CN114642975A - Metal-organic framework mixed matrix membrane and preparation method and application thereof - Google Patents

Metal-organic framework mixed matrix membrane and preparation method and application thereof Download PDF

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CN114642975A
CN114642975A CN202011511269.8A CN202011511269A CN114642975A CN 114642975 A CN114642975 A CN 114642975A CN 202011511269 A CN202011511269 A CN 202011511269A CN 114642975 A CN114642975 A CN 114642975A
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titanium
metal
uio
mixed matrix
organic framework
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CN114642975B (en
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缪晓春
高晓晨
柏诗哲
韩笑
吴征
高焕新
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • B01D67/0011—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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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Abstract

The invention discloses a metal-organic framework mixed matrix membrane and a preparation method and application thereof. The metal-organic framework mixed matrix membrane provided by the invention comprises titanium modified NH2‑UIO‑66、NH2ZIF-8 and polyimide. The MOFs filler in the metal-organic framework mixed matrix membrane has high compatibility with an organic continuous phase and no defect on an interface, greatly improves the stability of a system in the application of gas separation, has an outstanding separation effect and is CO2/CH4The large-scale preparation of the gas separation membrane provides a basis.

Description

Metal-organic framework mixed matrix membrane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of mixed matrix membrane preparation, and particularly relates to a metal-organic framework mixed matrix membrane and a preparation method and application thereof.
Background
The gas membrane separation technology utilizes different gases in mixed gas to have different permeation rates to a membrane material under the pushing of the pressure of the gases at two sides of the membrane, an enriched material of the gases which are easy to permeate is obtained at a permeation side, and a separated gas of the gases which are difficult to permeate is obtained at a non-permeation side, so that the purpose of gas separation is achieved. The currently used gas separation membrane materials are mainly organic membrane materials, and there is an upper limit in the gas separation process of the organic membrane materials, namely, the selectivity is weakened when the gas permeability is enhanced, and vice versa. To solve this problem, inorganic fillers are generally introduced into organic membrane materials to prepare composite membrane materials, and it is desirable that the prepared composite membranes have the advantages of high separation coefficient, high permeability coefficient, or both.
The Metal Organic Frameworks (MOFs) are a novel highly-crystallized material, and are a novel porous crystal material formed by combining metal ions (or metal clusters) and organic ligands through coordination bond bridging. MOFs have the characteristics of adjustable and controllable structure, large specific surface area, high porosity, unsaturated metal sites, various structures, easy functionalization and the like, and have good application prospects in the fields of gas storage and separation, liquid separation, gas storage, chemical sensors, functional luminescent materials and the like. However, when the MOFs is used as an inorganic filler and is blended with an organic matter to prepare a composite membrane material, the gas separation performance of the composite membrane is not a simple combination of the advantages of the inorganic filler and the organic matter, and the main problem is that the compatibility between a polymer and the inorganic filler is poor, so that the gas separation performance of the mixed matrix membrane is reduced.
The current method for improving the compatibility of inorganic filler and organic continuous phase mainly comprises the steps of forming hydrogen bonds between polymer modification and the inorganic filler, Advanced Materials,2016,28,3399 and 3405 disclose a method for improving the compatibility of polyimide organic phase and ZIF-8 filler, wherein an ultrathin polydopamine layer is coated on ZIF-8, and then ZIF-8 crystals coated with the polydopamine layer and organic polyimide are mixed to form a film, wherein the formation of the hydrogen bonds is formed between the polydopamine layer and the polyimide, so that the aim of improving the compatibility of ZIF-8 and the polyimide is fulfilled. However, the acting force of the hydrogen bond is weaker than that of the common chemical bond, so that the compatibility between two phases in the composite membrane material is not obviously improved. The compatibility between the inorganic filler and an organic continuous phase can also be improved by grafting functional groups on the surface of the polymer and growing the inorganic filler in situ, Journal of membrane science,2015,492,21-31 discloses a preparation method of a MOFs composite membrane, polyimide matrix is used as the organic continuous phase, imidazole groups are grafted on organic matter functionalization, then a precursor of ZIF-8 is added into a suspension of polymer particles for reaction, and the membrane is slowly formed in a DMF steam environment. After the reaction, a film was formed. However, this method is only suitable for MOF/polymer combinations with specific chemical structures, and is very difficult to be widely popularized in the gas separation industry.
