CN113750821A - Based on embedded porous few-layer g-C3N4Preparation method and application of/ZIF-8 mixed matrix membrane - Google Patents

Based on embedded porous few-layer g-C3N4Preparation method and application of/ZIF-8 mixed matrix membrane Download PDF

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CN113750821A
CN113750821A CN202111146082.7A CN202111146082A CN113750821A CN 113750821 A CN113750821 A CN 113750821A CN 202111146082 A CN202111146082 A CN 202111146082A CN 113750821 A CN113750821 A CN 113750821A
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CN113750821B (en
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张新儒
王永洪
李晋平
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Taiyuan University of 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
    • B01D69/14—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 multi-layer g-C based on embedded type porosity3N4A preparation method and application of a/ZIF-8 mixed matrix membrane. The preparation method comprises the following steps: first of all g-C is prepared by calcining melamine3N4Then the mixture is mixed with alcohols for hot reflux to strip and prepare the porous few-layer g-C3N4And in the porous small layer g-C3N4In-situ ZIF-8 growth is carried out between layers. Adding the prepared inorganic filler into a polymer matrix, and preparing the embedded porous few-layer g-C by adopting a solution casting method3N4A/ZIF-8 mixed matrix membrane. The porous few-layer structure formed by stripping can reduce the transfer resistance of gas molecules, and ZIF-8 can reduce the CO2Has high affinity, and the prepared mixed matrixThe membrane has excellent separation performance, breaks through the 'trade-off' effect and has excellent comprehensive performance.

Description

Based on embedded porous few-layer g-C3N4Preparation method and application of/ZIF-8 mixed matrix membrane
Technical Field
The invention relates to a multi-layer g-C based on embedded type multi-holes3N4A 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 continuously increasing, and fossil energy is largely burned. Over the past years fossil fuels have been used in excessMaking CO in air2The concentration of (b) rapidly increases, causing various ecological environmental problems. Capturing CO2In reducing CO in air2At the same time of concentration, CO can be utilized2Benefiting human life. In membrane separation, a mixed matrix membrane plays an important role, and the mixed matrix membrane with a proper inorganic filler and a proper polymer matrix can obtain excellent gas separation performance and break through the Robeson upper limit.
Polyether block amides, which consist of flexible Polyethers (PE) and relatively rigid Polyamides (PA), have been widely used as membrane materials in numerous fields. The PE phase, which has a high chain mobility, can increase permeability, facilitating rapid passage of gas molecules through the membrane, while the PA phase can provide high mechanical properties. Graphitic carbo-nitride (g-C)3N4) Has a layered structure similar to graphite, has good thermal stability and chemical stability, and can perform functional group modification or grafting between layers due to small van der Waals force between the layers. And for g-C3N4In the post-treatment, a slightly larger structural defect may be generated, the transfer resistance of the gas molecules is reduced, and a fast transfer channel is provided for the small molecules.
Disclosure of Invention
The invention prepares the g-C based on embedded porous few layers3N4the/ZIF-8 mixed matrix membrane provides a simple and efficient stripping of g-C3N4And a method of grafting ZIF-8. Applying the mixed matrix membrane to CO2/N2Separating to obtain higher CO2Permeability coefficient and separation factor.
g-C used in the present invention3N4To CO2Has affinity; after thermal refluxing treatment, g-C3N4The interlayer spacing is reduced, so that the transfer resistance of gas molecules is reduced; ZIF-8 successfully grafted to g-C3N4On the sheet layer; introduction of ZIF-8 in CO2/N2Is CO when separated2Providing a rapid passage and increasing CO2Permeability coefficient and separation factor.
In the present invention, first, g-C prepared3N4In alcoholsHot reflux stripping to form porous few-layer structure, and in-situ growth of ZIF-8 to prepare embedded porous few-layer g-C3N4ZIF-8, and mixing the embedded porous small layer g-C3N4the/ZIF-8 is introduced into a polymer matrix, and the embedded porous few-layer g-C is prepared by using a solution casting method3N4Mixed matrix membranes of/ZIF-8. The method is used for preparing the embedded porous-based few-layer g-C3N4The mixed matrix membrane of/ZIF-8 can further improve CO2Permeability and CO2/N2And (4) selectivity.
