CN113750821B - g-C based on embedded porous few layers 3 N 4 Preparation method and application of/ZIF-8 mixed matrix membrane - Google Patents
g-C based on embedded porous few layers 3 N 4 Preparation method and application of/ZIF-8 mixed matrix membrane Download PDFInfo
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 80
- 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 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 39
- 238000005266 casting Methods 0.000 claims abstract description 49
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 17
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010992 reflux Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 126
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 43
- 239000011521 glass Substances 0.000 claims description 36
- 229920002614 Polyether block amide Polymers 0.000 claims description 31
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 229920002530 polyetherether ketone Polymers 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000004570 mortar (masonry) Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000002000 scavenging effect Effects 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 claims description 2
- 238000011056 performance test Methods 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 239000011256 inorganic filler Substances 0.000 abstract description 2
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 93
- 239000010410 layer Substances 0.000 description 92
- 230000035699 permeability Effects 0.000 description 20
- 239000012043 crude product Substances 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012466 permeate Substances 0.000 description 7
- 238000007605 air drying Methods 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 5
- 229920005597 polymer membrane Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a g-C based on an embedded porous few layers 3 N 4 Preparation method and application of/ZIF-8 mixed matrix membrane. The preparation method comprises the following steps: first, g-C is prepared by calcining melamine 3 N 4 Then mixing with alcohols, and carrying out thermal reflux to strip to prepare the porous few-layer g-C 3 N 4 And in a porous minor layer g-C 3 N 4 And in-situ ZIF-8 growth is carried out between the layers. Adding the prepared inorganic filler into a polymer matrix, and adopting a solution casting method to prepare an embedded porous few-layer-based g-C 3 N 4 ZIF-8 mixed matrix membranes. The porous few-layer structure formed by stripping can reduce the transfer resistance of gas molecules and ZIF-8 to CO 2 The prepared mixed matrix membrane has excellent separation performance, breaks through the 'trade-off' effect and has excellent comprehensive performance.
Description
Technical Field
The invention relates to an embedded porous few-layer g-C based 3 N 4 A preparation method and application of a ZIF-8 mixed matrix membrane belong to the technical field of chemical engineering membrane separation.
Background
With the development of industrial revolution, global energy demand is increasing, and fossil energy is largely burned. Over the past few years, fossil fuels have been used in excess to make CO in air 2 The concentration of (c) increases rapidly, causing various ecological problems. CO capture 2 In reducing CO in air 2 At the same time of concentration, CO can also be utilized 2 Benefiting human life. In membrane separation, a mixed matrix membrane plays an important role, and a mixed matrix membrane with a proper inorganic filler and a polymer matrix can obtain excellent gas separation performance and break through the Robeson upper limit.
Polyether block amides, which are composed of flexible Polyethers (PE) and relatively rigid Polyamides (PA), have been widely used as film materials in a number of fields. The PE phase with high chain mobility may increase permeability, forcing gas molecules to pass through the membrane quickly, while the PA phase may provide high mechanical properties. Graphite carbon carbonitride (g-C) 3 N 4 ) The modified graphite-like composite material has a layered structure similar to graphite, has good thermal stability and chemical stability, and can be subjected to functional group modification or grafting between layers due to small van der Waals force between the layers. And for g-C 3 N 4 In the post-treatment of (2), a slightly larger structural defect may be generated, the transfer resistance of gas molecules is reduced, and a rapid transfer channel is provided for small molecules.
Disclosure of Invention
The invention prepares g-C based on embedded porous few layers 3 N 4 The ZIF-8 mixed matrix film provides a simple and efficient stripping g-C 3 N 4 And a method for grafting ZIF-8. Application of the mixed matrix membrane to CO 2 /N 2 Separation to obtain higher CO 2 Permeability coefficient and separation factor.
g-C used in the present invention 3 N 4 For CO 2 Has affinity; g-C after thermal reflux treatment 3 N 4 The interlayer spacing is reduced, so that the transfer resistance of gas molecules is reduced; ZIF-8 was successfully grafted to g-C 3 N 4 A sheet layer; incorporated ZIF-8 for CO 2 /N 2 CO during separation 2 Provides a fast path and improves CO 2 And a separation factor.
In the present invention, the prepared g-C is first 3 N 4 Thermal reflux stripping in alcohols to form a porous few-layer structure, and then preparing embedded porous few-layer g-C by in-situ growth ZIF-8 3 N 4 ZIF-8, and then g-C the embedded porous few layer 3 N 4 ZIF-8 is introduced into a polymer matrix and is prepared by a solution casting method based on embedded porous few-layer g-C 3 N 4 Mixed matrix membranes of ZIF-8. The method is based on embedded porous few-layer g-C 3 N 4 Mixed matrix membranes of/ZIF-8 can further enhance CO 2 Permeability and CO of (C) 2 /N 2 Selectivity.
The preparation method comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, weighing 1-200 g of melamine, placing the melamine into a tube furnace, heating the melamine to 400-600 ℃ at a heating rate of 1-10 ℃/min, and then keeping the melamine constant temperature in the air for 2-24 h. The yellow product was collected and ground in a mortar to a powder, designated product a. Then adding the product A into a mixture of the solvent B and the solvent C, wherein the concentration of the product A in the solvent B is 0.01-1 g/mL, and the volume ratio of the solvent B to the solvent C is (0.1-1): 1, and refluxing 1-12 h at 50-150 ℃. Then washing the powder with ethanol for 3-5 times, and drying in a blast drying oven at 30-100 ℃ for 8-24 h to prepare the porous few-layer g-C 3 N 4 The product D was noted.