Disclosure of Invention
The invention aims to solve the problems of poor compatibility between the conventional MOFs filler and an organic continuous phase and poor separation effect of a mixed matrix membrane with a single filler component, and provides a metal-organic framework mixed matrix membrane and a preparation method and application thereof. The MOFs filler in the metal-organic framework mixed matrix membrane has high compatibility with an organic continuous phase and a defect-free interface, the stability of the system is greatly improved in the application of gas separation, and the separation effect is remarkable.
In a first aspect, the invention provides a metal-organic framework mixed matrix membrane comprising titanium-modified NH2-UIO-66、NH2ZIF-8 and polyimide.
In the technical scheme, the quality of the metal-organic framework mixed matrix membrane is taken as a reference, and the titanium is used for modifying NH2-the mass content of UIO-66 is 5% to 20%; NH (NH)2-5% -20% of ZIF-8 by mass; the mass content of the polyimide is 60％-90％。
In the above technical scheme, titanium modified NH2-UIO-66, titanium content 0.28% -1.39% by mass.
In the technical scheme, the molar ratio of titanium to zirconium in the metal-organic framework mixed matrix membrane is 1:12-60, preferably 1: 15-35.
In the above technical solution, the thickness of the metal-organic framework mixed matrix film is 20-80 μm.
The second aspect of the present invention provides a method for preparing the metal-organic framework mixed matrix membrane, comprising the steps of:
modifying titanium with NH2UIO-66 and NH2Doping ZIF-8 into a polyamic acid solution, stirring to obtain a doped casting solution, and standing and defoaming; coating the processed casting film liquid on a glass plate to prepare a wet film, removing the solvent to solidify and form a film, and performing heat treatment to prepare the metal-organic framework mixed matrix film.
In the above technical scheme, the heat treatment conditions are as follows: the treatment temperature is 200-350 ℃, and the treatment time is 0.5-2 h.
In the technical scheme, the titanium is modified with NH2-a method for the preparation of UIO-66 comprising the steps of:
(1) dissolving zirconium salt in organic solvent A, adding 2-amino terephthalic acid, and reacting to obtain NH2-UIO-66；
(2) Dissolving titanium salt in chlorohydrocarbon, adding tetrahydrofuran in an inert atmosphere, uniformly mixing, adding a solvent B, filtering and drying to obtain tetrachlorobis (tetrahydrofuran) titanium (IV);
(3) dissolving titanium (IV) tetrachlorobis (tetrahydrofuran) prepared in the step (2) in an organic solvent C, and adding NH prepared in the step (1)2UIO-66, standing, filtering, washing and drying to obtain titanium modified NH2-UIO-66。
In the technical scheme, the titanium is modified with NH2-UIO-66, wherein in step (1) the zirconium salt is preferably one or both of zirconium tetrachloride and zirconium tetrabromide.
In the technical scheme, the titanium modified NH2-UIO-66, wherein the reaction in step (1) can be carried out at 80-150 ℃ for 20-30 hours; or the reaction time is 5 to 20 minutes under the microwave condition. Preferably, the reaction time is 5 to 20 minutes under microwave conditions.
In the technical scheme, the titanium is modified with NH2The UIO-66 can be prepared by filtering, washing and drying after the reaction in step (1), and can be treated by conventional means, and the filtering, washing and drying treatment in step (1) of the present invention is preferably carried out by centrifuging the product, extracting the product with an organic solvent such as absolute ethanol, and washing and filtering with absolute ethanol. Drying is carried out at 60-100 deg.C for 6-24 hr, preferably under vacuum.
In the technical scheme, the titanium is modified with NH2In the preparation method of UIO-66, the titanium salt in the step (2) is one or more of titanium tetrachloride, titanium tetrabromide and titanium isopropoxide.
