical engineering and separation. Methods such as liquid-liquid extraction, chemical precipitation, solid-liquid extraction, ion exchange and adsorption have been explored. Among them, the adsorption method has become a method for extracting lithium ions (Li) due to the advantages of simple operation, low cost, high adsorption efficiency, less generation of secondary pollutants, and the like+) The most widely used method. Whereas interfering ions (Na) in salt lakes+、K+、Ca2+、Mg2+Etc.) in large numbers relative to other cations, especially magnesium ions (Mg)2+) In other words, lithium ion (Li)+) The concentration is low, and the adsorption effect on the sodium chloride is not obvious. Therefore, an adsorbent having fast kinetic adsorption properties and excellent selectivity is urgently required for capturing lithium from a salt lake.
Double emulsions are considered to be multiphase systems consisting of droplets of one dispersed phase containing droplets or bubbles of another incompatible phase. In recent years, two types of double emulsions, water-in-oil-in-water (W/O/W) and oil-in-water-in-oil (O/W/O), have been widely used as templates for the preparation of microcapsules and macroporous polymers. Common double emulsion preparations typically require a two-step emulsification process, such that the combination between two specific surfactants or solid particles is involved throughout the emulsification process. However, as a thermodynamically unstable system with larger droplets, the two-step emulsification process can also result in the breaking of water droplets inside the double emulsion, even if relatively weak shear forces are used in the second emulsification step. In contrast, double emulsions prepared by a one-step emulsion process can avoid this instability and simplify the preparation process. For the preparation of double emulsions by the one-step emulsification method, appropriate amphiphilic emulsifiers are selected to simultaneously stabilize two different curvatures of the oil-water interface, such as polymethyl methacrylate-and-dimethylaminopropyl methacrylate amine, polypropylene dodecyl ester-and-acrylic acid, and poly (ethylene glycol-and-polystyrene). However, the type of amphiphilic block copolymer used to form the double emulsion is relatively fixed and the phase separation of the emulsion cannot be precisely controlled. Recently, studies have pointed out that the amphiphilicity of block copolymers can be regulated by supramolecular interaction, and thus a simple and versatile method has been developed. For example, in the presence of trifluoroacetic acid micromolecules, the amphipathy of the poly (styrene-o-tetravinyl pyridine) block copolymer is adjusted through the supermolecule action of carboxyl and pyridine groups, and a double-emulsion template can be prepared according to a one-step emulsification method to obtain a porous polymer with high specific surface area. At present, the preparation of a porous adsorbent capable of effectively extracting lithium by a double emulsion template emulsified by a one-step method is not reported.
Crown Ethers (CE) are a very useful class of ether macrocyclic ligands with a specific cavity structure capable of targeting Li via a "size-matching" relationship+The alkali metal and alkaline earth metal cations have excellent selectivity. Thus, CEs have been widely used as Li+An effective extractant for liquid-liquid extraction. In recent years, several strategies by graft polymerization, interfacial post-modification and co-deposition modification have been considered as important methods for immobilizing CEs on solid supports, the resulting adsorbent being directed towards Li+Has good performance. These curing techniques make the adsorbent susceptible to CE loss or low binding site density. The strategy of post-modification of synthetic interface is utilized to connect CEs and a solid carrier through covalent bond, thereby providing a more convenient and feasible way to obtain the Li+The recovered crown ether supported adsorbent.
The ultraviolet light initiated polymerization technology can not generate extra heat in the polymerization process, has high polymerization rate and is widely applied, and the preparation of the photoinitiated emulsion template has greater advantages, so that emulsion breaking caused by the instability of the emulsion in the preparation process can be prevented, and the expected shape cannot be obtained.
Disclosure of Invention
In order to solve the existing problems, the invention utilizes a strategy of combining a double-emulsion template with a supramolecular regulation one-step method and ultraviolet light to initiate polymerization to prepare the porous multi-cavity microsphere (Macro-GMA) with a large amount of epoxy groups on the surface, and then introduces 2-aminoethyl benzo-12-crown-4 (AB12C4) functional sites through a synthesis interface post-modification strategy to prepare the functionalized porous multi-cavity microsphere (Macro-GMA-AB12C4), namely the preparation method of the crown ether functionalized porous multi-cavity microsphere adsorbent is disclosed.