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in methanol at the concentration of 0.01-0.5 g/mL, and ultrasonic treatment at 20-70 deg.c and 20-50 KHz frequency for 0.5-24 h to disperse homogeneously. Zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 Mechanically stirring the solution in methanol at a rotation speed of 100-500 rpm for 0.5-12 h to obtain Zn (NO) 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 The concentration of O in the methanol solution is 0.001-0.1 g/mL; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1: (4-10), mechanically stirring at 20-90 ℃ for 12-48 h to make Zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 Crude product/ZIF-8. And washing the product with methanol for 3-5 times, and drying the product in an oven at 30-80 ℃ for 6-24 h. The resulting composite was designated product E.
(3) g-C based on embedded porous few layers 3 N 4 Preparation of a ZIF-8 mixed matrix film: the product is subjected to the following stepsE is added into a solvent F required by film preparation, and ultrasonic treatment is carried out at the temperature of 20-70 ℃ and the frequency of 20-50 KHz for 0.5-6 h to ensure that the solvent F is uniformly dispersed, and the solvent is named as solution G. Then adding the polymer matrix into the solution G, stirring 2-24H by a magnetic stirrer at the temperature of 20-80 ℃ and the rotating speed of 100-2000 rpm to completely dissolve the polymer, and standing and defoaming for 12-48H to obtain the uniform casting solution H. Wherein the polymer matrix accounts for (2-15)% of the casting solution, and the mass ratio of the product E to the polymer matrix in the casting solution is (0.01-0.1): 1. uniformly coating a casting solution H on a clean glass plate or a polytetrafluoroethylene plate by using a film coater, controlling the thickness of a wet film to be 300-1500 mu m, then placing the coated glass plate or polytetrafluoroethylene plate in a vacuum oven at 25-80 ℃ for vacuum drying 12-48H, and then drying 8-48H in the vacuum oven at 80-150 ℃; the film after the solvent is removed from the glass plate or the polytetrafluoroethylene plate and is properly stored for standby.
Further, in the step (1) of the preparation method, the solvent B is one of ethylene glycol and glycerol.
Further, in step (1) of the above preparation method, the solvent C is one of methanol, ethanol, n-propanol, and n-butanol.
In step (3) of the above preparation method, the solvent F required for film formation is one of N, N '-dimethylacetamide, N' -dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and tetrahydrofuran.
Further, in the step (3) of the preparation method, the polymer matrix is one of polyether block amide, sulfonated polyether ether ketone, polyimide, cellulose acetate and polydimethylsiloxane.
The g-C based on the embedded porous few layers 3 N 4 The thickness of the/ZIF-8 mixed matrix film is 20-200 mu m.
The invention also provides the embedded porous few-layer-based g-C prepared by the method 3 N 4 Separation of CO by ZIF-8 mixed matrix membrane 2 Is used in the field of applications.
Further, based onEmbedded porous few layer g-C 3 N 4 The gas separation performance test of the/ZIF-8 mixed matrix membrane adopts a constant pressure variable volume method, and the effective area of membrane permeation is 10-100 cm 2 Scavenging is carried out by H 2 The scavenging flow rate is 10-100 mL/min, the feeding gas flow rate is 10-60 mL/min, the flow rates of the raw material side and the permeation side are measured by flow meters, and the component content of the permeation side is tested by gas chromatography; the test temperature is 20-100 ℃ and the pressure difference is 0.1-1.5 MPa.
The invention has the beneficial effects that:
(1) Embedded porous few layer g-C 3 N 4 ZIF-8 materials provide a method of stripping, few layers, and adjustable layer spacing for CO 2 Has positive significance in the selective transmission of (a);
(2) g-C based on embedded porous few layers 3 N 4 the/ZIF-8 mixed matrix membrane can obviously improve CO 2 Permeability and CO 2 /N 2 、CO 2 /CH 4 Selectivity of (2);
(3) g-C based on embedded porous few layers 3 N 4 The temperature has a small effect on the permeability and selectivity of the membrane compared to the pure polymer membrane.
(4) g-C based on embedded porous few layers 3 N 4 The ZIF-8 mixed matrix membrane has low membrane preparation cost, uncomplicated preparation process, easy operation, good running stability and good industrial application potential.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Comparative example 1: the pure polyether block amide homogeneous polymer film comprises the following steps:
polyether block amide is dissolved in N, N-dimethylacetamide solvent to prepare polyether block amide which is dissolved in N, N-dimethylacetamide solvent with the mass percentage of 0.06: and (1) stirring the casting solution for 48 hours at the temperature of 70 ℃ at the rotation speed of 500rpm by adopting a magnetic stirrer to completely dissolve the casting solution to form uniform casting solution, and defoaming the uniform casting solution for 12 hours at the constant temperature of 25 ℃ for later use. The casting solution is uniformly scraped on a clean glass plate by a scraper, the thickness of a wet film is controlled to be 300 mu m, then the glass plate is placed at normal temperature to volatilize the solvent for 48 hours, and the glass plate is dried in a vacuum oven at 60 ℃ for 48 hours to remove the residual solvent. The film after the solvent is removed from the glass plate and is properly stored for later use.
The prepared polyether block amide homogeneous polymer film is tested under the conditions that the temperature is 25 ℃ and the pressure difference between the raw material side and the permeation side of the film is 0.2 MPa, and CO is measured 2 Permeability coefficient 162 Barrer, CO 2 /N 2 The separation factor was 26.
