CN114471177B - Anion exchange driven cation selective separation hybrid membrane and preparation and application thereof - Google Patents
Anion exchange driven cation selective separation hybrid membrane and preparation and application thereof Download PDFInfo
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- CN114471177B CN114471177B CN202210114311.5A CN202210114311A CN114471177B CN 114471177 B CN114471177 B CN 114471177B CN 202210114311 A CN202210114311 A CN 202210114311A CN 114471177 B CN114471177 B CN 114471177B
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- 238000000926 separation method Methods 0.000 title claims abstract description 89
- 239000012528 membrane Substances 0.000 title claims abstract description 83
- 150000001768 cations Chemical class 0.000 title claims abstract description 76
- 238000005349 anion exchange Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 45
- 238000005266 casting Methods 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000013384 organic framework Substances 0.000 claims abstract description 12
- 239000012267 brine Substances 0.000 claims abstract description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 238000000935 solvent evaporation Methods 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 239000013207 UiO-66 Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 13
- 229920002492 poly(sulfone) Polymers 0.000 claims description 12
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 11
- 239000012621 metal-organic framework Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000009396 hybridization Methods 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- 239000013310 covalent-organic framework Substances 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 150000003235 pyrrolidines Chemical class 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 17
- 230000004907 flux Effects 0.000 abstract description 14
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000012216 screening Methods 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 238000002791 soaking Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229920006380 polyphenylene oxide Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 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 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 230000032895 transmembrane transport Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- RAADBCJYJHQQBI-UHFFFAOYSA-N 2-sulfoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 RAADBCJYJHQQBI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
-
- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/42—Ion-exchange membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Manufacturing & Machinery (AREA)
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- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of separation membrane materials, and discloses an anion exchange driven cation selective separation hybrid membrane, and preparation and application thereof, wherein the anion exchange membrane is taken as a base membrane, and the membrane material with enhanced cation selective separation performance is obtained by doping porous materials such as an organic framework and the like; specifically, an anion exchange membrane polymer is dissolved in an organic solvent to prepare a polymer solution; adding organic frame material powder into a polymer solution and stirring to obtain uniform casting solution; preparing the obtained casting film liquid into a film by a solvent evaporation method; the prepared typical hybrid membrane has wide application prospect in the fields of salt lake brine lithium extraction, waste acid recovery and the like. The invention uses the difference of cation permeation rates in the anion exchange membrane to apply the anion exchange membrane to the selective separation of cations; the size screening and functional group screening of the organic frame material are utilized to improve the cation selective separation performance of the anion exchange membrane, so that the doped membrane has high cation transmission flux and selectivity.
Description
Technical Field
The invention belongs to the technical field of separation membrane materials, and particularly relates to a cation selective separation hybrid membrane, a preparation method and application thereof.
Background
Resource shortage and environmental pollution caused by rapid global development are significant challenges facing sustainable development in modern society. The selective extraction of certain cations from water resources such as seawater, salt lake brine and the like is an important way for relieving the crisis of resource shortage and meeting the demands of production and life; in addition, effective separation of useful resources from industrial wastewater can also improve the utilization rate of resources while reducing environmental pollution. In recent years, the application of cation separation in the fields of salt lake brine lithium extraction, acid recovery in acid pickling waste liquid and the like has been receiving attention.
Cation selective separation membranes are one of the effective methods for cation selective separation, and common cation selective separation membrane materials include organic membrane materials, inorganic membrane materials, and the like. The organic film material has the advantages of convenient film formation, compact film without defects, good flexibility and the like, but the ion selectivity of the organic film is lower. And the existing organic cation selective separation membrane has a counter relationship between ion transmission flux and ion selectivity, so that the cation transmission flux of the membrane is improved to reduce the selectivity of cations, and the transmission flux of the cations is also required to be sacrificed to improve the selectivity of the cations. Although the inorganic film material has higher ion selectivity, the film formation is easy to generate defects, and a large-scale and large-area production method is not available at present.