The technical scheme is as follows:
firstly, forming an amphiphilic surfactant through the supermolecule action of trifluoroacetic acid and a polystyrene-co-poly-tetraethyl pyridine (PS-b-P4VP, Mn (16031)) block copolymer, and preparing a water-in-oil (W/O/W) double emulsion by a one-step method by taking dichloromethane as an oil phase and deionized water as a water phase; wherein monomer Glycidyl Methacrylate (GMA), cross-linking agent Ethylene Glycol Dimethacrylate (EGDMA) and photoinitiator 2-hydroxy-2-methyl-1 phenyl-1-acetone (HMPP) are added in advance into methylene dichloride oil phase, and then the porous multi-cavity microsphere (Macro-GMA) is prepared by utilizing an ultraviolet light initiated polymerization strategy; and finally, synthesizing the functionalized porous multi-cavity microsphere (Macro-GMA-AB12C4) with 2-aminoethylbenzo-12-crown-4 (AB12C4) crown ether by adopting an interface post-modification method.
A preparation method of a crown ether functionalized porous multi-cavity microsphere (Macro-GMA-AB12C4) adsorbent comprises the following steps:
(1) adding monomer Glycidyl Methacrylate (GMA), cross-linking agent Ethylene Glycol Dimethacrylate (EGDMA) and photoinitiator 2-hydroxy-2-methyl-1 phenyl-1-acetone (HMPP) into dichloromethane, stirring uniformly to obtain dichloromethane solution, then respectively adding trifluoroacetic acid and polystyrene-poly-tetraethyl pyridine (PS-b-P4VP) into the dichloromethane solution, mixing uniformly, dropwise adding deionized water, and stirring uniformly at high speed to obtain water-in-oil-in-water (W/O/W) double emulsion;
(2) placing a water-in-oil-in-water (W/O/W) double emulsion under ultraviolet light initiation for polymerization for 60-120 min, rinsing the product with ethanol and water for several times, and performing vacuum drying at 40-60 ℃ for 240-360 min, preferably at 45 ℃ for 240min to obtain a Macro-GMA adsorbent substrate with a large amount of epoxy groups on the surface;
(3) adding a Macro-GMA adsorbent substrate into N, N dimethyl formamide (DMF), uniformly stirring, then adding 2-aminoethyl benzo-12-crown-4 (AB12C4) crown ether, uniformly mixing, heating in a constant-temperature water bath at 70 ℃ for reacting for 720-960 min, preferably 720min, and preparing the crown ether functionalized porous multi-cavity microsphere (Macro-GMA-AB12C4) adsorbent.
In a preferred embodiment of the invention, the volume ratio of the trifluoroacetic acid to the dichloromethane in the step (1) is 4.5-5 muL: 3.5-4 mL; the mass-volume ratio of PS-b-P4VP to dichloromethane is 5-6 mg: 5-5.5 mL; the ratio of trifluoroacetic acid, PS-b-P4VP, GMA, EGDMA, HMPP and deionized water is 100-110 muL, 300-320 muL, 5-10 muL, 20-30 muL, 5-10 muL and 400-2000 muL.
In the preferred embodiment of the invention, the high-speed stirring speed in the step (1) is 1000-2000 r/min.
In the preferred embodiment of the present invention, the monomer in step (1) can be selected from 4-nitrophenylacrylate, 2-hydroxyethyl methacrylate, 4-vinylbenzyl chloride, etc., so that the polymer material has a group with high reactivity. Glycidyl methacrylate is a high-reactivity monomer, contains an epoxy group, and the epoxy group can react with nucleophilic reagents such as amino and the like.
In the preferred embodiment of the present invention, the crosslinking agent in step (1) may also be Divinylbenzene (DVB).
In a preferred embodiment of the present invention, the photoinitiator in step (1) may also be an ultraviolet curing acrylic photoinitiator, such as DETX.
In the preferred embodiment of the invention, the mass-volume ratio of the Macro-GMA substrate, AB12C4 and DMF in the step (3) is 200-500 mg: 200-750 mg: 40-50 mL.
