CN114471177A - 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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- CN114471177A CN114471177A CN202210114311.5A CN202210114311A CN114471177A CN 114471177 A CN114471177 A CN 114471177A CN 202210114311 A CN202210114311 A CN 202210114311A CN 114471177 A CN114471177 A CN 114471177A
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- anion exchange
- selective separation
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- 239000012528 membrane Substances 0.000 title claims abstract description 125
- 238000000926 separation method Methods 0.000 title claims abstract description 92
- 150000001768 cations Chemical class 0.000 title claims abstract description 79
- 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 48
- 239000000463 material Substances 0.000 claims abstract description 45
- 238000005266 casting Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000013384 organic framework Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000002253 acid 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
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 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
- 238000011084 recovery Methods 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
- 239000002699 waste material Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 239000013207 UiO-66 Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 239000012621 metal-organic framework Substances 0.000 claims description 12
- 229920002492 poly(sulfone) Polymers 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- DJOSTUFCDFIBRL-UHFFFAOYSA-N C1=CC(=CC=C1N)N.C(=O)C1=C(C(=C(C(=C1O)C=O)O)C=O)O Chemical compound C1=CC(=CC=C1N)N.C(=O)C1=C(C(=C(C(=C1O)C=O)O)C=O)O DJOSTUFCDFIBRL-UHFFFAOYSA-N 0.000 claims description 3
- 239000013310 covalent-organic framework Substances 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 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
- 150000004693 imidazolium salts Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 17
- 230000004907 flux Effects 0.000 abstract description 14
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 238000012216 screening Methods 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- 238000005341 cation exchange Methods 0.000 abstract 1
- 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
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910001425 magnesium ion Inorganic materials 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005956 quaternization reaction Methods 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
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- 230000003204 osmotic effect Effects 0.000 description 3
- 238000001878 scanning electron 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
- 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 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
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- 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- 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
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method 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
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000010348 incorporation Methods 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
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 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
- 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
- 230000032895 transmembrane transport Effects 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
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- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
- B01D71/52—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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- 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
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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
- 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
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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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention belongs to the technical field of separation membrane materials, and discloses a cation selective separation hybrid membrane driven by anion exchange, and preparation and application thereof, wherein an anion exchange membrane is taken as a base membrane, and a membrane material with enhanced cation selective separation performance is obtained by doping porous materials such as an organic frame and the like; dissolving an anion exchange membrane polymer in an organic solvent to prepare a polymer solution; adding organic frame material powder into the polymer solution and stirring to obtain a uniform membrane casting solution; the obtained casting solution is prepared into a film by a solvent evaporation method; the prepared typical hybrid membrane has wide application prospect in the fields of lithium extraction from salt lake brine, waste acid recovery and the like. The invention utilizes the difference of cation permeability rate in the anion exchange membrane to apply the cation exchange membrane to the selective separation of cations; the size screening and functional group screening of the organic framework 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 as well as a preparation method and application thereof.
Background
Resource shortage and environmental pollution caused by global rapid development are major challenges for the sustainable development of modern society. Selectively extracting certain cations from water resources such as seawater, salt lake brine and the like is an important way for relieving the resource shortage crisis and meeting the production and living requirements; in addition, the 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 lithium extraction from salt lake brine, acid recovery from waste pickling liquid and the like is receiving wide attention.
Cation selective separation membranes are one of 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 membrane material has the advantages of convenient membrane formation, compact and defect-free membrane, good flexibility and the like, but the ion selectivity of the organic membrane is lower. And the existing organic cation selective separation membrane has a counter relationship between ion transmission flux and ion selectivity, the cation transmission flux of the membrane is increased to generally reduce the cation selectivity, and the cation transmission flux is generally sacrificed to improve the cation selectivity. Although inorganic membrane materials have high ion selectivity, the formation of the membrane is easy to generate defects, and a large-scale 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 considered at the same time, and provides an anion exchange-driven cation selective separation hybrid membrane, a preparation method and application thereof, wherein the cation selective separation hybrid membrane takes an anion exchange membrane as a membrane matrix, and based on an electric neutral principle and concentration diffusion, anion exchange transmission is carried out in the membrane by utilizing anions, and power is provided for selectively permeating the membrane for cations at the same time; among them, the Li prepared by the invention can effectively separate Li+/Mg2+、Fe2+/H+The cation separation membrane has good application value in the fields of lithium extraction from salt lake brine and waste acid recovery.