Disclosure of Invention
The invention aims to solve the technical problem that the ion selectivity and the transmission flux of the existing cation separation membrane are difficult to be compatible, and provides an anion exchange driven cation selective separation hybrid membrane, a preparation method and application thereof; wherein, the invention can effectively separate Li + /Mg 2+ 、Fe 2+ /H + The cation separation membrane has good application value in the fields of extracting lithium from salt lake brine and recovering waste acid.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the present invention, there is provided a method of forming an anion exchange membrane by doping an organic framework material, and which is obtained by the following preparation method:
(1) Preparing a casting solution: dissolving an anion exchange polymer in an organic solvent, and adding an organic frame material to obtain a casting solution with the organic frame material uniformly dispersed;
(2) Preparation of the film: and (3) preparing the casting solution into a film by a solvent evaporation method.
Further, the skeleton of the anion exchange polymer is one of polyphenyl ether, polysulfone and polyether-ether-ketone, and the anion exchange group of the anion exchange polymer is one of quaternary ammonium salt, imidazole salt and pyrrolidine salt.
Further, the organic framework material is a metal organic framework material or a covalent organic framework material.
Further, the organic solvent is N, N-dimethylformamide or N-methylpyrrolidone.
Further, the organic framework material comprises 5-40% by mass of the anion exchange polymer.
Further, in the step (1), the mass ratio of the anion exchange polymer to the organic solvent is 1:2.5-10; the membrane casting liquid is prepared by adopting ultrasonic dispersion or stirring dispersion, and the time of ultrasonic dispersion or stirring dispersion is 20-120 min.
Further, in the step (2), the drying temperature of the solvent evaporation method is 50-180 ℃ and the drying time is 6-48 h.
Further, the anion exchange polymer is one of quaternized polyphenyl ether or quaternized polysulfone; the organic framework material is one of UiO-66, sulfonated UiO-66, MOF-808, sulfonated MOF-808, tpPa-1 and TpPa-2.
According to another aspect of the present invention, there is provided a method for preparing the above-described cation selective separation hybrid membrane, comprising the steps of:
(1) Preparing a casting solution: dissolving an anion exchange polymer in an organic solvent, and adding an organic frame material to obtain a casting solution with the organic frame material uniformly dispersed;
(2) Preparation of the film: and (3) preparing the casting solution into a film by a solvent evaporation method.
According to another aspect of the invention, there is provided the use of the above-described cation selective separation hybrid membrane in salt lake brine lithium extraction and/or spent acid recovery; the anion exchange polymer is one of quaternized polyphenyl ether or quaternized polysulfone; the organic framework material is one of UiO-66, sulfonated UiO-66, MOF-808, sulfonated MOF-808, tpPa-1 and TpPa-2.
The beneficial effects of the invention are as follows:
according to the cation selective separation hybrid membrane and the preparation method thereof, the exchange of anions in the membrane drives the separation of cations in the membrane, and meanwhile, the concentration diffusion at two sides of the membrane is utilized to provide the driving force of anions and cations, so that energy is not required to be additionally provided, and the energy is saved and the environment is protected; the doping of the organic framework material provides screening sites for cations, and the selectivity of the cation separation membrane is improved by preferentially passing cations with smaller sizes such as hydrogen ions; the incorporation of the organic framework material also provides additional cation diffusion channels, which can improve the permeability of the membrane to anions and cations; and the raw materials and the preparation process are simple, and the membrane material for cation separation can be prepared simply in a large area.
The cation selective separation hybrid membrane can be used for extracting lithium ions in salt lake brine, reducing the magnesium-lithium ratio of the brine, or realizing the pre-enrichment of the lithium ions with high efficiency and energy conservation.
The cation selective separation hybridization membrane can efficiently recycle acid from waste acid in an energy-saving way, and has high acid permeation flux and selectivity.
Drawings
FIG. 1 is a scanning electron microscope image of a cation selective separation hybrid membrane prepared in example 1; wherein a is the surface of UiO-66@QPPO-10%, and b is the cross section of UiO-66@QPPO-10%;
FIG. 2 is a scanning electron microscope image of the cation selective separation hybrid membrane prepared in example 6; wherein a is HSO 3 -UiO-66@QPPO-5% surface, b is HSO 3 -UiO-66@qppo-5% section;
FIG. 3 is a scanning electron microscope image of the quaternized polyphenylene ether-based film prepared in comparative example 1; wherein a is a QPPO surface, and b is a QPPO section;
fig. 4 is a schematic structural view of the separation capability test apparatus.
