CN105013357B - Polymer-embedded metal organic framework film, and preparation method, device and application thereof - Google Patents
Polymer-embedded metal organic framework film, and preparation method, device and application thereof Download PDFInfo
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- CN105013357B CN105013357B CN201510378308.4A CN201510378308A CN105013357B CN 105013357 B CN105013357 B CN 105013357B CN 201510378308 A CN201510378308 A CN 201510378308A CN 105013357 B CN105013357 B CN 105013357B
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- organic framework
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- hollow fiber
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000012510 hollow fiber Substances 0.000 claims abstract description 65
- 239000000243 solution Substances 0.000 claims abstract description 57
- 239000012528 membrane Substances 0.000 claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 229920006112 polar polymer Polymers 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000013384 organic framework Substances 0.000 claims description 20
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 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 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 238000005576 amination reaction Methods 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 238000001514 detection method Methods 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- 238000005086 pumping Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 26
- 239000007789 gas Substances 0.000 description 24
- 238000001802 infusion Methods 0.000 description 12
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 12
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000004176 ammonification Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a polymer embedded metal organic framework film, a preparation method, a preparation device and application thereof, wherein the preparation method comprises the following steps: (1) packaging the hollow fiber membrane in a cross-flow membrane module to form a hollow fiber membrane module; (2) respectively dissolving metal salt and a ligand in a solvent to obtain a metal salt solution and a ligand solution; (3) respectively pumping a metal salt solution and a ligand solution into a shell pass and a tube pass of the hollow fiber membrane component simultaneously to synthesize a membrane, continuously pumping into the hollow fiber membrane component for 12-48 h at the temperature of 30-60 ℃, then respectively pumping an alcohol solvent or water into the shell pass and the tube pass of the hollow fiber membrane component to clean the membrane, and finally drying the membrane to obtain the polymer-embedded metal organic framework membrane; the membrane obtained by the invention can be applied to the separation of mixed gas; the polar polymer to be embedded is directly added in the synthesis of the metal organic framework film, so that the traditional mode of firstly synthesizing and then modifying is abandoned, and the method is simple, efficient and low in cost.
Description
(1) technical field
The present invention relates to a kind of metal organic framework film, its preparation method, preparation facilitiess and application are and in particular to a kind of gather
Metal organic framework film and its preparation method of large-scale production, preparation facilitiess and application that compound embeds, belong to perforated membrane
Preparation and gas separate the technical field applied.
(2) background technology
In recent years, the burning of substantial amounts of Fossil fuel causes the discharge of substantial amounts of carbon dioxide isothermal chamber gas, brings
Serious problem of environmental pollution.Therefore, for reducing greenhouse gas emission, the clean energy resource of a new generation is urgently developed.Hydrogen is
A kind of high new forms of energy of combustion value, and produce water using rear it is considered to be main follow-on clean energy resource.Therefore hydrogen energy source
Separation problem widely studied in recent years.Membrance separation has non-environmental-pollution, process is simple, separation efficiency is high, energy consumption is low
The advantages of.The gas separation membrane being used at present is mainly polymeric film, such as polyimide film, poly (ether sulfone) film, polysulfone membrane.But it is poly-
Compound film has that permeation flux is little, the low problem of selectivity.
Metallic organic framework is a kind of new porous supramolecular materials with metal node and organic ligand composition.Its tool
Adjustable pore passage structure, huge specific surface area, gas is had to select absorption, be easy to chemical modification and excellent hot, chemical steady
The characteristic such as qualitative.Therefore pass through the metal organic framework film being self-assembly of in recent years also by substantial amounts of detached for gas
During.But the film of this species is primarily present following two bottlenecks at present.(1) synthetic method, synthetic method master at present
If solvent-thermal process, there is high energy consumption in it, raw material utilization rate low it is difficult to amplify the shortcomings of.(2) separating effect, is made at present
Metallic organic framework gas separation membrane gas separation effect is poor, and the pore passage structure being had due to metallic organic framework is not
Completely increase continuously, such as Cu2(BTC)3, a kind of metal-organic framework materials being usually used in gas separation membrane preparation, its hole
Footpath is 0.9nm, and more than general micro-molecular gas, therefore its gas separating property is to rely on preferentially selective sorption mechanism, and it is right
H2/CO2、H2/O2、H2/N2、H2/CH4It is typically smaller than 20 Deng gas-selectively；And for example ZIF-8, one kind is usually used in gas separation membrane system
Standby metal-organic framework materials are although it has more suitable pore passage structure 0.34nm, but this metal organic framework film
Structure has flexibility, leads to its selectivity generally also and little.