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 for preparing an anion exchange membrane by doping an anion exchange membrane with an organic framework material, comprising:
(1) preparing a casting solution: dissolving an anion exchange polymer in an organic solvent, and adding an organic framework material to obtain a casting solution with the organic framework material uniformly dispersed;
(2) preparation of the film: and (3) preparing the membrane casting solution into a membrane by a solvent evaporation method.
Furthermore, 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 accounts for 5-40% of the 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; and (3) preparing the casting solution by adopting ultrasonic dispersion or stirring dispersion, wherein 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 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 framework material to obtain a casting solution with the organic framework material uniformly dispersed;
(2) preparation of the film: and (3) preparing the membrane casting solution into a membrane by a solvent evaporation method.
According to another aspect of the invention, the application of the cation selective separation hybrid membrane in the lithium extraction and/or waste acid recovery of salt lake brine is provided; 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 invention has the beneficial effects that:
according to the cation selective separation hybrid membrane and the preparation method thereof, the exchange of anions in the membrane is used for driving the separation of cations in the membrane, and meanwhile, the concentration diffusion at two sides of the membrane is used for providing the driving force of anions and cations, so that additional energy supply is not needed, and the membrane is energy-saving and environment-friendly; 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 through the cations with smaller sizes, such as hydrogen ions; the doping of the organic framework material also provides an additional cation diffusion channel, so that the permeability of the membrane to anions and cations can be improved; and the raw materials and the preparation process are simple, and the membrane material for cation separation can be simply prepared in a large area.
The cation selective separation hybrid membrane can be used for extracting lithium ions in salt lake brine with high efficiency and energy conservation, reducing the magnesium-lithium ratio of the brine, or realizing the pre-enrichment of the lithium ions.
The cation selective separation hybrid membrane can efficiently and energy-effectively recover acid from waste acid, and has high acid permeation flux and selectivity.
Drawings
FIG. 1 is a scanning electron micrograph of a cation selective separation hybrid membrane prepared in example 1; wherein, a is UiO-66@ QPPO-10% of surface, and b is UiO-66@ QPPO-10% of section;
FIG. 2 is a scanning electron micrograph of the cation selective separation hybrid membrane prepared in example 6; wherein a is HSO3-UiO-66@ QPPO-5% surface, b is HSO3-UiO-66@ QPPO-5% section;
FIG. 3 is a scanning electron micrograph of a 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 diagram of the separation capability test apparatus.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable those skilled in the art to more fully understand the present invention, but which are not intended to limit the invention 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 at the temperature of 25 ℃ for 24 hours, adding 15mg of UiO-66 powder, and performing ultrasonic dispersion for 20 minutes to obtain a casting solution with uniformly dispersed metal organic framework material;
wherein, the preparation of the brominated polyphenylene oxide comprises the following steps: dissolving 6g of polyphenyl ether, 0.25g of azodiisobutyronitrile and 7.2g N-bromosuccinimide in chlorobenzene in sequence to obtain a uniform mixed solution, heating the mixed solution in a three-necked flask at 135 ℃ for 4 hours, stopping reaction, cooling the mixed solution to room temperature, pouring a reaction product into absolute ethyl alcohol to obtain a precipitate, washing the precipitate for three times by using ethyl alcohol, and drying the precipitate at the temperature of 60 ℃ for 24 hours to obtain a fibrous polymer, 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 a solution 1, dissolving 0.5g of terephthalic acid in 5mL of N, N-dimethylformamide to obtain a solution 2, mixing the solution 1 and the solution 2, stirring for 30min, transferring to a 100mL hydrothermal reaction kettle, reacting at 120 ℃ for 24h, cooling to room temperature, washing the obtained product with ethanol for 3 times, soaking with acetone for one day, and drying at 100 ℃ for 12h to obtain white UiO-66 powder.
(2) Preparation of the film: and (2) spreading the casting solution prepared in the step (1) on a glass plate of 5cm multiplied by 5cm, drying the glass plate in an oven at the temperature of 80 ℃ for 12h, cooling the glass plate to room temperature along with the oven, taking down the membrane by using tweezers, and soaking the membrane in deionized water for 24h to remove the residual quaternizing reagent in the reaction, wherein the obtained cation selective separation hybrid membrane is marked as UiO-66@ QPPO-10%, and the scanning electron microscope pictures of the surface and the section of the hybrid membrane are shown in 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 resultant 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 resultant cation selective separation hybrid membrane was labeled UiO-66@ QPPO-30%.