In the preferred embodiment of the present invention, the crown ether in step (3) may be 14 crown 4 or 15 crown 4.
The products prepared with or without the addition of AB12C4 crown ether are designated Macro-GMA-AB12C4 or Macro-GMA, respectively, in the present invention.
It is still another object of the present invention to apply the prepared adsorbent to adsorption of lithium ions.
Intermittent simulation dynamic adsorption experiment: adding 5mL of 200mg/L LiCl solution into a centrifuge tube, respectively adding 5mg of crown ether modified and unmodified porous multi-cavity microsphere adsorbents, placing in a constant-temperature water bath tank at 25 ℃ for water bath oscillation for 6 hours, and absorbing Li+Measuring the content by an inductively coupled plasma emission spectrometer (ICP-OES), and calculating the adsorption capacity according to the result; after saturated adsorption, carrying out centrifugal separation by using a high-speed centrifuge at 5000-8000 r, drying, selecting several metal ion solutions with similar structures and properties as competitive adsorbates, and researching the identification performance of the polymer to prove the adsorption effect of the crown ether.
The formula for the calculation of the adsorption capacity is:
wherein Q ise(mg/L) adsorption capacity of adsorbent to adsorbate at equilibrium, C0(mg/L) is the original concentration of adsorbate in solution, Ce(mg/L) is the concentration of adsorbate in solution at equilibrium, V (mL) is the volume of test liquid; m (mg) is the mass of the adsorbent.
Advantageous effects
The invention uses hydrogen bond between polystyrene-and-poly tetraethyl pyridine (PS-b-P4VP) and trifluoroacetic acid to construct amphiphilic supermolecule emulsifier, water-in-oil-in-water (W/O/W) double emulsion obtained by one-step homogenization method is introduced into oil phase to prepare porous multi-cavity microsphere by ultraviolet light initiation, and 2-aminoethylbenzo-12-crown-4 (AB12C4) is used for post-modification of synthesized interface to prepare the functional porous multi-cavity microsphere. The invention also uses the prepared porous microspheres and functional microspheres as adsorbents to capture Li+. The material has a porous structure, excellent chemical and mechanical mass transfer dynamic performance, good acid-base response performance and Li resistance+Has specific adsorption capacity.
Drawings
FIG. 1 microscope image of the W/O/W double emulsion of example 1.
FIG. 2 SEM image of Macro-GMA in example 1.
FIG. 3 Infrared spectra of Macro-GMA and Macro-GMA-AB12C4 in example 1.
FIG. 4 of Macro-GMA and Macro-GMA-AB12C4 in example 113C NMR spectrum.
FIG. 5 is a graph showing adsorption kinetics of Macro-GMA and Macro-GMA-AB12C4 in Experimental example 1.
FIG. 6 is a graph showing isothermal adsorption equilibrium of Macro-GMA and Macro-GMA-AB12C4 in Experimental example 2.
FIG. 7 is a graph showing competitive attraction of Macro-GMA-AB12C4 in Experimental example 3.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
A method for preparing a crown ether functionalized porous multi-cavity microsphere (Macro-GMA-AB12C4) adsorbent comprises the following steps: firstly, respectively adding 5.0mgPs-b-P4VP into 5mL of dichloromethane solution and 4.0 muL of trifluoroacetic acid into 4mL of dichloromethane solution for uniform dissolution, sequentially adding 100 muL of trifluoroacetic acid solution, 300 muL of Ps-b-P4VP solution, 10 muL of glycidyl methacrylate, 20 muL of ethylene glycol dimethacrylate and 10 muL of HMPP photoinitiator into a centrifuge tube, then dropwise adding 2000 muL of deionized water under 1500r high-speed stirring, polymerizing the prepared water-in-oil-in-water (W/O/W) double emulsion for 5min under ultraviolet light for 120min, finally washing with ethanol and distilled water for multiple times, and drying in a vacuum oven at 60 ℃ for 360 min. Mixing 500mg of the product with 300mg of AB12C4 crown ether, adding into 50ml of mixed solution of DMF, uniformly dispersing for 4-6min by ultrasonic waves, and carrying out water bath reaction for 720min at 70 ℃ to obtain a final product Macro-GMA-AB12C 4.