Therefore, a kind of can the adjustable synthetic method of metallic organic framework pore passage structure of scale urgently develop.
(3) content of the invention
An object of the present invention is the metal organic framework film providing a kind of polymer to embed, and described polymer embeds
Metal organic framework film is modified theory using the synthesis theory of hollow fiber membrane contactorses with reference to metallic organic framework duct and is carried out
Large-scale production and modification.
For achieving the above object, the present invention adopts the following technical scheme that：
The metal organic framework film that a kind of polymer embeds, the metal organic framework film that described polymer embeds presses such as lower section
Method prepares：
(1) hollow-fibre membrane is packaged in the membrane module of cross-flow, forms hollow fiber film assembly, the hollow being formed is fine
In dimension membrane module, the space within hollow-fibre membrane is tube side, and the outside space and membrane module shell between of hollow-fibre membrane is
Shell side；Described hollow-fibre membrane is the polyvinylidene fluoride film or polyimide film after amination；
(2) slaine is dissolved in solvent, obtains metal salt solution；Part and polar polymer are dissolved in solvent, obtain
To ligand solution；Described slaine is FeCl3、AlCl3、Cr(NO3)3、Co(NO3)2、ZnCl2、Zn(NO3)2、Cu(NO3)2Or vinegar
Sour copper；Described part is benzimidazole, 2-methylimidazole, trimesic acid or p-phthalic acid；Described polar polymer is poly-
Ethylene glycol, polyvinyl alcohol, Polyvinylpyrrolidone, polysulfones, polyether sulfone or Polyetherimide；Described solvent is water, methanol, second
Alcohol, isopropanol, dimethylformamide or dimethyl acetylamide, or water/alcohol mixeding liquid；Slaine in described metal salt solution
Concentration be 1.25～125mmol/L；In described ligand solution the concentration of part be 2.5～250mmol/L, polar polymer
Concentration is 0.5～10g/L；
(3) metal salt solution obtaining step (2) respectively and ligand solution are with the flow of 0.5～5mL/min pump simultaneously
Enter the shell side of hollow fiber film assembly that step (1) obtains and tube side carries out the synthesis of film, persistently pump into 12 at 30～60 DEG C
After～48h, then alcoholic solvent or water are pumped into shell side and the pipe of hollow fiber film assembly respectively with the flow of 0.5～5mL/min
Film is finally dried by the cleaning of Cheng Jinhang film, obtains final product the metal organic framework film that described polymer embeds；Described alcoholic solvent is first
Alcohol, ethanol or isopropanol.
The metal organic framework film that polymer of the present invention embeds, in step (1), described hollow-fibre membrane is surface band
Polarized group is provided that the hollow-fibre membrane in heterogeneous nucleation site, such as：Polyvinylidene fluoride film after amination, polyimide film
Deng the preferably polyvinylidene fluoride film after amination.
The amination method of described polyvinylidene fluoride film is：Clip polyvinylidene fluoride film, is placed on 20wt%～30wt%
Ethylenediamine solution in, carry out under conditions of 100～200 DEG C seal heat treatment 12h, after natural cooling, by film spend from
It is dried after sub- water cleaning, obtain final product the polyvinylidene fluoride film after amination.
In step (2), in ligand solution, add polar polymer, it can be embedded into change duct in metallic organic framework
Structure, the seriality to improve film for the crosslinking degree of increase metallic organic framework simultaneously.