Example 4
An anion exchange driven cation selective separation hybrid membrane was prepared according to the method of 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 the metal organic framework material MOF-808 comprises the following steps: 2.8g of trimesic acid and 13.0g of zirconium oxychloride octahydrate were added to a mixed solution of 600mL of DMF and 600mL of formic acid and mixed well under magnetic stirring. And transferring the mixed solution into a high-temperature reaction kettle, sealing, and placing in a 140 ℃ oven for reaction for 48 hours. And after the reaction is finished, taking the hydrothermal reaction kettle out of 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. Thereafter, the solid was sequentially soaked in an acetone solution for 1 day to exchange the reaction solvent DMF. Then, the solid product after acetone soaking is filtered and then is dried in a vacuum oven at 100 ℃ for 24 hours.
Example 5
An anion exchange driven cation selective separation hybrid membrane was prepared according to the method of 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 according to the method of 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 type (QAPSF) anion exchange driven cation selective separation hybrid membrane was prepared according to the following procedure:
(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, followed by stirring at 25 ℃ for 24 hours. Then 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 the chloromethylated polysulfone comprises the following steps: dissolving 5g of polyphenyl ether, 3.4g of paraformaldehyde and 10mL of trimethylchlorosilane in chloroform in sequence to obtain a uniform mixed solution, placing the mixed solution in a three-necked flask, heating to 35 ℃, dropwise adding 0.27mL of anhydrous tin chloride into the solution, adjusting the temperature of a water bath to 40 ℃, heating for 40 hours, stopping reaction, cooling to room temperature, pouring a reaction product into anhydrous ethanol to obtain a white precipitate, washing the precipitate for three times with ethanol and deionized water, and drying at 60 ℃ for 24 hours to obtain a white polymer, namely the chloromethylated polysulfone.
(2) Preparation of the film: and (2) spreading the casting film liquid prepared in the step (1) on a glass plate of 5cm multiplied by 5cm, drying the glass plate in an oven at 50 ℃ for 48h, cooling the glass plate to room temperature along with the oven, taking down the film by using tweezers, and soaking the film in deionized water for 24h 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 according to the method of 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 hybrid cation selective separation membrane was prepared according to the method of example 7, except that 45mg of MOF-808 powder was added, and the resulting hybrid cation selective separation membrane was labeled MOF-808@ QAPSF-30%.
Example 10
An anion exchange driven cation selective separation hybrid membrane was prepared according to the method of 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 according to the method of example 7, except that 60mg of sulfonated MOF-808 powder was added, and the resulting cation selective separation hybrid membrane was labeled sulfonated MOF-808@ QAPSF-40% after drying in an oven at 180 ℃ for 6h in the preparation of the membrane.
Wherein, the preparation of the metal organic framework material sulfonated MOF-808 comprises the following steps: firstly, weighing1.0g of MOF-808 solid was added to 100mL of 0.1mol L-1And magnetically stirred at room temperature for 24 h. Next, the above solution was separated by filtration to obtain a solid, which was then washed three times with deionized water and soaked in an acetone solution for 1 day. Finally, the acetone soaked solid is dried for 24 hours in a vacuum oven at 100 ℃.
Comparative example 1
The quaternized polyphenylene ether-based film was prepared according to the following procedure:
(1) preparing a casting solution: dissolving a certain amount of 0.15g of brominated polyphenylene oxide in 5mL of N-methylpyrrolidone, adding 0.3mL of triethylamine solution, and stirring at the temperature of 25 ℃ for 24 hours to obtain uniform membrane casting solution;
(2) preparation of the film: and (3) spreading the prepared casting film liquid on a glass plate of 5cm multiplied by 5cm, drying in an oven at 80 ℃ for 12h, cooling to room temperature along with the oven, taking down the film by using forceps, and soaking in deionized water for 24h to remove the residual quaternization reagent in the reaction, so as to obtain the quaternization polyphenyl ether base film marked as QPPO, wherein the scanning electron microscope pictures of the surface and the section of the quaternization polyphenyl ether base film are shown in figure 3.