In the technical scheme, the titanium is modified with NH2-UIO-66, wherein the chlorinated hydrocarbon in step (2) is preferably dichloroethane.
In the technical scheme, the titanium is modified with NH2In the preparation method of UIO-66, the inert atmosphere in step (2) is preferably one or more of nitrogen, helium and argon.
In the technical scheme, the titanium is modified with NH2-UIO-66, wherein in the step (2), the solvent B is at least one of n-hexane, n-heptane and isohexane.
In the technical scheme, the titanium is modified with NH2-UIO-66 is prepared by releasing heat during the mixing of the individual starting materials in step (2), preferably by placing the mixture in an ice bath.
In the technical scheme, the titanium is modified with NH2In the method for producing UIO-66, the organic solvent A in step (1) and the organic solvent C in step (3) are each independently selected from one or more of N, N-dimethylformamide, N-methylacetamide and N-methylformamide.
In the technical scheme, the titanium is modified with NH2-UIO-66 preparation method, in step (3), tetrachlorobis (tetrahydrofuran) titanium (IV) solidBody and NH2UIO-66 in a molar ratio of 1:2 to 10, preferably 1:2 to 6.
In the technical scheme, the titanium is modified with NH2The UIO-66 is prepared by a method wherein the standing time in the step (3) is 5 to 15 days.
In the above technical solution, NH2-a process for preparing ZIF-8 comprising the steps of:
(1) the zinc salt solution is used as a water phase; taking a mixed solution of n-heptane and n-hexanol as an oil phase, adding a surfactant into the oil phase, and adding an organic ligand after mixing;
(2) adding the water phase into the oil phase, dispersing uniformly to form reverse microemulsion, standing, separating and washing to obtain NH2-ZIF-8。
In the above technical solution, in NH2In the preparation method of ZIF-8, the zinc salt in step (1) is at least one selected from the group consisting of zinc chloride and zinc nitrate.
In the above technical scheme, in NH2In the preparation method of the ZIF-8, the surfactant in the step (1) is selected from at least one of alkylphenol ethoxylate, high-carbon fatty alcohol ethoxylate and triton X-100.
In the above technical solution, in NH2The preparation method of ZIF-8, wherein the organic ligand in step (1) is selected from at least two of 2-methylimidazole, 2-aminobenzimidazole, methylimidazole, 3-methylimidazole, 4-aminobenzimidazole, 5-aminobenzimidazole, and at least one amino group and at least one non-amino group ligand such as, for example, but not limited to, 2-methylimidazole and 2-aminobenzimidazole.
In the above technical solution, in NH2In the preparation method of ZIF-8, the molar ratio of 2-methylimidazole to 2-aminobenzimidazole in step (1) is preferably 8 to 20: 1.
in the above technical scheme, the preparation method of the polyamic acid solution comprises the following steps:
mixing and dissolving dimethylacetamide and octadecylamine, adding pyromellitic dianhydride, and reacting to obtain the polyamic acid solution.
In the technical scheme, in the preparation method of the polyamic acid solution, the mass ratio of the octadecyl amine to the pyromellitic dianhydride is 1:2-2: 1.
In the above technical scheme, in the preparation method of the polyamic acid solution, the reaction conditions are as follows: reacting for 8-24h at 0-20 ℃.
In the technical scheme, the mass concentration of the polyamic acid solution is 10-25%.
In the above technical solution, in the preparation method of the metal-organic framework mixed matrix film, the processes of standing, defoaming, film casting, and curing to form a film may be performed by a conventional method in the art.
The third aspect of the invention provides a method for separating CO by using the metal-organic framework mixed matrix membrane2/CH4A method of producing a gas.
In the above technical scheme, CO2/CH4Volume ratio of gas 1:2-2: 1; the pressure difference is 0-0.1MPa, and the temperature is 20-50 ℃.
In the technical scheme, the thickness of the metal-organic framework mixed matrix membrane is 20-80 μm.