The samples prepared with 0mg and 300mg of AB12C4 crown ether were designated Macro-GMA and Macro-GMA-AB12C4, respectively.
Example 2
A method for preparing a crown ether functionalized porous multi-cavity microsphere (Macro-GMA-AB12C4) adsorbent comprises the following steps: firstly, respectively adding 5.0mgPs-b-P4VP into 5mL of dichloromethane solution and 4.0 muL of trifluoroacetic acid into 4mL of dichloromethane solution for uniform dissolution, sequentially adding 100 muL of trifluoroacetic acid solution, 300 muL of Ps-b-P4VP solution, 10 muL of glycidyl methacrylate, 20 muL of ethylene glycol dimethacrylate and 10 muL of HMPP photoinitiator into a centrifuge tube, then dropwise adding 2000 muL of deionized water under 1500r high-speed stirring, placing the prepared water-in-oil-in-water (W/O/W) double emulsion under ultraviolet light for polymerization for 120min after 5min, finally washing with ethanol and distilled water for multiple times, and placing in a vacuum oven at 60 ℃ for drying for 300 min. Mixing 500mg of the product with 500mg of AB12C4 crown ether, adding into 50ml of mixed solution of DMF, uniformly dispersing for 4-6min by ultrasonic waves, and carrying out water bath reaction for 840min at 70 ℃ to obtain a final product Macro-GMA-AB12C 4.
The samples prepared with 0mg and 500mg of AB12C4 crown ether were designated Macro-GMA and Macro-GMA-AB12C4, respectively.
Example 3
A method for preparing a crown ether functionalized porous multi-cavity microsphere (Macro-GMA-AB12C4) adsorbent comprises the following steps: firstly, respectively adding 5.0mgPs-b-P4VP into 5mL of dichloromethane solution and 4.0 muL of trifluoroacetic acid into 4mL of dichloromethane solution for uniform dissolution, sequentially adding 100 muL of trifluoroacetic acid solution, 300 muL of Ps-b-P4VP solution, 10 muL of glycidyl methacrylate, 20 muL of ethylene glycol dimethacrylate and 10 muL of HMPP photoinitiator into a centrifuge tube, then dropwise adding 2000 muL of deionized water under 1500r high-speed stirring, placing the prepared water-in-oil-in-water (W/O/W) double emulsion under ultraviolet light for polymerization for 120min after 5min, finally washing with ethanol and distilled water for multiple times, and placing in a vacuum oven at 60 ℃ for drying for 240 min. Mixing 500g of the product with 750gAB12C4 crown ether, adding the mixture into 50ml of mixed solution of sulfuric acid and sulfuric acid, uniformly dispersing the mixture for 4 to 6 minutes by using ultrasonic waves, and carrying out water bath reaction for 960 minutes at 70 ℃ to obtain a final product Macro-GMA-AB12C 4.
The samples prepared with 0m g and 750mg of AB12C4 crown ether were designated Macro-GMA and Macro-GMA-AB12C4, respectively.
The identification performance evaluation in the embodiment of the present invention is detailed in experimental examples 1 to 3.
Test example 1
Adding 5mL of LiCl solution with the initial concentration of 200mg/L into a centrifuge tube, respectively adding 10mg of Macro-GMA-AB12C4 in example 1, placing the test solution in a water bath oscillator at 25 ℃, and respectively taking out at 5min, 10min, 20min, 30min, 60min, 120min, 180min, 360min and 480 min; separating porous multi-cavity microsphere adsorbent (Macro-GMA-AB12C4) from the solution by high-speed centrifuge, and collecting Li in the solution+The concentration is determined by ICP-OES, and the adsorption capacity is calculated according to the result; from the results shown in FIG. 4, the adsorption process of Macro-GMA-AB12C4 had a fast adsorption phase in the first 60min due to fast adsorption kinetics, whereas 60min to 360min adsorption slowed down due to the decrease in adsorption sites, and when adsorption reached equilibrium at 480min, the effect of crown ether binding sites on adsorption was demonstrated, possessing fast adsorption kinetics.