The preparation method comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, weighing 1-200 g of melamine, placing the melamine in a tube furnace, heating the melamine to 400-600 ℃ at a heating rate of 1-10 ℃/min, and then keeping the temperature in the air for 2-24 hours. The yellow product was collected and ground to a powder in a mortar and designated product a. And then adding the product A into a mixture of a solvent B and a 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 for 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 hours to obtain the porous few-layer g-C3N4And is marked as a product D.
(2) Embedded porous few layer g-C3N4Preparation of ZIF-8: and dispersing the product D in methanol, wherein the concentration of the product D in the methanol is 0.01-0.5 g/mL, and performing ultrasonic treatment at the frequency of 20-50 KHz and the temperature of 20-70 ℃ for 0.5-24 h to uniformly disperse the product D. Adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4Mechanically stirring the solution in methanol at a rotation speed of 100 to 500rpm for 0.5 to 12 hours to allow Zn (NO) to be present3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.001-0.1 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: (4-10), mechanically stirring for 12-48 h at the temperature of 20-90 ℃ to ensure that Zn (NO) is added3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4Crude ZIF-8 product. Washing the product with methanol for 3-5 times, and drying in an oven at 30-80 ℃ for 6-24 h. The resulting composite was designated product E.
(3) Based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: and adding the product E into a solvent F required by film preparation, and carrying out ultrasonic treatment for 0.5-6 h at the temperature of 20-70 ℃ and the frequency of 20-50 KHz to uniformly disperse, namely named as solution G. And then adding the polymer matrix into the solution G, stirring for 2-24 hours by using a magnetic stirrer at the temperature of 20-80 ℃ and the rotating speed of 100-2000 rpm to completely dissolve the polymer, standing and defoaming for 12-48 hours to obtain a uniform casting solution H. Wherein the polymer matrix accounts for (2-15)% of the mass of the membrane casting solution, and the mass ratio of the product E in the membrane casting solution to the polymer matrix is (0.01-0.1): 1. uniformly coating the casting solution H on a clean glass plate or a polytetrafluoroethylene plate by using a 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 for 12-48H, and then drying in the vacuum oven at 80-150 ℃ for 8-48H; and (4) removing the film after the solvent is removed from the glass plate or the polytetrafluoroethylene plate, and keeping the film properly for later use.
Further, in the step (1) of the preparation method, the solvent B is one of ethylene glycol and glycerol.
Further, in the step (1) of the preparation method, the solvent C is one of methanol, ethanol, n-propanol and n-butanol.
In step (3) of the above production 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 invention is based on embedded porous few-layer g-C3N4The thickness of the/ZIF-8 mixed matrix membrane is 20-200 mu m.
The invention also provides the embedded porous few-layer g-C prepared by the method3N4ZIF-8 mixed matrix membrane for separating CO2The use of (1).
Further, g-C based on embedded porous few layers3N4The gas separation performance test of the/ZIF-8 mixed matrix membrane adopts a constant-pressure variable-volume method, and the effective permeation area of the membrane is 10-100 cm2The scavenging gas is H2The scavenging flow rate is 10-100 mL/min, the feeding flow rate is 10-60 mL/min, the flow of the raw material side and the flow of the permeation side are measured by flow meters, and the component content of the permeation side is measured by gas chromatography; the testing 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-C3N4the/ZIF-8 material provides a method for stripping, reducing the number of layers and regulating the interlayer distance, and the method is used for treating CO2The selective delivery of (a) has positive significance;
(2) based on embedded porous few-layer g-C3N4the/ZIF-8 mixed matrix membrane can obviously improve CO2Permeability and CO2/N2、CO2/CH4Selectivity of (a);
(3) based on embedded porous few-layer g-C3N4the/ZIF-8 mixed matrix membranes have less temperature effect on membrane permeability and selectivity than pure polymer membranes.
(4) Based on embedded porous few-layer g-C3N4the/ZIF-8 mixed matrix membrane has the advantages of low membrane preparation cost, uncomplicated preparation process, easiness in operation, good running stability and good industrial application potential.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Comparative example 1: a pure polyether block amide homogeneous polymer film, comprising the steps of:
dissolving polyether block amide in an N, N-dimethylacetamide solvent to obtain a polyether block amide, wherein the mass percent of the polyether block amide dissolved in the N, N-dimethylacetamide solvent is 0.06: and (3) stirring the casting solution of 1 for 48 hours at the rotation speed of 500rpm and the temperature of 70 ℃ by using a magnetic stirrer to completely dissolve the casting solution to form a uniform casting solution, and defoaming the uniform casting solution at the constant temperature of 25 ℃ for 12 hours for later use. Uniformly scraping the casting solution on a clean glass plate by using a scraper, controlling the thickness of a wet film to be 300 mu m, then placing the glass plate at normal temperature to volatilize the solvent for 48h, and drying for 48h in a vacuum oven at 60 ℃ to remove the residual solvent. The film after the solvent removal is taken off from the glass plate and is properly kept for standby.