The invention has the following beneficial effects:
1. the metal-organic framework mixed matrix membrane is titanium modified NH2UIO-66 and NH2The mixed matrix membrane of the ZIF-8 and the polyimide is compounded, so that the separation effect is greatly improved compared with that of any pure membrane and a mixed matrix membrane with a single component, and the stability of the system is greatly improved in the application of gas separation.
2. Because the problem of weak compatibility between polyimide and MOF materials exists in the preparation process of the polyimide, UIO-66 and ZIF-8 mixed membrane, the gas separation performance of the prepared composite membrane material is reduced, the invention synthesizes NH by respectively modifying amino functional groups on metal organic framework materials UIO-66 and ZIF-82UIO-66 and NH2ZIF-8 and NH with titanium2-UIO-66 as an inorganic disperse phase after modification, polyimide as an organic continuous phase, and NH modified by titanium of the inorganic disperse phase2UIO-66 and NH2-ZIF-8 and organo-onium saltsAnd (3) mixing the phases, preparing an inorganic-organic mixed matrix membrane material, and further enhancing the compatibility of the inorganic dispersed phase and the organic continuous phase, so that the composite membrane material prepared based on the method greatly improves the stability of the system and improves the separation effect in the application of gas separation.
3. The metal-organic framework mixed matrix membrane prepared by the invention has CO under normal pressure2Has excellent trapping ability for CO2And CH4The separation selectivity is good, and the recycling capability is good.
Drawings
FIG. 1 is surface (e) and cross-section (f) of SEM image of mixed matrix membrane of example 6;
FIG. 2 shows the NH modified with titanium of comparative example 12-XRD diffractogram of UIO-66;
FIG. 3 shows comparative example 4NH2-XRD diffractogram of ZIF-8.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, but the scope of the present invention is not limited by the examples. In the present invention, wt% is a mass fraction.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
In the present invention, a Scanning Electron Microscope (SEM) photograph of a sample was taken on a Nigri S-4800 type II scanning electron microscope.
In the invention, the test conditions of XRD are as follows: the crystal phase analysis of the molecular sieve was carried out by using an X-ray diffractometer of Rigaku-Ultima type in Japan. CuK α radiation, wavelength λ 0.15432 nm. The scanning range 2 theta of the X-ray diffraction pattern is 5-50 DEG, and the scanning speed is 10 DEG/min.
Comparative example 1
1. Titanium modified NH2The preparation steps of UIO-66 are as follows:
(1) accurately weighing 1.50 g of zirconium tetrachloride, dissolving in 30mL of DMF solvent, dissolving in a magnetic stirring manner, adding 1.56 g of 2-amino-p-benzeneStirring dicarboxylic acid with magnetic force for 10min, placing the above solution into a microwave oven, reacting for 10min under microwave condition, centrifuging the product, extracting the product with anhydrous ethanol for 20h to remove unreacted 2-amino terephthalic acid, washing with anhydrous ethanol for 5 times, filtering, and vacuum drying at 80 deg.C overnight to obtain product NH2-UIO-66。
(2) Weighing 5.0 g of titanium tetrachloride, dissolving the titanium tetrachloride in 50mL of dichloroethane, adding 7.62 g of tetrahydrofuran under the nitrogen protection atmosphere, stirring the mixture in ice bath to form a yellow solution, adding 100mL of n-hexane to form a yellow precipitate, filtering the yellow precipitate, washing the precipitate with 100mL of n-hexane, and vacuumizing and drying the precipitate.
(3) 0.10 g of titanium (IV) tetrachlorobis (tetrahydrofuran) solid was weighed out, dissolved in 50ml of DMF and 2.1 g of NH were added2Standing UIO-66 for 10 days, centrifuging, washing the precipitate with DMF for 10 times, soaking the washed solid in methanol for 3 days, centrifuging, and vacuum drying at 40 deg.C for 24 hr to obtain titanium modified NH2-UIO-66. The XRD diffractogram is shown in FIG. 2.
2. The preparation of the polyamic acid was as follows:
50ml of dimethylacetamide is placed in a three-neck flask, 5g of octadecylamine is added, stirring is carried out for 10 minutes until complete dissolution is achieved, 2.5g of pyromellitic dianhydride is slowly added under stirring at 6 ℃ (300 r/minute), and reaction is carried out for 12 hours, so as to obtain the polyamic acid solution.