Test example 2
In the study of adsorption kinetics and adsorption equilibrium, the adsorption capacity of Macro-GMA-AB12C4 was studied. In adsorption equilibrium experiments, 10mg of Macro-GMA-AB12C4 were placed in centrifuge tubes to prepare different concentrations (20 mgL)-1,30mgL-1,50mgL-1,100mgL-1,200mgL-1) LiCl solution at pH 6. Then, 10mL of Li was added+The test solution was added to the centrifuge tube and the mixture was transferred to a 25 ℃ constant temperature water bath shaking box for 360 min. OscillationAfter a suitable time, Macro-GMA-AB12C4 was collected by high speed centrifugation and the remaining solution was filtered through a microporous nitrocellulose filter membrane (pore size 0.22 μm) to remove suspended particles. Measurement of Li in the obtained filtrate by ICP-OES+And (4) concentration. The whole process should be repeated at least three times, and the results can be derived from FIG. 5, with Li+And the actual adsorption effect of the adsorbent is similar to the fitting result.
Test example 3
Selecting LiCl, KCl and MgCl2、NaCl、CaCl2Separately preparing LiCl, KCl and MgCl for competing adsorbed metal compounds2、NaCl、CaCl2Aqueous solution, the concentration of each competitive adsorbent is 100mg/L, 10mL of prepared solution is added into a centrifuge tube, 10mg of Macro-GMA-AB12C4 adsorbent in example 1 is respectively added, a test solution is put into a constant temperature water bath shaking box at 25 ℃ to be shaken for 360min, after the adsorption time is finished, the test solution is separated and collected by a high-speed centrifuge, the concentration of various non-adsorbed competitive adsorption metal ions is determined by ICP-OES, the result can be obtained from the graph of FIG. 7, and the Macro-GMA-AB12C4 adsorbent is used for Li+、Na+、K+、Ca2+、Mg2+The adsorption capacities of (1) and (2) were 13.6mg/g, 2.6mg/g,1.6mg/g, 2.2mg/g and 3.5mg/g, respectively, at a pH of 6. Indicating Macro-GMA-AB12C4 vs Li+Has obvious specific recognition compared with other competitors, and the adsorption capacity is higher than that of other metal ions. Macro-GMA-AB12C4 vs Li at pH 6+The porous multi-cavity microsphere adsorbent has more excellent adsorption effect, and can prove the successful synthesis of the crown ether modified porous multi-cavity microsphere adsorbent.
From the image of fig. 1, a water-in-oil-in-water (W/O/W) double emulsion microscopic image of different morphologies obtained by adjusting the oil-to-water ratio can be observed, which proves the success of double emulsion preparation.
As can be seen from FIG. 2, the double emulsions obtained by different oil-water ratios are polymerized under the initiation of ultraviolet light to obtain SEM images with different shapes. As can be seen from the figure, the Macro-GMA surface has a large number of micropores and the interior has a structure in which a large number of cavities are connected, thus proving the successful preparation of the porous multi-cavity microspheres.
From Macro-GMA and GMA of FIG. 3The infrared spectrum of the Macro-GMA-AB12C4 can be clearly observed that the epoxy group is 907cm-1And 804cm-1The absorption band of (A), which illustrates the successful introduction of GMA as a functional monomer, compared to the Macro-GMA, which has a C-O six-membered ring AB12C4 at 1060cm on AB12C4-1A new absorption peak appeared, and the peak intensity of the epoxy group was also reduced, indicating that the AB12C4 crown was successfully modified on Macro-GMA.