In step (2), the metal in described slaine is transition metal, and preferably described slaine is Zn (NO3)2Or Cu
(NO3)2；Described part is Carboxylic acid ligand or imidazole ligands, and preferably described part is 2-methylimidazole or trimesic acid；Described
Polar polymer is polar organic polymers, and preferably described polar polymer is Polyethylene Glycol, polyvinyl alcohol or polyvinyl pyrrole
Alkanone；And, preferably described solvent is water, methanol, ethanol or dimethylformamide, or water/ethanol volume ratio 1：1 mixing
Liquid.
In step (2), in preferably described metal salt solution, the concentration of slaine is 12.5～125mmol/L；Preferably described
In ligand solution the concentration of part be 25～250mmol/L, the concentration of polar polymer be 1～10g/L.
Present invention also offers a kind of special purpose device preparing the metal organic framework film that described polymer embeds, described dress
Put including a hollow fiber film assembly, heater, two feed tanks, two recovery ponds, two infusion pump, four valves
And connecting pipe；Wherein, the first feed tank, hollow fiber film assembly, the first recovery pond pass sequentially through connecting pipe and connect, the
Two feed tanks, hollow fiber film assembly, the second recovery pond pass sequentially through connecting pipe and connect, and, described first feed tank, the
One recovery pond is connected with the tube side of hollow fiber film assembly, described second feed tank, the second recovery pond and hollow fiber film assembly
Shell side connection；Connect and be respectively equipped with infusion pump a, valve a on the first feed tank and the connecting pipe of hollow fiber film assembly, even
The connecting pipe connecing the first recovery pond with hollow fiber film assembly is provided with valve b, connects the second feed tank and hollow-fibre membrane
Infusion pump b, valve c are respectively equipped with the connecting pipe of assembly, connect the connecting tube of the second recovery pond and hollow fiber film assembly
Road is provided with valve d；The outside of described hollow fiber film assembly is provided with heater.
The metal organic framework film that Inventive polymers embed can be applicable to the separation of mixed gas, described mixed gas
For H2/CO2、H2/O2、H2/N2、H2/ methane, H2/ ethane or H2/ propane etc.；The separation of described mixed gas adopts Wicke-
Kallenbach technology, with gas chromatogram (GC 1690) detectable concentration.
Compared with prior art, the beneficial effects of the present invention is：
(1) present invention employs hollow fiber membrane contactorses process, abandon the synthesis of traditional hydro-thermal or solvent thermal
Method is so that the building-up process of metal organic framework film is easy to amplify；
(2) present invention is by the precursor solution of metal organic framework film, during that is, metal salt solution and ligand solution are respectively placed in
The both sides of hollow fiber film, so that it carries out the synthesis of metal organic framework film in the way of non-direct contact, have prevented in solution
The formation of metallic organic framework granule, simultaneously the precursor solution of metal organic framework film may be recovered utilization, substantially increase
The utilization ratio of raw material；
(3) present invention adopts low temperature to synthesize, and has abandoned traditional high-temperature nuclei, greatly reduces the energy required for synthesis
Amount, reduces the synthesis cost of metal organic framework film；
(4) present invention employs the pore passage structure that the embedded mode of polar polymer changes metal organic framework film, with
When increased seriality, eliminate pin hole there is a possibility that, and then substantially increase gas separation selectivity；
(5) present invention is directly added into polar polymer to be embedded in the synthesis of metal organic framework film, has abandoned biography
The synthesis and the modification step that first synthesize the mode modified afterwards, be effectively simplified metal organic framework film of system.
(4) brief description
Fig. 1 is synthesizer schematic diagram of the present invention；
Wherein：1- first feed tank, 2- second feed tank, 3- second recovery pond, 4- first recovery pond, 5- hollow-fibre membrane
Assembly, 6- heater, 7- connecting pipe, 8- infusion pump a, 9- valve a, 10- infusion pump b, 11- valve c, 12- valve d, 13- valve
Door b.
(5) specific embodiment
Below in conjunction with the accompanying drawings, by specific embodiment, technical scheme is described further, but the present invention
Protection domain not limited to this.