Comparative example 2
The quaternized polysulfone-based membrane was prepared according to the following steps:
(1) preparing a casting solution: dissolving 0.15g of chloromethylated polysulfone (CMPSF) in 5mL of N, N-Dimethylformamide (DMF), adding 0.3mL of triethylamine solution, and stirring at 25 ℃ for 24 hours to obtain a uniform membrane casting solution;
(2) preparation of the film: and (3) flatly paving the prepared casting membrane liquid on a glass plate with the thickness of 5cm multiplied by 5cm, drying the casting membrane liquid in an oven at the temperature of 80 ℃ for 24 hours, cooling the casting membrane liquid to room temperature along with the oven, taking down the membrane by using tweezers, and soaking the membrane in deionized water for 24 hours to remove the residual quaternizing agent in the reaction, thereby obtaining the quaternizing polysulfone base membrane labeled as QAPSF.
The base membranes prepared in comparative examples 1 to 2 and the cation selective separation hybrid membranes prepared in examples 1 to 11 were separately subjected to Fe2+/H+The separation ability test is carried out under the system, the separation ability test device is shown in figure 4, the separation membrane is fixed between two diffusion chambers by a clamp, and the effective area of the membrane is 1.766cm2To avoid solutionsLeakage, sealing between membrane and compartment using gaskets. The feeding phase is 150mL of mixed solution of 0.25mol/L ferrous chloride and 1mol/L hydrochloric acid, the discharging phase is 150mL of deionized water, and under the push of osmotic pressure, Fe2+And H+From the feed side to the discharge side through the membrane, and H in the discharge liquid is measured by a pH meter+The concentration of Fe in the discharge solution is measured by an ultraviolet-visible spectrophotometer2+Is finally calculated to obtain H+Ion flux and H+/Fe2+The results of the experiments are shown in Table 1.
The result shows that the invention realizes the selective separation of cations for the first time by utilizing an anion exchange membrane, and the QPPO base membrane is used for H+/Fe2+Separation selectivity of 100, QAPSF-based Membrane pair H+/Fe2+Has a separation selectivity of 300. Acid flux and H of the doped metal organic framework material UiO-66 to the separation membrane+/Fe2+There is a certain lift. H when the doping amount is 10-40 percent+/Fe2+Separation selectivity is significantly improved and H+The flux is obviously improved to different degrees. When the diffusion dialysis method is used for acid separation and recovery, the membrane can be used for remarkably improving the permeation flux and the separation ratio of 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, 0.3mL of triethylamine solution was added thereto, and after stirring at 25 ℃ for 24 hours, 7.5mg of HSO was added thereto3-UiO-66 powder, and performing ultrasonic dispersion for 120min to obtain a casting solution with uniformly dispersed metal organic framework material;
wherein, the preparation of the brominated polyphenylene oxide comprises the following steps: dissolving 6g of polyphenyl ether, 0.25g of azodiisobutyronitrile and 7.2g N-bromosuccinimide in chlorobenzene in sequence to obtain a uniform mixed solution, heating the mixed solution in a three-necked flask at 135 ℃ for 4 hours, stopping reaction, cooling the mixed solution to room temperature, pouring a reaction product into absolute ethyl alcohol to obtain a precipitate, washing the precipitate for three times by using ethyl alcohol, and drying the precipitate at the temperature of 60 ℃ for 24 hours to obtain a fibrous polymer, namely the brominated polyphenyl ether.
Wherein the metal organic framework material HSO3Preparation of UiO-66: adding 0.29g of zirconium chloride and 2.1mL of acetic acid into 15mL of N, N-dimethylformamide, uniformly mixing to obtain a solution 3, dissolving 0.33g of 2-sulfonic acid terephthalic acid in 0.2mL of HCl, adding 3mL of deionized water, uniformly mixing to obtain a solution 4, mixing the solution 3 and the solution 4, stirring for 30min, transferring to a 50mL hydrothermal reaction kettle, reacting at 120 ℃ for 24h, cooling to room temperature, washing the obtained product with ethanol for 3 times, soaking with acetone for one day, and drying at 100 ℃ for 12h to obtain white HSO3-UiO-66 powder.