From the solid nuclear magnetic spectrum of fig. 4, it can be seen that the chemical shifts of Macro-GMA-AB12C4 appear as two new peaks at 74.07 and 118.8, corresponding to the crown ether ring of AB12C4 and the carbon corresponding to the benzene ring, respectively, compared with Macro-GMA. At the same time, the peak around 60 shifted, probably due to the ring-opening reaction of the amino group on AB12C4 with the epoxy bond of Macro-GMA. These phenomena demonstrate the successful immobilization of crown ethers on the surface of porous microsphere materials.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A preparation method of a crown ether functionalized porous multi-cavity microsphere adsorbent is characterized by comprising the following steps:
(1) adding monomer glycidyl methacrylate GMA, cross-linking agent ethylene glycol dimethacrylate EGDMA and photoinitiator 2-hydroxy-2-methyl-1 phenyl-1-acetone HMPP into dichloromethane, stirring uniformly to form dichloromethane solution, then respectively adding trifluoroacetic acid and polystyrene-poly-tetraethyl pyridine PS-b-P4VP into the dichloromethane solution, mixing uniformly, dropwise adding deionized water, and stirring uniformly at high speed to obtain water-in-oil-in-water (W/O/W) double emulsion;
(2) placing a water-in-oil-in-water (W/O/W) double emulsion under ultraviolet light initiation for polymerization for 60-120 min, rinsing the product with ethanol and water for several times, and drying in vacuum at 40-60 ℃ for 240-360 min to obtain a Macro-GMA adsorbent substrate with a large number of epoxy groups on the surface;
(3) adding a Macro-GMA adsorbent substrate into N, N dimethyl formamide DMF (dimethyl formamide) and uniformly stirring, then adding 2-aminoethyl benzo-12-crown-4 (AB12C4) crown ether and uniformly mixing, heating in a constant-temperature water bath at 70 ℃ and reacting for 720-960 min, preferably 720min, thus obtaining the product.
2. The preparation method of the crown ether functionalized porous multi-cavity microsphere adsorbent according to claim 1, which is characterized by comprising the following steps: the volume ratio of the trifluoroacetic acid to the dichloromethane in the step (1) is 4.5-5 muL: 3.5-4 mL; the mass-volume ratio of PS-b-P4VP to dichloromethane is 5-6 mg: 5-5.5 mL; the ratio of trifluoroacetic acid, PS-b-P4VP, GMA, EGDMA, HMPP and deionized water is 100-110 muL to 300-320 muL to 5-10 muL to 20-30 muL to 5-10 muL to 400-2000 muL.
3. The preparation method of the crown ether functionalized porous multi-cavity microsphere adsorbent according to claim 1, which is characterized by comprising the following steps: the high-speed stirring speed in the step (1) is 1000-2000 r/min.
4. The preparation method of the crown ether functionalized porous multi-cavity microsphere adsorbent according to claim 1, which is characterized by comprising the following steps: the monomer in the step (1) can also be selected from 4-nitrophenylacrylate, 2-hydroxyethyl methacrylate and 4-vinylbenzyl chloride.
5. The preparation method of the crown ether functionalized porous multi-cavity microsphere adsorbent according to claim 1, which is characterized by comprising the following steps: the crosslinking agent in step (1) may also be Divinylbenzene (DVB).
6. The preparation method of the crown ether functionalized porous multi-cavity microsphere adsorbent according to claim 1, which is characterized by comprising the following steps: the photoinitiator in the step (1) can also be an ultraviolet curing acrylic photoinitiator.
7. The preparation method of the crown ether functionalized porous multi-cavity microsphere adsorbent according to claim 1, which is characterized by comprising the following steps: and (3) rinsing the product in the step (2) with ethanol and water for several times, and performing vacuum drying at 45 ℃ for 240 min.
8. The preparation method of the crown ether functionalized porous multi-cavity microsphere adsorbent according to claim 1, which is characterized by comprising the following steps: in the step (3), the mass-volume ratio of the Macro-GMA substrate, AB12C4 and DMF is 200-500 mg: 200-750 mg: 40-50 mL.
9. The preparation method of the crown ether functionalized porous multi-cavity microsphere adsorbent according to claim 1, which is characterized by comprising the following steps: the crown ether in step (3) may also be crown 14 or crown 4 15.