Detailed Description
The present invention is described in further detail below by way of specific examples, which will enable those skilled in the art to more fully understand the invention, but are not limited in any way.
Example 1
An anion exchange driven cation selective separation hybrid membrane was prepared according to the following steps:
(1) Preparing a casting solution: dissolving 0.15g of brominated polyphenylene oxide in 5mL of N-methylpyrrolidone, adding 0.3mL of triethylamine solution, stirring for 24 hours at 25 ℃, adding 15mg of UiO-66 powder, and performing ultrasonic dispersion for 20 minutes to obtain casting solution with uniformly dispersed metal organic frame materials;
wherein, preparation of brominated polyphenylene oxide: 6g of polyphenyl ether, 0.25g of azodiisobutyronitrile and 7.2g N-bromosuccinimide are sequentially dissolved in chlorobenzene to obtain a uniform mixed solution, the mixed solution is placed in a three-neck flask, the reaction is stopped after the mixed solution is heated for 4 hours at 135 ℃, after the mixed solution is cooled to room temperature, a reaction product is poured into absolute ethyl alcohol to obtain a precipitate, the precipitate is washed three times by ethyl alcohol and then dried for 24 hours at 60 ℃, and finally a fibrous polymer is obtained, namely the brominated polyphenyl ether.
Wherein, the preparation of the metal organic framework material UIO-66: adding 0.7g of zirconium chloride, 5.6mL of acetic acid and 0.27mL of deionized water into 30mL of N, N-dimethylformamide, uniformly mixing to obtain solution 1, dissolving 0.5g of terephthalic acid into 5mL of N, N-dimethylformamide to obtain solution 2, mixing the solution 1 and the solution 2, stirring for 30min, transferring to a 100mL hydrothermal reaction kettle, reacting for 24h at 120 ℃, cooling to room temperature, washing the obtained product with ethanol for 3 times, soaking in acetone for one day, and finally drying at 100 ℃ for 12h to obtain white UIO-66 powder.
(2) Preparation of the film: spreading the casting film liquid prepared in the step (1) on a 5cm multiplied by 5cm glass plate, drying the casting film liquid in an oven at 80 ℃ for 12 hours, cooling the casting film to room temperature along with the oven, taking down the casting film by forceps, soaking the casting film in deionized water for 24 hours to remove the residual quaternizing agent in the reaction, and marking the obtained cation selective separation hybridization film as UiO-66@QPPO-10%, wherein a scanning electron microscope picture of the surface and the section of the casting film is shown in the attached figure 1.
Example 2
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 1 except that 30mg of UiO-66 powder was added and the resulting cation selective separation hybrid membrane was labeled UiO-66@qppo-20%.
Example 3
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 1 except that 45mg of UiO-66 powder was added and the resulting cation selective separation hybrid membrane was labeled UiO-66@qppo-30%.
Example 4
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 1 except that 15mg of MOF-808 powder was added and the resulting cation selective separation hybrid membrane was labeled MOF-808@QPPO-10%.
Wherein, the preparation of metal organic framework material MOF-808: 2.8g of trimesic acid and 13.0g of zirconium oxychloride octahydrate are taken and added to a mixed solution of 600mL of DMF and 600mL of formic acid, and the mixture is uniformly mixed under the condition of magnetic stirring. And transferring the mixed solution into a high-temperature reaction kettle, sealing, and then placing the mixed solution into a 140 ℃ oven for reaction for 48 hours. And after the reaction is finished, taking out the hydrothermal reaction kettle from the oven, and opening the hydrothermal reaction kettle after the hydrothermal reaction kettle is naturally cooled to room temperature. The white solid product formed by the reaction was isolated from the solution by filtration and washed three times with DMF solution. Thereafter, the solid was sequentially immersed in an acetone solution for 1 day to exchange a reaction solvent DMF. Then, the solid product after the acetone soaking is filtered and then is placed in a vacuum oven at 100 ℃ for drying for 24 hours.
Example 5
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 1 except that 30mg of MOF-808 powder was added and the resulting cation selective separation hybrid membrane was labeled MOF-808@QPPO-20%.
Example 6
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 1 except that 45mg of MOF-808 powder was added and the resulting cation selective separation hybrid membrane was labeled MOF-808@QPPO-30%.