Comparative example 2: the preparation method of the pure sulfonated polyether-ether-ketone homogeneous polymer membrane comprises the following steps:
the sulfonated polyether-ether-ketone is weighed and added into N, N-dimethylformamide solvent to prepare the sulfonated polyether-ether-ketone and the N, N-dimethylformamide with the mass percentage of 0.1:1, magnetically stirring the solution at 25 ℃ for 24h to obtain a homogeneous sulfonated polyether-ether-ketone solution, filtering out indissoluble impurities by using a screen, standing for 2h for defoaming, pouring the solution on a clean and flat glass plate, controlling the thickness of a wet film to be 300 mu m, standing the glass plate poured with the film casting solution in the environment for 10 min, transferring the glass plate into a 60 ℃ oven for drying for 12h, and then carrying out heat treatment at 100 ℃ for 4h to obtain the sulfonated polyether-ether-ketone homogeneous polymer film, and properly keeping the film for later use.
The prepared pure sulfonated polyether-ether-ketone homogeneous polymer membrane is tested under the conditions that the temperature is 25 ℃ and the pressure difference between the membrane raw material side and the permeation side is 0.1 MPa, and CO is measured 2 Permeability coefficient of 364 Barrer, CO 2 /N 2 The separation factor was 27.
Example 1:
g-C based on embedded porous few layers 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, 10 g melamine is weighed and placed in a tube furnace, heated to 550 ℃ at a heating rate of 2 ℃/min, and then kept at a constant temperature in air for 8 hours. The yellow product was collected and ground in a mortar to a powder, designated product a. Then adding the product A into a mixture of glycerol and ethanol, wherein the concentration of the product A in the glycerol is 0.15 g/mL, and the glycerolThe volume ratio of the ethanol to the ethanol is 0.33:1, reflux 6 h at 90 ℃. Then washing the powder with ethanol for 3 times, and drying in a blast drying oven at 60deg.C for 12 hr to obtain porous few-layer g-C 3 N 4 Designated as product D.
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in methanol at concentration of 0.067/g/mL, and ultrasonic treating at frequency of 30 KHz and temperature of 25deg.C for 2h to obtain uniform dispersion. Zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 In methanol solution, zn (NO) was mechanically stirred at a rotation speed of 100rpm for 4. 4h 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 O has the concentration of 0.01 g/mL in the methanol solution; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:4 mechanically stirring 24h at 25 ℃ to obtain Zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 Crude product/ZIF-8. The product was washed 3 times with methanol and dried in an oven at 40 ℃ 12 h. The resulting composite was designated product E.
(3) g-C based on embedded porous few layers 3 N 4 Preparation of a ZIF-8 mixed matrix film: product E was added to solvent N, N-dimethylacetamide and dispersed uniformly by sonication at a temperature of 30℃and a frequency of 40 KHz at 0.5. 0.5 h, designated solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring 8H by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, and standing for defoaming for 24H to obtain the uniform casting solution H. Wherein the polyether block amide accounts for 6% of the mass of the casting solution, and the mass ratio of the product E to the polyether block amide in the casting solution is 0.01:1. coating the casting solution H on a clean glass plate uniformly by using a film coater, controlling the thickness of a wet film to be 300 mu m, then placing the coated glass plate in a vacuum oven at 45 ℃ for vacuum drying 24H, and drying in a vacuum oven at 80 ℃ for 12 h; and removing the film after the solvent is removed from the surface of the glass plate, and properly keeping the film for later use.
Prepared g-C based on embedded porous few layers 3 N 4 The ZIF-8 mixed matrix membrane was tested at a temperature of 25deg.C under a pressure differential of 0.2 MPa on the membrane feed side and on the permeate side to obtain CO 2 Permeability coefficient of 292Barrer, CO 2 /N 2 The separation factor was 61.
Example 2:
g-C based on embedded porous few layers 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, 10 g melamine is weighed and placed in a tube furnace, heated to 550 ℃ at a heating rate of 2 ℃/min, and then kept at a constant temperature of 8h in air. The yellow product was collected and ground in a mortar to a powder, designated product a. Product a was then added to a mixture of glycerol and ethanol, wherein the concentration of product a in glycerol was 0.15 g/mL and the volume ratio of glycerol to ethanol was 0.33:1, reflux 6 h at 90 ℃. Then washing the powder with ethanol for 3 times, and drying in a blast drying oven at 60deg.C for 12 hr to obtain porous few-layer g-C 3 N 4 Designated as product D.
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in methanol at concentration of 0.033 g/mL, and ultrasonic treating at frequency of 30 KHz and temperature of 25deg.C for 2h to obtain uniform dispersion. Zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 In methanol solution, zn (NO) was mechanically stirred at a rotation speed of 100rpm for 4. 4h 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 O has the concentration of 0.01 g/mL in the methanol solution; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:4 mechanically stirring 24h at 25 ℃ to obtain Zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 /ZIF-8 crude product. The product was washed 3 times with methanol and dried in an oven at 40 ℃ 12 h. The resulting composite was designated product E.