10. Use of a crown ether functionalized porous multi-cavity microsphere adsorbent prepared according to any one of claims 1 to 9, wherein: the method is applied to the adsorption of lithium ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010060930.1A CN111229183B (en) | 2020-01-19 | 2020-01-19 | Preparation method of crown ether functionalized porous multi-cavity microsphere adsorbent and application of adsorbent in lithium ion adsorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010060930.1A CN111229183B (en) | 2020-01-19 | 2020-01-19 | Preparation method of crown ether functionalized porous multi-cavity microsphere adsorbent and application of adsorbent in lithium ion adsorption |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111229183A true CN111229183A (en) | 2020-06-05 |
| CN111229183B CN111229183B (en) | 2021-11-23 |
Family
ID=70863531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010060930.1A Active CN111229183B (en) | 2020-01-19 | 2020-01-19 | Preparation method of crown ether functionalized porous multi-cavity microsphere adsorbent and application of adsorbent in lithium ion adsorption |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111229183B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112642412A (en) * | 2020-12-18 | 2021-04-13 | 江苏大学 | Method for preparing crown ether functionalized porous microsphere adsorbent by one-step double-emulsion template method |
| CN113634238A (en) * | 2021-07-15 | 2021-11-12 | 江苏大学 | Flexible porous boron affinity copolymer adsorbent and preparation method and application thereof |
| CN113634239A (en) * | 2021-07-23 | 2021-11-12 | 江苏大学 | Method for preparing crown ether functionalized nanosheet by one-step Pickering double-emulsion method and application of crown ether functionalized nanosheet in lithium extraction |
| CN114522674A (en) * | 2021-12-20 | 2022-05-24 | 南京亘闪生物科技有限公司 | Preparation method of microsphere with ultrahigh specific surface area for amine substance adsorption |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443088A (en) * | 2011-09-22 | 2012-05-09 | 中国科学院过程工程研究所 | Uniform-size small-particle-size super-macroporous polymer microspheres and preparation method thereof |
| CN103374143A (en) * | 2012-04-28 | 2013-10-30 | 中国科学院过程工程研究所 | Super macroporous polymer microspheres and preparation method thereof |
| CN107115846A (en) * | 2017-05-11 | 2017-09-01 | 清华大学 | A kind of immobilized glass fiber material of crown ether and preparation method thereof |
| WO2019161171A1 (en) * | 2018-02-16 | 2019-08-22 | Sperovie Biosciences, Inc. | Nanoparticle formulations of sting agonists |
| CN110227424A (en) * | 2019-06-28 | 2019-09-13 | 江苏大学 | A kind of preparation method and applications of covalent modification high density crown ether functionalization porous adsorbent |
| CN110404514A (en) * | 2019-06-28 | 2019-11-05 | 江苏大学 | A kind of method of the light-initiated preparation high density crown ether site porous adsorbent in surface |
-
2020
- 2020-01-19 CN CN202010060930.1A patent/CN111229183B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443088A (en) * | 2011-09-22 | 2012-05-09 | 中国科学院过程工程研究所 | Uniform-size small-particle-size super-macroporous polymer microspheres and preparation method thereof |
| CN103374143A (en) * | 2012-04-28 | 2013-10-30 | 中国科学院过程工程研究所 | Super macroporous polymer microspheres and preparation method thereof |
| CN107115846A (en) * | 2017-05-11 | 2017-09-01 | 清华大学 | A kind of immobilized glass fiber material of crown ether and preparation method thereof |
| WO2019161171A1 (en) * | 2018-02-16 | 2019-08-22 | Sperovie Biosciences, Inc. | Nanoparticle formulations of sting agonists |
| CN110227424A (en) * | 2019-06-28 | 2019-09-13 | 江苏大学 | A kind of preparation method and applications of covalent modification high density crown ether functionalization porous adsorbent |
| CN110404514A (en) * | 2019-06-28 | 2019-11-05 | 江苏大学 | A kind of method of the light-initiated preparation high density crown ether site porous adsorbent in surface |
Non-Patent Citations (7)
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112642412A (en) * | 2020-12-18 | 2021-04-13 | 江苏大学 | Method for preparing crown ether functionalized porous microsphere adsorbent by one-step double-emulsion template method |
| CN113634238A (en) * | 2021-07-15 | 2021-11-12 | 江苏大学 | Flexible porous boron affinity copolymer adsorbent and preparation method and application thereof |
| CN113634238B (en) * | 2021-07-15 | 2023-09-26 | 江苏大学 | Flexible porous boron affinity copolymer adsorbent and preparation method and application thereof |
| CN113634239A (en) * | 2021-07-23 | 2021-11-12 | 江苏大学 | Method for preparing crown ether functionalized nanosheet by one-step Pickering double-emulsion method and application of crown ether functionalized nanosheet in lithium extraction |