4. The preparation steps of the metal-organic framework mixed matrix membrane are as follows:
modifying the ground titanium with NH2UIO-66 is doped into the polyamic acid solution with the doping amount of 20 wt%, and the doped casting solution is obtained by ultrasonic stirring and is subjected to standing and defoaming treatment. Coating the treated casting solution on a glass plate at room temperature to prepare a wet film with the thickness of 500 mu m, placing the wet film in deionized water (0 ℃) for 6 hours, replacing and removing the solvent to cure and form a film, taking out the film, drying the film at room temperature, and then placing the film in an oven. The temperature is raised from 30 ℃ to 280 ℃ at the speed of 1 ℃/minute, and the constant temperature is kept at 280 ℃ for 1 hour, thus obtaining the polyimide mixed matrix membrane. The thickness of the metal-organic framework mixed matrix film is about 50 μm.
Comparative example 2
1. The UIO-66 material was prepared as follows:
accurately weighing 1.50 g of zirconium tetrachloride, dissolving the zirconium tetrachloride in 30mL of DMF solvent, dissolving the zirconium tetrachloride by magnetic stirring, adding 1.43 g of terephthalic acid, stirring by magnetic stirring for 10min, putting the solution into a microwave oven, reacting for 10min under the microwave condition, centrifuging a product, extracting the product by absolute ethyl alcohol for 20h to remove unreacted terephthalic acid, washing and coating the product by absolute ethyl alcohol for 5 times, filtering, and drying the product in vacuum at 80 ℃ overnight to obtain the product UIO-66 material.
2. The preparation steps of the metal-organic framework mixed matrix membrane are as follows:
subsequent films were prepared as in example 1. The thickness of the metal-organic framework mixed matrix film was about 50 μm.
Comparative example 3
1、NH2-the UIO-66 material is prepared as follows:
accurately weighing 1.50 g of zirconium tetrachloride, dissolving in 30mL of DMF solvent, dissolving by magnetic stirring, adding 1.56 g of 2-aminoterephthalic acid, stirring for 10min by magnetic stirring, putting the solution into a microwave oven, reacting for 10min under the microwave condition, centrifuging the product, extracting the product with absolute ethyl alcohol for 20h to remove unreacted 2-aminoterephthalic acid, washing with absolute ethyl alcohol for 5 times, filtering, and drying in vacuum at 80 ℃ overnight to obtain a product NH2-UIO-66 material.
2. The preparation steps of the metal-organic framework mixed matrix membrane are as follows:
subsequent films were prepared as in example 1. The thickness of the metal-organic framework mixed matrix film was about 50 μm.
Comparative example 4
1、NH2The preparation steps of the ZIF-8 material are as follows:
4.38 grams of zinc acetate dihydrate were dissolved in 40ml of deionized water as the aqueous phase. The oil phase consisted of n-heptane and n-hexanol in a volume ratio of 3:1, containing 0.2mol/L triton X-100 as surfactant, and dissolved 0.738 g 2-methylimidazole and 0.133 g 2-aminobenzimidazole as organic ligands. After the oil phase and the water phase are prepared, adding the water phase into the oil phase, and vibrating to ensure that the water solution is inThe oil phase is uniformly dispersed into the oil phase under the action of the surfactant to form stable reverse microemulsion. After the microemulsion is prepared, standing the microemulsion for a period of time at room temperature, then collecting the product by centrifugal separation, and washing the product for several times by using water and ethanol alternately to obtain NH2-ZIF-8 material. The XRD diffractogram is shown in FIG. 3.
2. The preparation method of the metal-organic framework mixed matrix membrane comprises the following steps:
the subsequent films were prepared as in example 1. The thickness of the metal-organic framework mixed matrix film is about 50 μm.