Example 7
A quaternized polysulfone (QAPSF) anion-exchange driven cation-selective separation hybrid membrane was prepared according to the following steps:
(1) Preparing a casting solution: 0.15g of chloromethylated polysulfone (CMPSF) was dissolved in 15mL of N, N-Dimethylformamide (DMF) and 0.3mL of triethylamine solution was added thereto, and the mixture was stirred at 25℃for 24 hours. Adding 15mg of MOF-808 powder, and stirring for 60min to obtain a casting solution with uniformly dispersed covalent organic framework materials;
wherein, the preparation of chloromethylated polysulfone: 5g of polyphenyl ether, 3.4g of paraformaldehyde and 10mL of trimethylchlorosilane are sequentially dissolved in chloroform to obtain a uniform mixed solution, the mixed solution is placed in a three-neck flask, after the temperature is raised to 35 ℃, 0.27mL of anhydrous tin chloride is added dropwise into the solution, then the water bath temperature is adjusted to 40 ℃, the reaction is stopped after the water bath temperature is heated for 40 hours, after the reaction product is cooled to room temperature, the reaction product is poured into absolute ethyl alcohol to obtain a white precipitate, the precipitate is washed three times by ethanol and deionized water and then dried for 24 hours at the temperature of 60 ℃, and finally the white polymer is chloromethylated polysulfone.
(2) Preparation of the film: spreading the casting film liquid prepared in the step (1) on a 5cm multiplied by 5cm glass plate, drying the casting film liquid in an oven at 50 ℃ for 48 hours, cooling the casting film to room temperature along with the oven, taking down the casting film by forceps, and soaking the casting film in deionized water for 24 hours to remove the residual quaternizing agent in the reaction, wherein the obtained cation selective separation hybrid film is marked as MOF-808@QAPSF-10%.
Example 8
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 7 except that 30mg of MOF-808 powder was added and the resulting cation selective separation hybrid membrane was labeled MOF-808@QAPSF-20%.
Example 9
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 7 except that 45mg of MOF-808 powder was added and the resulting cation selective separation hybrid membrane was labeled MOF-808@QAPSF-30%.
Example 10
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 7 except that 60mg of MOF-808 powder was added and the resulting cation selective separation hybrid membrane was labeled MOF-808@QAPSF-40%.
Example 11
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 7 except that 60mg of sulfonated MOF-808 powder was added and the membrane was prepared after drying in an oven at 180℃for 6 hours, the resulting cation selective separation hybrid membrane was labeled sulfonated MOF-808@QAPSF-40%.
Wherein, the preparation of metal organic framework material sulfonated MOF-808: first, 1.0g of MOF-808 solid was weighed and added to 100mL of 0.1mol L -1 And magnetically stirred at room temperature for 24h. Next, the above solution was separated by filtration to obtain a solid, which was then washed three times with deionized water and immersed in an acetone solution for 1 day. Finally, the acetone-soaked solid was passed and placed in a vacuum oven at 100 ℃ for drying for 24 hours.
Comparative example 1
The quaternized polyphenylene ether based film was prepared as follows:
(1) Preparing a casting solution: taking a certain amount of 0.15g of brominated polyphenylene oxide, dissolving the brominated polyphenylene oxide in 5mL of N-methylpyrrolidone, adding 0.3mL of triethylamine solution, and stirring for 24 hours at 25 ℃ to obtain uniform casting solution;
(2) Preparation of the film: spreading the prepared casting film liquid on a 5cm multiplied by 5cm glass plate, drying in an oven at 80 ℃ for 12 hours, cooling to room temperature along with the oven, taking down the film with tweezers, and soaking in deionized water for 24 hours to remove the quaternizing reagent remained in the reaction, thereby obtaining the quaternized polyphenyl ether-based film marked as QPPO, and the scanning electron microscope pictures of the surface and the section of the quaternized polyphenyl ether-based film are shown in figure 3.
Comparative example 2
A quaternized polysulfone-based membrane was prepared according to the following steps:
(1) Preparing a casting solution: 0.15g of chloromethylated polysulfone (CMPSF) was dissolved in 5mL of N, N-Dimethylformamide (DMF) and 0.3mL of triethylamine solution was added thereto, followed by stirring at 25℃for 24 hours to obtain a uniform casting solution;
(2) Preparation of the film: the prepared casting solution is spread on a 5cm multiplied by 5cm glass plate, dried in an oven at 80 ℃ for 24 hours, cooled to room temperature along with the oven, and the membrane is taken down by tweezers and soaked in deionized water for 24 hours to remove the quaternizing agent remained in the reaction, so that the quaternized polysulfone-based membrane is marked as QAPSF.