| CN113634239B (en) * | 2021-07-23 | 2023-05-05 | 江苏大学 | Method for preparing crown ether functionalized nano-sheet by one-step Pickering double-emulsion method and lithium extraction application thereof |
| CN114522674A (en) * | 2021-12-20 | 2022-05-24 | 南京亘闪生物科技有限公司 | Preparation method of microsphere with ultrahigh specific surface area for amine substance adsorption |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111229183B (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111229183B (en) | Preparation method of crown ether functionalized porous multi-cavity microsphere adsorbent and application of adsorbent in lithium ion adsorption | |
| US7955592B2 (en) | Selective separation of heavy metal ion using metal ion imprinted polymer (MIIP) | |
| JP5131911B2 (en) | Monolithic organic porous body, production method thereof, and monolithic organic porous ion exchanger | |
| Yang et al. | Capturing lithium using functional macroporous microspheres with multiple chambers from one-step double emulsion via a tailoring supramolecular route and postsynthetic interface modification | |
| WO2009020649A1 (en) | Suspension homopolymerization of an isocyanurate | |
| CN112023899A (en) | Preparation method of hydrophilic flexible porous boron affinity imprinted hydrogel adsorbent | |
| CN104910313B (en) | Prepare method and the application of Modified with Polar Monomer hypercrosslinked polymeric resin | |
| CN104262521B (en) | The preparation method of styrene divinylbenzene copolymer hydrophobic catalyst carrier | |
| CN110227424B (en) | Preparation method and application of covalent modification high-density crown ether functionalized porous adsorbent | |
| CN111437798A (en) | Amidoxime group hypercrosslinked microporous resin efficient uranium adsorbent and preparation method thereof | |
| CN106749830A (en) | A kind of preparation method of magnetic porous molecularly imprinted polymer | |
| CN107973873A (en) | A kind of preparation method of super-hydrophobic high resistance to compression styrene diethylene benzene copoly mer catalyst carrier | |
| Yang et al. | One-step double emulsion via amphiphilic SeN supramolecular interactions: Towards porous multi-cavity beads for efficient recovery lithium from brine | |
| CN115490879A (en) | EDTA (ethylene diamine tetraacetic acid) -modified UIO-66 (Zr) metal organic framework material as well as preparation method and application thereof | |
| Hu et al. | Hierarchically porous MOFs self-supporting copolymers for ultrafast transport and precise recognition of flavonoids: A triple interfacial crosslinking strategy based on microreactors | |
| Cejner et al. | Ion-imprinted polymers: synthesis, characterization and applications | |
| CN112642412A (en) | Method for preparing crown ether functionalized porous microsphere adsorbent by one-step double-emulsion template method | |
| CN113634238B (en) | Flexible porous boron affinity copolymer adsorbent and preparation method and application thereof | |
| CN107570124A (en) | Function monomer for preparing bisphenol-A trace mesoporous material and preparation method thereof | |
| CN114736338B (en) | Cationic covalent organic framework material and preparation method and application thereof | |
| CN114160103B (en) | Preparation method of three-dimensional large Kong Xiean oximation ion gel adsorbent | |
| CN106512877B (en) | A kind of preparation method of the propionating chitosan microball of ethylenediamine | |
| CN109320662A (en) | Magnetic blotting is crosslinked the preparation of AA/AM/BA grafting esterification cyanoethyl tapioca microballoon and the absorption to copper ion | |
| JP4315337B2 (en) | Non-particulate organic porous material having optical resolution and method for producing the same | |
| CN113634239B (en) | Method for preparing crown ether functionalized nano-sheet by one-step Pickering double-emulsion method and lithium extraction application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230803 Address after: 230000 Room 203, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee after: Hefei Jiuzhou Longteng scientific and technological achievement transformation Co.,Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: JIANGSU University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231127 Address after: Room 581, Port Building, No. 2001 Gaolan Port Avenue, Gaolan Port Economic Zone, Zhuhai City, Guangdong Province, 519000 Patentee after: Zhuhai Chenyu New Material Technology Co.,Ltd. Address before: 230000 Room 203, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee before: Hefei Jiuzhou Longteng scientific and technological achievement transformation Co.,Ltd. |