(3) g-C based on embedded porous few layers 3 N 4 Preparation of a ZIF-8 mixed matrix film: product E was added to solvent N, N-dimethylacetamide and dispersed uniformly by sonication at a temperature of 30℃and a frequency of 40 KHz at 0.5. 0.5 h, designated solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring 8H by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, and standing for defoaming for 24H to obtain the uniform casting solution H. Wherein the polyether block amide accounts for 6% of the mass of the casting solution, and the mass ratio of the product E to the polyether block amide in the casting solution is 0.01:1. uniformly coating the casting solution H on a clean glass plate by using a film coater, controlling the thickness of a wet film to be 300 mu m, then placing the coated glass plate in a vacuum oven at 45 ℃ for vacuum drying 24H, and drying 12H in the vacuum oven at 80 ℃; and removing the film after the solvent is removed from the surface of the glass plate, and properly keeping the film for later use.
Prepared g-C based on embedded porous few layers 3 N 4 The ZIF-8 mixed matrix membrane was tested at a temperature of 25deg.C under a pressure differential of 0.2 MPa on the membrane feed side and on the permeate side to obtain CO 2 Permeability coefficient of 315 Barrer, CO 2 /N 2 The separation factor is 76.
Example 3:
g-C based on embedded porous few layers 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, 10 g melamine is weighed and placed in a tube furnace, heated to 550 ℃ at a heating rate of 2.5 ℃/min, and then kept at a constant temperature of 12h in air. The yellow product was collected and ground in a mortar to a powder, designated product a. Product a was then added to a mixture of ethylene glycol and ethanol, wherein the concentration of product a in ethylene glycol was 0.12 g/mL and the volume ratio of ethylene glycol to ethanol was 0.33:1, reflux 6 h at 80 ℃. The powder was then washed 3 times with ethanol at 80℃Drying 8. 8h in a forced air drying oven to obtain porous few layers g-C 3 N 4 Designated as product D.
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in methanol with concentration of 0.0167/g/mL, and ultrasonic treating at frequency of 40 KHz and temperature of 30deg.C for 1h to obtain uniform dispersion. Zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 In methanol solution, zn (NO) was mechanically stirred at 200 rpm for 4. 4h 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 O has the concentration of 0.01 g/mL in the methanol solution; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:4 mechanically stirring 24h at 25 ℃ to obtain Zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 Crude product/ZIF-8. The product was washed 3 times with methanol and dried in an oven at 50 ℃ for 12 h. The resulting composite was designated product E.
(3) g-C based on embedded porous few layers 3 N 4 Preparation of a ZIF-8 mixed matrix film: the product E is added into solvent N, N-dimethylacetamide, and the mixture is subjected to ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse, and the mixture is named solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring 8H by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, and standing for defoaming for 24H to obtain the uniform casting solution H. Wherein the polyether block amide accounts for 6% of the mass of the casting solution, and the mass ratio of the product E to the polyether block amide in the casting solution is 0.02:1. uniformly coating the casting solution H on a clean glass plate by using a film coater, controlling the thickness of a wet film to be 300 mu m, then placing the coated glass plate in a vacuum oven at 45 ℃ for vacuum drying 24H, and drying 12H in the vacuum oven at 80 ℃; and removing the film after the solvent is removed from the surface of the glass plate, and properly keeping the film for later use.
Prepared g-C based on embedded porous few layers 3 N 4 The ZIF-8 mixed matrix membrane was tested at a temperature of 25deg.C under a pressure differential of 0.2 MPa on the membrane feed side and on the permeate side to obtain CO 2 Permeability coefficient 366 Barrer, CO 2 /N 2 The separation factor is 82.
Example 4:
g-C based on embedded porous few layers 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, 10 g melamine is weighed and placed in a tube furnace, heated to 600 ℃ at a heating rate of 2 ℃/min, and then kept at a constant temperature of 18 h in air. The yellow product was collected and ground in a mortar to a powder, designated product a. Product a was then added to a mixture of glycerol and ethanol, wherein the concentration of product a in glycerol was 0.15 g/mL and the volume ratio of glycerol to ethanol was 0.33:1, reflux 6 h at 80 ℃. Then washing the powder with ethanol for 3 times, and drying in a forced air drying oven at 80deg.C for 8h to obtain porous few-layer g-C 3 N 4 Designated as product D.
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in methanol with concentration of 0.0167/g/mL, and ultrasonic treating at frequency of 40 KHz and temperature of 30deg.C for 1h to obtain uniform dispersion. Zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 In methanol solution, zn (NO) was mechanically stirred at 200 rpm for 4. 4h 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 O has the concentration of 0.01 g/mL in the methanol solution; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:6 mechanically stirring 24h at a temperature of 30 ℃ to effect a reduction in Zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 Crude product/ZIF-8. The product was washed 3 times with methanol and dried 24h in an oven at 50 ℃. The obtained composite material is recorded as the productAnd E.
(3) g-C based on embedded porous few layers 3 N 4 Preparation of a ZIF-8 mixed matrix film: the product E is added into solvent N, N-dimethylformamide, and is subjected to ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse, and the product is named as solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring 8H by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, and standing for defoaming for 24H to obtain the uniform casting solution H. Wherein the polyether block amide accounts for 6% of the mass of the casting solution, and the mass ratio of the product E to the polyether block amide in the casting solution is 0.005:1. uniformly coating the casting solution H on a clean glass plate by using a film coater, controlling the thickness of a wet film to be 300 mu m, then placing the coated glass plate in a vacuum oven at 45 ℃ for vacuum drying 24H, and drying 12H in the vacuum oven at 80 ℃; and removing the film after the solvent is removed from the surface of the glass plate, and properly keeping the film for later use.