The base films prepared in comparative examples 1 to 2 and the cation-selective separation hybrid films prepared in examples 1 to 11 were each prepared in Fe 2+ /H + The separation capacity test is carried out under the system, the separation capacity test device is shown in figure 4, the separation membrane is fixed between the two diffusion chambers by a clamp, and the effective area of the membrane is 1.766cm 2 To avoid leakage of the solution, gaskets are used to seal the membrane and compartments. The feeding phase is 150mL of mixed solution of 0.25mol/L ferrous chloride and 1mol/L hydrochloric acid, the discharging phase is 150mL deionized water, and Fe is carried out under the pushing of osmotic pressure 2+ And H + From the feed side to the discharge side through transmembrane transport, H in the feed liquid was measured by a pH meter + The concentration of Fe in the feed liquid is measured by an ultraviolet-visible spectrophotometer 2+ Is finally calculated to obtain H + Ion flux and H of (2) + /Fe 2+ The permeation selectivity of (c) and the experimental results are shown in table 1.
The result shows that the invention realizes the selective separation of cations by utilizing the anion exchange membrane for the first time, and the QPPO base membrane is used for H + /Fe 2+ Has a separation selectivity of 100, QAPSF base film vs. H + /Fe 2+ The separation selectivity of (2) was 300. Acid flux and H of separation membrane by doping metal organic framework material UiO-66 + /Fe 2+ Has a certain lifting. H at doping amount of 10-40% + /Fe 2+ Separation selectivity is obviously improved and H + The flux is obviously improved to different degrees. When the acid is separated and recovered by the diffusion dialysis method, the membrane can be used for remarkably improving the permeation flux and the separation ratio of the acid and remarkably improving the efficiency of acid separation and recovery.
Table 1:
example 12
An anion exchange driven cation selective separation hybrid membrane was prepared according to the following steps:
(1) Preparing a casting solution: 0.15g of brominated polyphenylene ether was dissolved in 5mL of N-methylpyrrolidone and 0.3mL of triethylamine solution was added thereto, and after stirring at 25℃for 24 hours, 7.5mg of HSO was further added 3 -UiO-66 powder, ultrasonically dispersing for 120min to obtain a casting solution with uniformly dispersed metal-organic framework material;
wherein, preparation of brominated polyphenylene oxide: 6g of polyphenyl ether, 0.25g of azodiisobutyronitrile and 7.2g N-bromosuccinimide are sequentially dissolved in chlorobenzene to obtain a uniform mixed solution, the mixed solution is placed in a three-neck flask, the reaction is stopped after the mixed solution is heated for 4 hours at 135 ℃, after the mixed solution is cooled to room temperature, a reaction product is poured into absolute ethyl alcohol to obtain a precipitate, the precipitate is washed three times by ethyl alcohol and then dried for 24 hours at 60 ℃, and finally a fibrous polymer is obtained, namely the brominated polyphenyl ether.
Wherein the metal organic framework material HSO 3 -preparation of UiO-66: 0.29g of zirconium chloride and 2.1mL of acetic acid are added into 15mL of N, N-dimethylformamide and mixed uniformly to obtain solution 3,0.33g of 2-sulfoterephthalic acid is dissolved in 0.2mL of HCl and 3mL of deionized water is added and mixed uniformly to obtain solution 4, and then the solution 3 and the solution 4 are mixed and stirred for 30min, transferring into a 50mL hydrothermal reaction kettle, reacting at 120 ℃ for 24 hours, cooling to room temperature, washing the obtained product with ethanol for 3 times, soaking in acetone for one day, and finally drying at 100 ℃ for 12 hours to obtain white HSO 3 -UiO-66 powder.
(2) Preparation of the film: spreading the prepared casting solution on a 5cm×5cm glass plate, drying in an oven at 80deg.C for 12 hr, cooling to room temperature with the oven, taking off the film with forceps, soaking in deionized water for 24 hr to remove the quaternizing agent remained in the reaction, and marking the obtained cation selective separation hybrid film as HSO 3 -UiO-66@QPPO-5%, and a scanning electron microscope picture of the surface and the section of the composite material is shown in figure 2.