Comparative example 5
1. The preparation steps of the ZIF-8 material are as follows:
4.38 grams of zinc acetate dihydrate were dissolved in 40ml of deionized water as the aqueous phase. The oil phase 160ml consists of n-heptane and n-hexanol in a volume ratio of 3:1, containing 0.2mol/L triton X-100 as surfactant and dissolved 0.82 g 2-methylimidazole as organic ligand. After the preparation of the oil phase and the water phase is finished, the water phase is added into the oil phase, and the water solution is uniformly dispersed into the oil phase under the action of the surfactant through oscillation to form stable reverse microemulsion. And after the microemulsion is prepared, standing the microemulsion for a period of time at room temperature, then collecting a product through centrifugal separation, and washing the product for several times by using water and ethanol alternately to obtain the ZIF-8 material.
2. The preparation steps of the metal-organic framework mixed matrix membrane are as follows:
subsequent films were prepared as in example 1. The thickness of the metal-organic framework mixed matrix film is about 50 μm.
Example 1
Titanium modified NH2UIO-66 preparation same as comparative example 1, NH2Preparation of ZIF-8 is the same as comparative example 4, preparation of the polyamic acid solution is the same as comparative example 1, preparation of the mixed matrix membrane is the same as comparative example 1, and the doping amount of the two metal organic frameworks is 5%. (percentages are by mass relative to the pure film)
Example 2
Titanium modified NH2UIO-66 preparation same as comparative example 1, NH2Preparation of-ZIF-8 Polyamic acid in the same manner as in comparative example 4The solution was prepared as in comparative example 1, and the mixed matrix membrane was prepared as in comparative example 1. The thickness of the metal-organic framework mixed matrix film was about 50 μm.
The doping amount of the two metal organic frameworks is 10 percent.
Example 3
Titanium modified NH2UIO-66 preparation same as comparative example 1, NH2Preparation of ZIF-8 As in comparative example 4, preparation of a polyamic acid solution as in comparative example 1, and preparation of a mixed matrix membrane as in comparative example 1. The thickness of the metal-organic framework mixed matrix film was about 50 μm.
The doping amount of the two metal organic frameworks is 15 percent.
Example 4
Titanium modified NH2UIO-66 preparation same as comparative example 1, NH2Preparation of ZIF-8 As in comparative example 4, preparation of a polyamic acid solution as in comparative example 1, and preparation of a mixed matrix membrane as in comparative example 1. The thickness of the metal-organic framework mixed matrix film was about 50 μm.
The doping amount of the two metal organic frameworks is 20 percent.
Example 5
Titanium modified NH2UIO-66 preparation same as comparative example 1, NH2Preparation of ZIF-8 As in comparative example 4, preparation of a polyamic acid solution as in comparative example 1, and preparation of a mixed matrix membrane as in comparative example 1. The thickness of the metal-organic framework mixed matrix film was about 50 μm.
NH 210% of each UIO-66 material, NH2The doping amount of the ZIF-8 material is 20%.
Example 6
Titanium modified NH2UIO-66 preparation same as comparative example 1, NH2Preparation of ZIF-8 As in comparative example 4, preparation of a polyamic acid solution as in comparative example 1, and preparation of a mixed matrix membrane as in comparative example 1. The thickness of the metal-organic framework mixed matrix film was about 50 μm.
NH2UIO-66 in a 20% NH content2The doping amount of ZIF-8 is 10%.
Example 7
Titanium modified NH2UIO-66 preparation as in comparative example 1, where modification was carried outTitanium (IV) tetrachlorobis (tetrahydrofuran) was weighed 0.1 g, NH21.6 grams of UIO-66 material. The thickness of the metal-organic framework mixed matrix film is about 50 μm.
NH2Preparation of ZIF-8 As in comparative example 4, preparation of a polyamic acid solution as in comparative example 1, and preparation of a mixed matrix membrane as in comparative example 1.
Titanium modified NH2UIO-66 in a 20% NH content2The doping amount of ZIF-8 is 10%.
Example 8
Titanium modified NH2UIO-66 preparation As in comparative example 1, wherein 0.1 g of titanium (IV) tetrachlorobis (tetrahydrofuran) was weighed during the modification, NH2UIO-662.63 g.