Prepared g-C based on embedded porous few layers 3 N 4 The ZIF-8 mixed matrix membrane was tested at a temperature of 25deg.C under a pressure differential of 0.2 MPa on the membrane feed side and on the permeate side to obtain CO 2 Permeability coefficient 269 Barrer, CO 2 /N 2 The separation factor was 71.
Example 5:
g-C based on embedded porous few layers 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, 10 g melamine is weighed and placed in a tube furnace, heated to 550 ℃ at a heating rate of 3 ℃/min, and then kept at a constant temperature of 12h in air. The yellow product was collected and ground in a mortar to a powder, designated product a. Product a was then added to a mixture of ethylene glycol and ethanol, wherein the concentration of product a in ethylene glycol was 0.15 g/mL and the volume ratio of ethylene glycol to ethanol was 0.33:1, reflux 12h at 80 ℃. Then washing the powder with ethanol for 3 times, and drying in a forced air drying oven at 80deg.C for 8h to obtain porous few-layer g-C 3 N 4 Designated as product D.
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in methanol with concentration of 0.0167/g/mL, and ultrasonic treating at frequency of 40 KHz and temperature of 30deg.C for 1h to obtain uniform dispersion. Zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 In methanol solution, zn (NO) was mechanically stirred at 200 rpm for 8h 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 O has the concentration of 0.01 g/mL in the methanol solution; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:4 mechanically stirring 24h at 25 ℃ to obtain Zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 Crude product/ZIF-8. The product was washed 5 times with methanol and dried 24h in an oven at 50 ℃. The resulting composite was designated product E.
(3) g-C based on embedded porous few layers 3 N 4 Preparation of a ZIF-8 mixed matrix film: the product E is added into solvent N, N-dimethylacetamide, and the mixture is subjected to ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse, and the mixture is named solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring 8H by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, and standing for defoaming for 24H to obtain the uniform casting solution H. Wherein the polyether block amide accounts for 6% of the mass of the casting solution, and the mass ratio of the product E to the polyether block amide in the casting solution is 0.01:1. uniformly coating the casting solution H on a clean glass plate by using a film coater, controlling the thickness of a wet film to be 300 mu m, then placing the coated glass plate in a vacuum oven at 45 ℃ for vacuum drying 24H, and drying 12H in the vacuum oven at 80 ℃; and removing the film after the solvent is removed from the surface of the glass plate, and properly keeping the film for later use.
Prepared g-C based on embedded porous few layers 3 N 4 ZIF-8 mixed matrix membrane at 25deg.CThe pressure difference between the material side and the permeation side is 0.5 MPa, and CO is measured 2 Permeability coefficient 471Barrer, CO 2 /N 2 The separation factor is 110.
Example 6:
g-C based on embedded porous few layers 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, 10 g melamine is weighed and placed in a tube furnace, heated to 550 ℃ at a heating rate of 2.5 ℃/min, and then kept at a constant temperature of 12h in air. The yellow product was collected and ground in a mortar to a powder, designated product a. Product a was then added to a mixture of ethylene glycol and ethanol, wherein the concentration of product a in ethylene glycol was 0.12 g/mL and the volume ratio of ethylene glycol to ethanol was 0.33:1, reflux 6 h at 80 ℃. Then washing the powder with ethanol for 3 times, and drying in a forced air drying oven at 80deg.C for 8h to obtain porous few-layer g-C 3 N 4 Designated as product D.
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in methanol with concentration of 0.0167/g/mL, and ultrasonic treating at frequency of 40 KHz and temperature of 30deg.C for 1h to obtain uniform dispersion. Zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 In methanol solution, zn (NO) was mechanically stirred at 200 rpm for 4. 4h 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 O has the concentration of 0.01 g/mL in the methanol solution; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:4 mechanically stirring 24h at a temperature of 30 ℃ to obtain Zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 Crude product/ZIF-8. The product was washed 3 times with methanol and dried 8h in an oven at 80 ℃. The resulting composite was designated product E.
(3) g-C based on embedded porous few layers 3 N 4 ZIF-8 blendsPreparation of the composite matrix film: the product E is added into solvent N, N-dimethylacetamide, and the mixture is subjected to ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse, and the mixture is named solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring 8H by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, and standing for defoaming for 24H to obtain the uniform casting solution H. Wherein the polyether block amide accounts for 6% of the mass of the casting solution, and the mass ratio of the product E to the polyether block amide in the casting solution is 0.03:1. uniformly coating the casting solution H on a clean glass plate by using a film coater, controlling the thickness of a wet film to be 300 mu m, then placing the coated glass plate in a vacuum oven at 45 ℃ for vacuum drying 24H, and drying 12H in the vacuum oven at 80 ℃; and removing the film after the solvent is removed from the surface of the glass plate, and properly keeping the film for later use.
Prepared g-C based on embedded porous few layers 3 N 4 The ZIF-8 mixed matrix membrane was tested at a temperature of 25deg.C under a pressure differential of 0.3 MPa on the membrane feed side and on the permeate side to obtain CO 2 Permeability coefficient of 410 Barrer, CO 2 /N 2 The separation factor was 91.
Example 7:
g-C based on embedded porous few layers 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, 10 g melamine is weighed and placed in a tube furnace, heated to 550 ℃ at a heating rate of 2.5 ℃/min, and then kept at a constant temperature of 12h in air. The yellow product was collected and ground in a mortar to a powder, designated product a. Product a was then added to a mixture of ethylene glycol and ethanol, wherein the concentration of product a in ethylene glycol was 0.12 g/mL and the volume ratio of ethylene glycol to ethanol was 0.33:1, reflux 6 h at 80 ℃. Then washing the powder with ethanol for 3 times, and drying in a forced air drying oven at 80deg.C for 8h to obtain porous few-layer g-C 3 N 4 Designated as product D.