Example 13
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 12 except that 15mg of UiO-66 powder was added and the resulting cation selective separation hybrid membrane was labeled HSO 3 -UiO-66@QPPO-10％。
Example 14
An anion exchange driven cation selective separation hybrid membrane was prepared as in example 12 except that 30mg of UiO-66 powder was added and the resulting cation selective separation hybrid membrane was labeled HSO 3 -UiO-66@QPPO-20％。
The QPPO base film produced in comparative example 1 and the cation-selective separation hybrid films produced in examples 12 to 14 were each prepared in Li + /Mg 2+ The separation capacity test is carried out under the system, the separation capacity test device is shown in figure 4, the separation membrane is fixed between the two diffusion chambers by a clamp, and the effective area of the membrane is 1.766cm 2 The feeding phase is 150mL of mixed solution of 1mol/L lithium chloride and 1mol/L magnesium chloride, the discharging phase is 150mL of deionized water, and under the pushing of osmotic pressure, li + And Mg (magnesium) 2+ From the feeding side to the discharging side through trans-membrane transport, the ionic concentration of the feed liquid is measured by ICP-OES, and Li is obtained through calculation + Ion flux and Li + /Mg 2+ The permeation selectivity and the experimental results are shown in Table 2.
Table 2:
the results show that the QPPO base film is specific to Li + /Mg 2+ Has better separation and selection performance, and Li under the condition of the case of the invention + /Mg 2+ Has a separation ratio of 3.97, li + Flux of 0.25 mol.m -2 ·h -1 Incorporation of metal organic framework materials HSO 3 Li of-UiO-66 pair separation film + Flux and Li + /Mg 2+ The separation selectivity is obviously improved. In the range of 5% -20% doping amount, li of the separation film is separated along with the increase of doping amount + The flux is increased because the metal organic frame material forms an ion rapid transmission channel in the membrane, so that the ion transmission capacity of the separation membrane is improved; li (Li) + /Mg 2+ The separation selectivity is significantly improved due to the sulfonic acid groups on the metal organic framework material ligands which are specific to Li + Is greater than Mg 2+ Thereby for Li + /Mg 2+ Has obvious separation performance. Therefore, in the process of extracting lithium from salt lake brine with high magnesium-lithium ratio, the anion exchange driven membrane is adopted to carry out diffusion dialysis on the brine, so that the magnesium-ion ratio of the brine can be obviously reduced, and the lithium ions are pre-enriched and selectively extracted, thereby being an energy-saving and environment-friendly lithium extraction method without additional energy input.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative, not restrictive, and many changes may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the appended claims, which are to be construed as falling within the scope of the present invention.
Claims (9)
1. An anion exchange driven cation selective separation hybrid membrane formed by doping an organic framework material to an anion exchange membrane and obtained by the following preparation method:
(1) Preparing a casting solution: dissolving an anion exchange polymer in an organic solvent, and adding an organic frame material to obtain a casting solution with the organic frame material uniformly dispersed;
wherein the skeleton of the anion exchange polymer is one of polyphenyl ether, polysulfone and polyether-ether-ketone, and the anion exchange group of the anion exchange polymer is one of quaternary ammonium salt, imidazole salt and pyrrolidine salt;
wherein the organic framework material is one of UiO-66, sulfonated UiO-66, MOF-808, sulfonated MOF-808, tpPa-1 and TpPa-2;
(2) Preparation of the film: and (3) preparing the casting solution into a film by a solvent evaporation method.
2. The anion exchange driven cation selective separation hybridization membrane according to claim 1, wherein the organic framework material is a metal organic framework material or a covalent organic framework material.
3. An anion exchange driven cation selective separation hybrid membrane according to claim 1 wherein the organic solvent is N, N-dimethylformamide or N-methylpyrrolidone.
4. An anion exchange driven cation selective separation hybrid membrane according to claim 1 wherein the organic framework material comprises from 5% to 40% by mass of the anion exchange polymer.