The present invention prepares the special purpose device of the metal organic framework film that described polymer embeds as shown in figure 1, described device
Including a hollow fiber film assembly, heater, two feed tanks, two recovery ponds, two infusion pump, four valves with
And connecting pipe；Wherein, the first feed tank 1, hollow fiber film assembly 5, the first recovery pond 4 pass sequentially through connecting pipe 7 and connect,
Second feed tank 2, hollow fiber film assembly 5, the second recovery pond 3 pass sequentially through connecting pipe 7 and connect, and, described first enters
Material pond 1, the first recovery pond 4 are connected with the tube side of hollow fiber film assembly 5, described second feed tank 2, the second recovery pond 4 with
The shell side connection of hollow fiber membrane module 5；Connect and be respectively equipped with the first feed tank 1 and the connecting pipe 7 of hollow fiber film assembly 5
Infusion pump a8, valve a9, the connecting pipe 7 connecting the first recovery pond 4 with hollow fiber film assembly 5 is provided with valve b13, connects
It is respectively equipped with infusion pump b10, valve c11 on second feed tank 2 and the connecting pipe 7 of hollow fiber film assembly 5, connect second time
Receives pond 3 is provided with valve d12 with the connecting pipe 7 of hollow fiber film assembly 5；The outside of described hollow fiber film assembly 5 is provided with
Heater 6.
Described device for prepare polymer embed metal organic framework film when, its operational approach is：Part is molten
Liquid, metal salt solution be respectively placed in the first feed tank 1, in the second feed tank 2, and passes through infusion pump a8, infusion pump b10 pump respectively
Enter the preparation that hollow fiber film assembly 5 carries out film, wherein, the tube side that ligand solution flows through hollow fiber film assembly 5 enters first
Recovery pond 4, the shell side that metal salt solution flows through hollow fiber film assembly 5 enters the second recovery pond 3, and the solution in recovery pond can be straight
Tap into row recycling；After the completion of film preparation, by the ligand solution in the first feed tank 1, the second feed tank 2 and metal salt solution
All it is replaced by alcoholic solvent or water, alcoholic solvent or water are pumped into hollow fiber film assembly 5 by infusion pump a8, infusion pump b10 respectively
Tube side and shell side carry out the cleaning of film, after cleaning, film is dried, both the metal organic framework film that embeds of described polymer.
The preparation of embodiment 1 metallic organic framework ZIF-8 film
(1) Pvdf Microporous Hollow Fiber Membrane of clip 6cm length, is placed in the ethylenediamine solution of 30wt%,
Under conditions of 100 DEG C, sealing carries out ammonification 12h, takes the film out after natural cooling, and deionized water is dried, by it after cleaning three times
It is packaged in the membrane module of cross-flow, form hollow fiber film assembly.
(2) preparing metal organic backbone precursor solution：By 2-methylimidazole (0.21g, 2.5mmol) and Zn (NO3)2·
6H2O (0.37g, 1.25mmol) is dissolved in 1000ml deionized water respectively, obtains 2-methylimidazole solution and Zn (NO3)2Solution.
(3) preparation of film：Heater outside hollow fiber film assembly 5 pre-sets 30 DEG C, the 2- that step (2) is obtained
Methyl imidazole solution and Zn (NO3)2Solution is respectively placed in first feed tank 1 and the second feed tank 2 of synthesizer, and with
The flow of 0.5mL/min pumps into hollow fiber film assembly 5 simultaneously, and 2-methylimidazole solution flows through the tube side of hollow fiber film assembly
Enter the first recovery pond 4, Zn (NO3)2The shell side that solution flows through hollow fiber film assembly enters the second recovery pond 3, persistently pumps into
After 48h, the precursor solution in the first feed tank 1 and the second feed tank 2 is replaced by methanol, by methanol with the stream of 0.5mL/min
Amount pumps into the shell side of hollow fiber film assembly respectively and tube side carries out the cleaning of film, film is dried, obtains final product metal after cleaning 60min
Organic backbone ZIF-8 film.
Gained metallic organic framework ZIF-8 film is carried out H2/CO2Mixed gas separating property is tested, and test adopts Wicke-
Kallenbach technology, with gas chromatogram (GC 1690) detectable concentration.The H of described film2Flux is 1.42 × 10-5mol s-1m- 2Pa-1, H2/CO2Selectivity is 5.23.