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in firstIn alcohol, the concentration of the product D in methanol is 0.0167 g/mL, and the product D is uniformly dispersed by ultrasonic treatment at a frequency of 40 KHz and a temperature of 30 ℃ for 1 h. Zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 In methanol solution, zn (NO) was mechanically stirred at 200 rpm for 4. 4h 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 O has the concentration of 0.01 g/mL in the methanol solution; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:4 mechanically stirring 24h at 25 ℃ to obtain Zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 Crude product/ZIF-8. The product was washed 3 times with methanol and dried in an oven at 50 ℃ for 12 h. The resulting composite was designated product E.
(3) g-C based on embedded porous few layers 3 N 4 Preparation of a ZIF-8 mixed matrix film: the product E is added into dimethyl sulfoxide solvent, and the mixture is subjected to ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse, and the mixture is named as solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring 8H by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, and standing for defoaming for 24H to obtain the uniform casting solution H. Wherein the polyether block amide accounts for 6% of the mass of the casting solution, and the mass ratio of the product E to the polyether block amide in the casting solution is 0.04:1. uniformly coating the casting solution H on a clean glass plate by using a film coater, controlling the thickness of a wet film to be 300 mu m, then placing the coated glass plate in a vacuum oven at 45 ℃ for vacuum drying 24H, and drying 12H in the vacuum oven at 80 ℃; and removing the film after the solvent is removed from the surface of the glass plate, and properly keeping the film for later use.
Prepared g-C based on embedded porous few layers 3 N 4 The ZIF-8 mixed matrix membrane was tested at a temperature of 70deg.C and a pressure difference between the membrane material side and the permeate side of 0.2 MPa to measure CO 2 Permeability coefficient of 459 Barrer, CO 2 /N 2 The separation factor was 78.
Example 8:
g-C based on embedded porous few layers 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, 10 g melamine is weighed and placed in a tube furnace, heated to 550 ℃ at a heating rate of 2.5 ℃/min, and then kept at a constant temperature of 12h in air. The yellow product was collected and ground in a mortar to a powder, designated product a. Product a was then added to a mixture of ethylene glycol and ethanol, wherein the concentration of product a in ethylene glycol was 0.12 g/mL and the volume ratio of ethylene glycol to ethanol was 0.33:1, reflux 6 h at 80 ℃. Then washing the powder with ethanol for 3 times, and drying in a forced air drying oven at 80deg.C for 8h to obtain porous few-layer g-C 3 N 4 Designated as product D.
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in methanol with concentration of 0.0167/g/mL, and ultrasonic treating at frequency of 40 KHz and temperature of 30deg.C for 1h to obtain uniform dispersion. Zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 In methanol solution, zn (NO) was mechanically stirred at 200 rpm for 4. 4h 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 O has the concentration of 0.01 g/mL in the methanol solution; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:4 mechanically stirring 24h at a temperature of 30 ℃ to obtain Zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 Crude product/ZIF-8. The product was washed 3 times with methanol and dried 8h in an oven at 80 ℃. The resulting composite was designated product E.
(3) g-C based on embedded porous few layers 3 N 4 Preparation of a ZIF-8 mixed matrix film: adding the product E into solvent N, N-dimethylacetamide at 30 deg.C and 40 KHz frequencyThe mixture was sonicated for 1h to disperse the mixture evenly and designated solution G. And then adding the polymer matrix sulfonated polyether-ether-ketone into the solution G, stirring 8H by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, and standing and defoaming for 24H to obtain the uniform casting solution H. Wherein the sulfonated polyether-ether-ketone accounts for 10% of the mass of the casting solution, and the mass ratio of the product E to the sulfonated polyether-ether-ketone in the casting solution is 0.03:1. uniformly coating the casting solution H on a clean glass plate by using a film coater, controlling the thickness of a wet film to be 300 mu m, then placing the coated glass plate in a vacuum oven at 45 ℃ for vacuum drying 24H, and drying 12H in the vacuum oven at 80 ℃; and removing the film after the solvent is removed from the surface of the glass plate, and properly keeping the film for later use.
Prepared g-C based on embedded porous few layers 3 N 4 The ZIF-8 mixed matrix membrane was tested at a temperature of 25deg.C under a pressure differential of 0.2 MPa on the membrane feed side and on the permeate side to obtain CO 2 Permeability coefficient of 610 Barrer, CO 2 /N 2 The separation factor was 39.
From comparative studies of comparative example 1 and examples 1 to 7, it was found that the prepared embedded porous few-layer-based g-C 3 N 4 Compared with polyether block amide homogeneous polymer membrane, the ZIF-8 mixed matrix membrane is prepared by using CO 2 Permeability coefficient and CO 2 /N 2 The separation factors are greatly improved. In particular CO in comparative example 5 2 The permeability coefficient reaches 471Barrer, CO 2 /N 2 The separation factor reaches 110. CO with polyether block amide homogeneous polymer film 2 Permeability coefficient of 162 Barrer compared with CO 2 The permeability coefficient is improved by 191%; CO of homogeneous polymer film compared to polyether block amide 2 /N 2 The separation factor 26 was increased by 323%. From comparative studies of comparative example 2 and example 8, it was found that the prepared embedded porous few-layer-based g-C 3 N 4 Compared with sulfonated polyether-ether-ketone homogeneous polymer membrane, the ZIF-8 mixed matrix membrane is characterized by CO 2 Permeability coefficient and CO 2 /N 2 The separation factor is also significantly improved.