5. The anion exchange driven cation selective separation hybrid membrane of claim 1, wherein in step (1), the mass ratio of the anion exchange polymer to the organic solvent is 1:2.5-10; the membrane casting liquid is prepared by adopting ultrasonic dispersion or stirring dispersion, and the time of ultrasonic dispersion or stirring dispersion is 20-120 min.
6. The anion exchange driven cation selective separation hybrid membrane of claim 1, wherein in step (2), the drying temperature of the solvent evaporation method is 50-180 ℃ and the drying time is 6-48 h.
7. The anion exchange driven cation selective separation hybridization membrane according to claim 1, wherein the anion exchange polymer is one of quaternized polyphenylene ether or quaternized polysulfone.
8. A method of preparing an anion exchange driven cation selective separation hybrid membrane according to any one of claims 1 to 7, comprising the steps of:
(1) Preparing a casting solution: dissolving an anion exchange polymer in an organic solvent, and adding an organic frame material to obtain a casting solution with the organic frame material uniformly dispersed;
(2) Preparation of the film: and (3) preparing the casting solution into a film by a solvent evaporation method.
9. Use of an anion exchange driven cation selective separation hybrid membrane according to any one of claims 1 to 7 for extraction of lithium from salt lake brine and/or recovery of spent acid.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816814A (en) * | 2014-03-06 | 2014-05-28 | 北京工业大学 | Porous granule MCM-41-ZIF-8/PDMS pervaporation hybrid membrane, preparation and application |
| CN110433673A (en) * | 2019-07-08 | 2019-11-12 | 淮阴师范学院 | A kind of quaternary ammonium salt functionalization polysulfones-nano-attapulgite stone hybrid anion exchange membrane and preparation method thereof |
| CN111249928A (en) * | 2020-02-27 | 2020-06-09 | 山东科技大学 | Mixed matrix cation exchange membrane based on metal organic framework compound and preparation method thereof |
| CN111718504A (en) * | 2020-06-19 | 2020-09-29 | 长春工业大学 | ZIF-67-based polyaryletherketone anion exchange membrane and preparation method thereof |
| WO2021041514A1 (en) * | 2019-08-27 | 2021-03-04 | Board Of Regents, The University Of Texas System | Methods of fabricating polymer films and membranes |
| WO2021051849A1 (en) * | 2019-09-20 | 2021-03-25 | 青岛理工大学 | Cationic metal-organic framework membrane material and preparation method and application |
| CN113078341A (en) * | 2021-03-30 | 2021-07-06 | 长春工业大学 | Polyether-ether-ketone/cationic metal-organic framework crosslinked film and preparation method thereof |
| CN113368697A (en) * | 2021-04-07 | 2021-09-10 | 中国海洋大学 | Monovalent cation selective separation membrane modified by metal organic framework material and preparation method and application thereof |
-
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816814A (en) * | 2014-03-06 | 2014-05-28 | 北京工业大学 | Porous granule MCM-41-ZIF-8/PDMS pervaporation hybrid membrane, preparation and application |
| CN110433673A (en) * | 2019-07-08 | 2019-11-12 | 淮阴师范学院 | A kind of quaternary ammonium salt functionalization polysulfones-nano-attapulgite stone hybrid anion exchange membrane and preparation method thereof |
| WO2021041514A1 (en) * | 2019-08-27 | 2021-03-04 | Board Of Regents, The University Of Texas System | Methods of fabricating polymer films and membranes |
| WO2021051849A1 (en) * | 2019-09-20 | 2021-03-25 | 青岛理工大学 | Cationic metal-organic framework membrane material and preparation method and application |
| CN111249928A (en) * | 2020-02-27 | 2020-06-09 | 山东科技大学 | Mixed matrix cation exchange membrane based on metal organic framework compound and preparation method thereof |
| CN111718504A (en) * | 2020-06-19 | 2020-09-29 | 长春工业大学 | ZIF-67-based polyaryletherketone anion exchange membrane and preparation method thereof |
| CN113078341A (en) * | 2021-03-30 | 2021-07-06 | 长春工业大学 | Polyether-ether-ketone/cationic metal-organic framework crosslinked film and preparation method thereof |
| CN113368697A (en) * | 2021-04-07 | 2021-09-10 | 中国海洋大学 | Monovalent cation selective separation membrane modified by metal organic framework material and preparation method and application thereof |
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