The preparation of the metallic organic framework ZIF-8 film that embodiment 2 polyvinyl alcohol embeds
(1) Pvdf Microporous Hollow Fiber Membrane of clip 6cm length, is placed in the ethylenediamine solution of 30wt%,
Under conditions of 100 DEG C sealing carry out ammonification 12h, take the film out after natural cooling, cleaned with water after three times and be dried, be encapsulated in
In the membrane module of cross-flow, form hollow fiber film assembly.
(2) preparing metal organic backbone precursor solution：By 2-methylimidazole (0.21g, 2.5mmol) and Zn (NO3)2·
6H2O (0.37g, 1.25mmol) is dissolved in the deionized water of 1000ml respectively, and adds 0.5g in 2-methylimidazole solution
Polyvinyl alcohol, obtains the 2-methylimidazole solution containing polyvinyl alcohol and Zn (NO3)2Solution.
(3) preparation of film：Heater outside hollow fiber film assembly 5 pre-sets 60 DEG C, by containing that step (2) obtains
There are 2-methylimidazole solution and the Zn (NO of polyvinyl alcohol3)2The first feed tank 1 and second that solution is respectively placed in synthesizer enters
In material pond 2, and hollow fiber film assembly 5 is pumped into the flow of 0.5mL/min simultaneously, the 2-methylimidazole containing polyvinyl alcohol is molten
The tube side through hollow fiber film assembly for the liquor stream enters the first recovery pond 4, Zn (NO3)2Solution flows through the shell side of hollow fiber film assembly
Enter the second recovery pond 3, after persistently pumping into 24h, the precursor solution in the first feed tank 1 and the second feed tank 2 is replaced by second
Alcohol, ethanol is pumped into the shell side of hollow fiber film assembly respectively with the flow of 0.5mL/min and tube side carries out the cleaning of film, cleaning
After 60min, film is dried, obtains final product the metallic organic framework ZIF-8 film that polyvinyl alcohol embeds.
The metallic organic framework ZIF-8 film that gained polyvinyl alcohol is embedded carries out H2/CO2Mixed gas separating property is tested,
Test adopts Wicke-Kallenbach technology, with gas chromatogram (GC 1690) detectable concentration.The H of described film2/CO2Selectivity
For 30.12.This value is far longer than the ZIF-8 film that embodiment 1 does not add polyvinyl alcohol polymer matter.This is because embedded gathers
Vinyl alcohol can change the pore passage structure of film and the seriality improving film.
The preparation of the metallic organic framework ZIF-8 film that embodiment 3 Polyethylene Glycol embeds
(1) Pvdf Microporous Hollow Fiber Membrane of clip 6cm length, is placed in the ethylenediamine solution of 30wt%,
Under conditions of 100 DEG C sealing carry out ammonification 12h, take the film out after natural cooling, cleaned with water after three times and be dried, be encapsulated in
In the membrane module of cross-flow, form hollow fiber film assembly.
(2) preparing metal organic backbone precursor solution：By molten for 2-methylimidazole (21g, 250mmol) and Zn (NO3)2·
6H2O (37g, 125mmol) is dissolved in the deionized water of 1000ml respectively, and adds gathering of 10g in 2-methylimidazole solution
Ethylene glycol, obtains the 2-methylimidazole solution containing Polyethylene Glycol and Zn (NO3)2Solution.
(3) preparation of film：Heater outside hollow fiber film assembly 5 pre-sets 30 DEG C, by containing that step (2) obtains
There are 2-methylimidazole solution and the Zn (NO of Polyethylene Glycol3)2The first feed tank 1 and second that solution is respectively placed in synthesizer enters
In material pond 2, and hollow fiber film assembly 5 is pumped into the flow of 5mL/min simultaneously, the 2-methylimidazole solution containing Polyethylene Glycol
The tube side flowing through hollow fiber film assembly enters the first recovery pond 4, Zn (NO3)2The shell side that solution flows through hollow fiber film assembly enters
Enter the second recovery pond 3, after persistently pumping into 12h, the precursor solution in the first feed tank 1 and the second feed tank 2 is replaced by isopropyl
Alcohol, isopropanol is pumped into the shell side of hollow fiber film assembly respectively with the flow of 5mL/min and tube side carries out the cleaning of film, cleaning
After 60min, film is dried, obtains final product the metallic organic framework ZIF-8 film that Polyethylene Glycol embeds.