Although the present invention has been described above, the present invention is not limited to the above-described embodiment, which is merely illustrative and not restrictive, and various modifications may be made by those ordinarily skilled in the art without departing from the gist of the present invention, which fall within the protection of the present invention.
Claims (6)
1. g-C based on embedded porous few layers 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane is characterized by comprising the following steps: first, the prepared g-C 3 N 4 Stripping under reflux in alcohol, and then stripping the porous few layer g-C 3 N 4 In-situ growth of ZIF-8 to prepare embedded porous few-layer g-C 3 N 4 ZIF-8, and then g-C the embedded porous few layer 3 N 4 ZIF-8 is introduced into a polymer matrix and is prepared by a solution casting method based on embedded porous few-layer g-C 3 N 4 Mixed matrix membranes of ZIF-8;
the embedded porous few-layer-based g-C 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane comprises the following steps:
(1) Porous few layer g-C 3 N 4 Is prepared from the following steps: firstly, weighing 1-200 g of melamine, placing the melamine into a tube furnace, heating the melamine to 400-600 ℃ at a heating rate of 1-10 ℃/min, and then keeping the melamine constant temperature in the air for 2-24 h; the yellow product was collected and ground in a mortar to a powder, designated product a; then adding the product A into a mixture of the solvent B and the solvent C, wherein the concentration of the product A in the solvent B is 0.01-1 g/mL, and the volume ratio of the solvent B to the solvent C is (0.1-1): 1, refluxing 1-12 h at 50-150 ℃; then washing the powder with ethanol for 3-5 times, and drying in a blast drying oven at 30-100 ℃ for 8-24 h to prepare the porous few-layer g-C 3 N 4 The product is marked as a product D; the solvent B is one of glycol and glycerol; the solvent C is one of methanol, ethanol, n-propanol and n-butanol;
(2) Embedded porous few layer g-C 3 N 4 Preparation of ZIF-8: dispersing the product D in methanol with concentration of 0.01-0.5 g/mL, frequency of 20-50 KHz,Ultrasound is carried out at the temperature of 20-70 ℃ for 0.5-24 h to ensure that the dispersion is uniform; zn (NO) 3 ) 2 ·6H 2 O is added to the porous few layer g-C 3 N 4 Mechanically stirring the solution in methanol at a rotation speed of 100-500 rpm for 0.5-12 h to obtain Zn (NO) 3 ) 2 ·6H 2 O was dispersed uniformly and named solution E, in which Zn (NO 3 ) 2 ·6H 2 The concentration of O in the methanol solution is 0.001-0.1 g/mL; 2-methylimidazole was added to solution E, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1: (4-10) mechanically stirring 12-48 h at 20-90 ℃ to obtain Zn (NO) 3 ) 2 ·6H 2 O and 2-methylimidazole react to generate embedded porous few-layer g-C 3 N 4 Crude ZIF-8; washing the product with methanol for 3-5 times, and drying in a baking oven at 30-80 ℃ for 6-24 h, wherein the obtained composite material is denoted as a product E;
(3) g-C based on embedded porous few layers 3 N 4 Preparation of a ZIF-8 mixed matrix film: adding the product E into a solvent F required by film preparation, and carrying out ultrasonic treatment at the temperature of 20-70 ℃ and the frequency of 20-50 KHz for 0.5-6 h to uniformly disperse, and naming the solution G; then adding a polymer matrix into the solution G, stirring 2-24H by a magnetic stirrer at the temperature of 20-80 ℃ and the rotating speed of 100-2000 rpm to completely dissolve the polymer, and standing and defoaming for 12-48H to obtain a uniform casting solution H; wherein the polymer matrix accounts for (2-15)% of the casting solution, and the mass ratio of the product E to the polymer matrix in the casting solution is (0.01-0.1): 1, a step of; uniformly coating a casting solution H on a clean glass plate or a polytetrafluoroethylene plate by using a film coater, controlling the thickness of a wet film to be 300-1500 mu m, then placing the coated glass plate or polytetrafluoroethylene plate in a vacuum oven at 25-80 ℃ for vacuum drying 12-48H, and then drying 8-48H in the vacuum oven at 80-150 ℃; the film after the solvent is removed from the glass plate or the polytetrafluoroethylene plate and is properly stored for standby.
2. The embedded porous few-layer based g-C of claim 1 3 N 4 ZIF-8 blendsThe preparation method of the matrix film is characterized in that: in the step (3), the solvent F required for film preparation is one of N, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran.
3. The embedded porous few-layer based g-C of claim 1 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane is characterized by comprising the following steps: in the step (3), the polymer matrix is one of polyether block amide, sulfonated polyether ether ketone, polyimide, cellulose acetate and polydimethylsiloxane.
4. The embedded porous few-layer based g-C of claim 1 3 N 4 The preparation method of the ZIF-8 mixed matrix membrane is characterized by comprising the following steps: the thickness of the prepared mixed matrix film is 20-200 mu m.
5. An embedded porous few-layer-based g-C prepared by the method of any one of claims 1-4 3 N 4 Separation of CO by ZIF-8 mixed matrix membrane 2 Is used in the field of applications.