(2) Preparation of the film: spreading the prepared casting membrane liquid on a glass plate of 5cm multiplied by 5cm, drying in an oven at 80 ℃ for 12h, cooling to room temperature along with the oven, taking down the membrane by using tweezers, soaking in deionized water for 24h to remove the residual quaternization reagent, and marking the obtained cation selective separation hybrid membrane as HSO3-UiO-66@ QPPO-5%, and the scanning electron microscope pictures of the surface and the section are 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 designated as HSO3-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 designated as HSO3-UiO-66@QPPO-20％。
The QPPO-based membranes prepared in comparative example 1 and the cation selective separation hybrid membranes prepared in examples 12 to 14 were separately subjected to Li+/Mg2+The separation ability test is carried out under the system, the separation ability test device is shown in figure 4, the separation membrane is fixed between two diffusion chambers by a clamp, and the effective area of the membrane is 1.766cm2The feeding phase is 150mL of a 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 Mg2+Transferring from the feeding side to the discharging side through transmembrane transport, measuring the ion concentration of the discharging liquid by utilizing ICP-OES, and obtaining Li through calculation+Ion flux and Li+/Mg2+The osmotic selectivity, the experimental results are shown in table 2.
Table 2:
the results show that QPPO-based membranes are specific for Li+/Mg2+Has better separation and selection performance, under the condition of the case of the invention, Li+/Mg2+Has a separation ratio of 3.97, Li+The flux was 0.25 mol. m-2·h-1Incorporation of metal organic framework materials HSO3-UiO-66 vs Li of separation membrane+Flux and Li+/Mg2+The separation selectivity is obviously improved. In the range of 5% -20% doping amount, with the increase of doping amount, Li of the separation membrane+The flux is increased because the metal organic framework material forms an ion rapid transmission channel in the membrane, so that the ion transmission capability of the separation membrane is improved; li+/Mg2+The separation selectivity is obviously improved because of the sulfonic acid group on the ligand of the metal organic framework material and the Li+Has an attractive force greater than that of Mg2+Thus to Li+/Mg2+Has obvious separation performance. Therefore, in the process of extracting lithium from the 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 lithium ions are pre-enriched and selectively extracted, thus the method is an energy-saving and environment-friendly lithium extraction method without external 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 and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (10)
1. An anion exchange driven cation selective separation hybrid membrane, which is characterized by being formed by doping an anion exchange membrane with an organic framework material and being obtained by the following preparation method:
(1) preparing a casting solution: dissolving an anion exchange polymer in an organic solvent, and adding an organic framework material to obtain a casting solution with the organic framework material uniformly dispersed;
(2) preparation of the film: and (3) preparing the membrane casting solution into a membrane by a solvent evaporation method.
2. The anion-exchange driven cation selective separation hybrid membrane according to claim 1, wherein the framework of the anion-exchange polymer is one of polyphenylene oxide, polysulfone and polyetheretherketone, and the anion-exchange group of the anion-exchange polymer is one of quaternary ammonium salt, imidazolium salt and pyrrolidine salt.
3. The anion exchange driven cation selective separation hybrid membrane according to claim 1, wherein the organic framework material is a metal organic framework material or a covalent organic framework material.
4. The anion exchange driven cation selective separation hybrid membrane according to claim 1, wherein the organic solvent is N, N-dimethylformamide or N-methylpyrrolidone.
5. The anion exchange driven cation selective separation hybrid membrane according to claim 1, wherein the organic framework material is 5 to 40% by mass of the anion exchange polymer.
6. The anion-exchange driven cation selective separation hybrid membrane according to claim 1, wherein in the step (1), the mass ratio of the anion exchange polymer to the organic solvent is 1: 2.5-10; and (3) preparing the casting solution by adopting ultrasonic dispersion or stirring dispersion, wherein the time of ultrasonic dispersion or stirring dispersion is 20-120 min.
7. The anion-exchange driven cation selective separation hybrid membrane according to claim 1, wherein in the step (2), the drying temperature of the solvent evaporation method is 50-180 ℃, and the drying time is 6-48 h.
8. The anion exchange driven cation selective separation hybrid membrane according to claim 1, wherein the anion exchange polymer is one of quaternized polyphenylene 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.
9. A method for preparing the cation selective separation hybrid membrane according to any one of claims 1 to 8, comprising the steps of:
(1) preparing a casting solution: dissolving an anion exchange polymer in an organic solvent, and adding an organic framework material to obtain a casting solution with the organic framework material uniformly dispersed;
(2) preparation of the film: and (3) preparing the membrane casting solution into a membrane by a solvent evaporation method.
10. Use of the cation selective separation hybrid membrane according to claim 8 in lithium extraction from salt lake brine and/or recovery of waste acid.
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