The metallic organic framework ZIF-8 film that gained Polyethylene Glycol is embedded carries out H2/CO2Mixed gas separating property is tested,
Test adopts Wicke-Kallenbach technology, with gas chromatogram (GC 1690) detectable concentration.The H of described film2/CO2Selectivity
For 52.13.This value is far longer than the ZIF-8 film that embodiment 1 does not add polyethylene glycol polymer.This is due to embedded poly- second
Glycol can change the pore passage structure of film and the seriality improving film.
The metallic organic framework Cu that embodiment 4 Polyethylene Glycol embeds2(BTC)3The preparation of film
(1) Pvdf Microporous Hollow Fiber Membrane of clip 6cm length, is placed in the ethylenediamine solution of 30wt%,
Under conditions of 100 DEG C sealing carry out ammonification 12h, take the film out after natural cooling, cleaned with water after three times and be dried, be encapsulated in
In the membrane module of cross-flow, form hollow fiber film assembly.
(2) preparing metal organic backbone precursor solution：Trimesic acid (10mmol) is dissolved in 1000mL deionized water/second
Alcohol volume ratio 1：In 1 mixed solvent, simultaneously by Cu (NO3)2·3H2O (15mmol) is dissolved in 100mL deionized water/ethanol volume
Ratio 1：In 1 mixed solvent, and add 1g Polyethylene Glycol in trimesic acid solution, obtain the equal benzene containing Polyethylene Glycol
Front three acid solution and Cu (NO3)2Solution.
(3) preparation of film：Heater outside hollow fiber film assembly 5 pre-sets 30 DEG C, by containing that step (2) obtains
There are trimesic acid solution and the Cu (NO of Polyethylene Glycol3)2The first feed tank 1 and second that solution is respectively placed in synthesizer enters
In material pond 2, and hollow fiber film assembly 5 is pumped into the flow of 5mL/min simultaneously, the trimesic acid solution containing Polyethylene Glycol
The tube side flowing through hollow fiber film assembly enters the first recovery pond 4, Cu (NO3)2The shell side that solution flows through hollow fiber film assembly enters
Enter the second recovery pond 3, after persistently pumping into 24h, the precursor solution in the first feed tank 1 and the second feed tank 2 be replaced by ethanol,
Ethanol is pumped into the shell side of hollow fiber film assembly respectively with the flow of 5mL/min and tube side carries out the cleaning of film, clean 60min
Afterwards film is dried, obtains final product the metallic organic framework Cu that Polyethylene Glycol embeds2(BTC)3Film.
The metallic organic framework Cu that gained Polyethylene Glycol is embedded2(BTC)3Film carries out H2/CO2Mixed gas separating property
Test, test adopts Wicke Kallenbach technology, with gas chromatogram (GC 1690) detectable concentration.The H of described film2/CO2Choosing
Selecting property is 9.21.
Claims (9)
1. a kind of polymer embed metal organic framework film it is characterised in that described polymer embed metallic organic framework
Film is prepared as follows obtaining：
(1) hollow-fibre membrane is packaged in the membrane module of cross-flow, forms hollow fiber film assembly, the hollow-fibre membrane being formed
In assembly, the space within hollow-fibre membrane is tube side, and the outside space and membrane module shell between of hollow-fibre membrane is shell side；
Described hollow-fibre membrane is the polyvinylidene fluoride film or polyimide film after amination；
(2) slaine is dissolved in solvent, obtains metal salt solution；Part and polar polymer are dissolved in solvent, are joined
Liquid solution；Described slaine is FeCl3、AlCl3、Cr(NO3)3、Co(NO3)2、ZnCl2、Zn(NO3)2、Cu(NO3)2Or Schweinfurt green；
Described part is benzimidazole, 2-methylimidazole, trimesic acid or p-phthalic acid；Described polar polymer is poly- second two
Alcohol, polyvinyl alcohol, Polyvinylpyrrolidone, polysulfones, polyether sulfone or Polyetherimide；Described solvent is water, methanol, ethanol, different
Propanol, dimethylformamide or dimethyl acetylamide, or water/alcohol mixeding liquid；In described metal salt solution, slaine is dense
Spend for 1.25～125mmol/L；In described ligand solution the concentration of part be 2.5～250mmol/L, the concentration of polar polymer
For 0.5～10g/L；
(3) metal salt solution obtaining step (2) and ligand solution pump into step respectively with the flow of 0.5～5mL/min respectively
Suddenly the shell side of the hollow fiber film assembly that (1) obtains and tube side carry out the synthesis of film, persistently pump into 12～48h at 30～60 DEG C
Afterwards, then by alcoholic solvent or water pumps into the shell side of hollow fiber film assembly respectively with the flow of 0.5～5mL/min and tube side is carried out
Film is finally dried by the cleaning of film, obtains final product the metal organic framework film that described polymer embeds；Described alcoholic solvent is methanol, second
Alcohol or isopropanol.