6. The use according to claim 5, characterized in that: the gas separation performance test adopts a constant pressure variable volume method, and the effective area of membrane permeation is 10-100 cm 2 Scavenging is carried out by H 2 The scavenging flow rate is 10-100 mL/min, the feeding gas flow rate is 10-60 mL/min, the flow rates of the raw material side and the permeation side are measured by flow meters, and the component content of the permeation side is tested by gas chromatography; the test temperature is 20-100 ℃ and the pressure difference is 0.1-1.5 MPa.
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| CN114515519B (en) * | 2022-03-16 | 2022-10-04 | 南京工业大学 | Mixed matrix carbon molecular sieve membrane, preparation method and composite membrane prepared by using same 2 H 4 /C 2 H 6 Use in separations |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090033733A (en) * | 2007-10-01 | 2009-04-06 | 한국화학연구원 | A preparation of asymmetric porous peba membrane for composite membrane |
| JP2014177378A (en) * | 2013-03-14 | 2014-09-25 | Nissan Chem Ind Ltd | Method for producing porous carbon nitride |
| CN105195191A (en) * | 2015-07-20 | 2015-12-30 | 黑龙江大学 | Method for synthesizing lamella g-C3N4 and TiO2 nanorod composite material through assistance of ultrasonic wave |
| WO2017049005A1 (en) * | 2015-09-16 | 2017-03-23 | Lockheed Martin Corporation | Separation membranes formed from perforated graphene and methods for use thereof |
| CN108745004A (en) * | 2018-06-08 | 2018-11-06 | 太原理工大学 | A kind of preparation method and application of the mixed substrate membrane containing nano-grade molecular sieve with lamella and caged collaboration sieving actoion |
| CN108816059A (en) * | 2018-06-08 | 2018-11-16 | 太原理工大学 | A kind of preparation method and application of the mixed substrate membrane containing nano-grade molecular sieve of doped graphite carbonitride |
| CN110327792A (en) * | 2019-06-15 | 2019-10-15 | 太原理工大学 | A kind of mixed substrate membrane containing nano-grade molecular sieve of tree and its preparation method and application of bi-component nanometer additive building |
| CN110828191A (en) * | 2019-09-27 | 2020-02-21 | 西安交通大学 | Carbon nitride/graphene/nickel disulfide supercapacitor material with porous layered structure and preparation method thereof |
| CN112808031A (en) * | 2021-01-11 | 2021-05-18 | 大连理工大学 | Two-dimensional nanoscale ZIF-90/C3N4Preparation method of mixed matrix membrane of nano-sheet composite material |
| CN112897484A (en) * | 2021-01-14 | 2021-06-04 | 华南理工大学 | g-C without defect3N4Nanosheets, two-dimensional g-C3N4Nano sheet film, preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108745404B (en) * | 2018-06-14 | 2020-12-04 | 苏州大学 | Carbon nitride film composite material based on black phosphorus/metal organic framework modification, preparation method thereof and application thereof in waste gas treatment |
-
2021
- 2021-09-28 CN CN202111146082.7A patent/CN113750821B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090033733A (en) * | 2007-10-01 | 2009-04-06 | 한국화학연구원 | A preparation of asymmetric porous peba membrane for composite membrane |
| JP2014177378A (en) * | 2013-03-14 | 2014-09-25 | Nissan Chem Ind Ltd | Method for producing porous carbon nitride |
| CN105195191A (en) * | 2015-07-20 | 2015-12-30 | 黑龙江大学 | Method for synthesizing lamella g-C3N4 and TiO2 nanorod composite material through assistance of ultrasonic wave |
| WO2017049005A1 (en) * | 2015-09-16 | 2017-03-23 | Lockheed Martin Corporation | Separation membranes formed from perforated graphene and methods for use thereof |
| CN108745004A (en) * | 2018-06-08 | 2018-11-06 | 太原理工大学 | A kind of preparation method and application of the mixed substrate membrane containing nano-grade molecular sieve with lamella and caged collaboration sieving actoion |
| CN108816059A (en) * | 2018-06-08 | 2018-11-16 | 太原理工大学 | A kind of preparation method and application of the mixed substrate membrane containing nano-grade molecular sieve of doped graphite carbonitride |
| CN110327792A (en) * | 2019-06-15 | 2019-10-15 | 太原理工大学 | A kind of mixed substrate membrane containing nano-grade molecular sieve of tree and its preparation method and application of bi-component nanometer additive building |
| CN110828191A (en) * | 2019-09-27 | 2020-02-21 | 西安交通大学 | Carbon nitride/graphene/nickel disulfide supercapacitor material with porous layered structure and preparation method thereof |
| CN112808031A (en) * | 2021-01-11 | 2021-05-18 | 大连理工大学 | Two-dimensional nanoscale ZIF-90/C3N4Preparation method of mixed matrix membrane of nano-sheet composite material |
| CN112897484A (en) * | 2021-01-14 | 2021-06-04 | 华南理工大学 | g-C without defect3N4Nanosheets, two-dimensional g-C3N4Nano sheet film, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Facile one-step synthesis of porous graphene-like g-C3N4 rich in nitrogen vacancies for enhanced H2 production from photocatalytic aqueous-phase reforming of methanol;Ruiyi Wang, et al;international journal o f hydrogen energy;197-208 * |
| One‐Pot Exfoliation of Graphitic C3N4 Quantum Dots for Blue QLEDs by Methylamine Intercalation;Xingchen He, et al;Small;1902735（1-8） * |
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