NH2Preparation of-ZIF-8 Material in the same manner as in comparative example 4, preparation of Mixed matrix Membrane in the same manner as in comparative example 1, titanium-modified NH2UIO-66 in a 20% NH content2The doping amount of-ZIF-8 is 10%. The thickness of the metal-organic framework mixed matrix film was about 50 μm.
Cutting the mixed matrix membrane to a diameter of about 2cm, placing the mixed matrix membrane into a membrane separation tester, introducing carbon dioxide/methane (the volume ratio of carbon dioxide to nitrogen is 50:50), keeping the pressure difference between two sides of the membrane at 1bar, testing the flow of the carbon dioxide/methane after the temperature is kept stable at 25 ℃, and calculating to obtain the carbon dioxide/methane selection coefficient, wherein the result is shown in table 1:
the calculation formula of the carbon dioxide/methane selection coefficient is as follows: the selection coefficient (%) is carbon dioxide volume flow/(carbon dioxide volume flow + methane volume flow) × 100%.
TABLE 1 examples and comparative examples
Figure BDA0002846479930000081
Figure BDA0002846479930000091
Note: the pure membrane is a membrane without any MOF-doped material added, and the preparation process is the same as that of comparative example 1.

Claims (10)

1. A metal-organic framework mixed matrix film comprising titanium modified NH2-UIO-66、NH2ZIF-8 and polyimide.
2. The metal-organic framework mixed matrix membrane according to claim 1, wherein the titanium-modified NH is based on the mass of the metal-organic framework mixed matrix membrane2-the mass content of UIO-66 is 5% to 20%; NH (NH)2-5% -20% of ZIF-8 by mass; the mass content of the polyimide is 60-90%.
3. The metal-organic framework mixed matrix membrane according to claim 1, wherein titanium-modified NH2-UIO-66, titanium content 0.28% -1.39% by mass.
4. The metal-organic framework mixed matrix membrane according to claim 1, wherein the molar ratio of titanium to zirconium in the metal-organic framework mixed matrix membrane is 1:12 to 60, preferably 1:15 to 35.
5. A method for producing a metal-organic framework mixed matrix membrane according to any one of claims 1 to 4, comprising the steps of:
modification of titanium with NH2UIO-66 and NH2Doping ZIF-8 into a polyamic acid solution, stirring to obtain a doped casting solution, and standing and defoaming; coating the processed casting film liquid on a glass plate to prepare a wet film, removing the solvent to solidify and form a film, and performing heat treatment to prepare the metal-organic framework mixed matrix film.
6. The method according to claim 5, wherein the heat treatment conditions are as follows: the treatment temperature is 200-350 ℃, and the treatment time is 0.5-2 h.
7. The method of claim 5, wherein the titanium-modified NH is2-UIO-66, comprising the steps of:
(1) dissolving zirconium salt in organic solvent A, adding 2-amino terephthalic acid, and reacting to obtain NH2-UIO-66；
(2) Dissolving titanium salt in chlorohydrocarbon, adding tetrahydrofuran in an inert atmosphere, uniformly mixing, adding a solvent B, filtering and drying to obtain tetrachlorobis (tetrahydrofuran) titanium (IV);
(3) dissolving titanium (IV) tetrachlorobis (tetrahydrofuran) prepared in the step (2) in an organic solvent C, and adding NH prepared in the step (1)2UIO-66, standing, filtering, washing and drying to obtain titanium modified NH2-UIO-66。
8. The process according to claim 7, wherein the titanium (IV) tetrachlorobis (tetrahydrofuran) solid is reacted with NH in the step (3)2UIO-66 in a molar ratio of 1:2 to 10, preferably 1:2 to 6.
9. Use of the metal-organic framework mixed matrix membrane according to any one of claims 1 to 4 for separating CO2/CH4A method of producing a gas.
10. The method of claim 9, wherein the CO is2/CH4Volume ratio of gas 1:2-2: 1; the pressure difference is 0-0.1MPa, and the temperature is 20-50 ℃.
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