2. the metal organic framework film that polymer as claimed in claim 1 embeds it is characterised in that in step (1), described hollow
Fibrous membrane is the polyvinylidene fluoride film after amination.
3. polymer as claimed in claim 2 embeds metal organic framework film is it is characterised in that described polyvinylidene fluoride film
Amination method is：Clip polyvinylidene fluoride film, is placed in the ethylenediamine solution of 20wt%～30wt%, 100～200
Carry out under conditions of DEG C sealing heat treatment 12h, after natural cooling, be dried after film deionized water is cleaned, after obtaining final product amination
Polyvinylidene fluoride film.
4. the metal organic framework film that polymer as claimed in claim 1 embeds it is characterised in that in step (2), described metal
Salt is Zn (NO3)2Or Cu (NO3)2.
5. the metal organic framework film that polymer as claimed in claim 1 embeds it is characterised in that in step (2), described part
For 2-methylimidazole or trimesic acid.
6. the metal organic framework film that polymer as claimed in claim 1 embeds it is characterised in that in step (2), described polarity
Polymer is Polyethylene Glycol, polyvinyl alcohol or Polyvinylpyrrolidone.
7. the metal organic framework film that polymer as claimed in claim 1 embeds it is characterised in that in step (2), described solvent
For water, methanol, ethanol or dimethylformamide, or water/ethanol volume ratio 1：1 mixed liquor.
8. the metal organic framework film that polymer as claimed in claim 1 embeds it is characterised in that in step (2), described metal
In saline solution, the concentration of slaine is 12.5～125mmol/L；In described ligand solution, the concentration of part is 25～250mmol/
L, the concentration of polar polymer are 1～10g/L.
9. application in the separation of mixed gas for the metal organic framework film that polymer as claimed in claim 1 embeds, it is special
Levy and be, described mixed gas are H2/CO2、H2/O2、H2/N2、H2/ methane, H2/ ethane or H2/ propane；Described mixed gas
Separation adopt Wicke-Kallenbach technology, with GC 1690 gas chromatographic detection concentration.
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| CN109731481B (en) * | 2019-01-22 | 2021-10-19 | 宁波石墨烯创新中心有限公司 | Composite membrane material, preparation method thereof and filtering membrane |
| CN110129290B (en) * | 2019-04-03 | 2022-10-28 | 江苏大学 | Metal organic framework material immobilized laccase as well as preparation method and application thereof |
| CN110538636B (en) * | 2019-09-16 | 2020-09-15 | 中国科学院生态环境研究中心 | Porous metal organic framework gel, preparation method and application thereof |
| CN114082312B (en) * | 2021-10-22 | 2024-02-20 | 广州白云山汉方现代药业有限公司 | Hollow fiber membrane with chiral selectivity and method for separating metoprolol enantiomer by using same |
| CN115634580B (en) * | 2022-10-31 | 2023-10-17 | 中国科学院赣江创新研究院 | Preparation method of hollow fiber composite membrane based on rare earth coordination |
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| JP2005298695A (en) * | 2004-04-13 | 2005-10-27 | Daicel Chem Ind Ltd | Preparation method of polymer solution |
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