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 measured2Permeability coefficient of 162 Barrer, CO2/N2The separation factor was 26.
Comparative example 2: a pure sulfonated polyether ether ketone homogeneous polymer membrane is prepared by the following steps:
weighing sulfonated polyether ether ketone, adding the sulfonated polyether ether ketone into an 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 for 24 hours at 25 ℃ to obtain a homogeneous sulfonated polyether ether ketone solution, filtering out some insoluble impurities by using a screen, standing for 2 hours for defoaming, pouring the solution onto a clean and flat glass plate, controlling the thickness of a wet film to be 300 mu m, standing the glass plate with the poured casting film liquid for 10 minutes in the environment, transferring the glass plate into a 60 ℃ drying oven for drying for 12 hours, and then carrying out heat treatment for 4 hours at 100 ℃ to obtain a sulfonated polyether ether ketone homogeneous polymer film which is properly kept 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 measured2Permeability coefficient of 364 Barrer, CO2/N2The separation factor was 27.
Example 1:
based on embedded porous few-layer g-C3N4The preparation method of the/ZIF-8 mixed matrix membrane comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, 10 g of melamine is weighed and placed in a tube furnace, heated to 550 ℃ at the heating rate of 2 ℃/min, and then kept at the constant temperature in the air for 8 hours. The yellow product was collected and ground to a powder in a mortar and 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 volume ratio of the glycerol to the ethanol is 0.33: 1, refluxing at 90 ℃ for 6 h. Then, the powder was washed with ethanol 3 times and dried in a forced air drying oven at 60 ℃ for 12 hours to prepare porous small layer g-C3N4Is marked as product D.
(2) Embedded porous few layer g-C3N4Preparation of ZIF-8: and taking a product D to disperse in methanol, wherein the concentration of the product D in the methanol is 0.067 g/mL, and performing ultrasonic treatment for 2h at the frequency of 30 KHz and the temperature of 25 ℃ to uniformly disperse. Adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4In the methanol solution, Zn (NO) was mechanically stirred at 100rpm for 4 hours3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.01 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 4, mechanically stirring at 25 ℃ for 24h to allow Zn (NO)3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4Crude ZIF-8 product. The product was washed 3 times with methanol and dried in an oven at 40 ℃ for 12 h. The resulting composite was designated product E.
(3) Based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: adding the product E into a solvent N, N-dimethylacetamide, and carrying out ultrasonic treatment for 0.5 h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse the product E, namely, obtaining a solution G. Then adding the polymer matrix polyether block amide into the solution G, stirring for 8 hours by using a magnetic stirrer under the conditions that the temperature is 30 ℃ and the rotating speed is 200 rpm to completely dissolve the polymer, standing and defoaming for 24 hours to obtain a uniform casting filmAnd (4) liquid H. Wherein the polyether block amide accounts for 6% of the mass of the casting solution, and the mass ratio of the product E in the casting solution to the polyether block amide is 0.01: 1. uniformly coating the casting solution H on a clean glass plate by using a 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 for 24H, and then drying in a vacuum oven at 80 ℃ for 12H; and removing the film after the solvent is removed from the surface of the glass plate, and keeping the film properly for later use.
Prepared embedded porous-based few-layer g-C3N4the/ZIF-8 mixed matrix membrane 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 membrane is 0.2 MPa, and CO is measured2Permeability coefficient 292Barrer, CO2/N2The separation factor was 61.
Example 2:
based on embedded porous few-layer g-C3N4The preparation method of the/ZIF-8 mixed matrix membrane comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, 10 g of melamine is weighed and placed in a tube furnace, heated to 550 ℃ at the heating rate of 2 ℃/min, and then kept at the constant temperature in the air for 8 hours. The yellow product was collected and ground to a powder in a mortar and 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 volume ratio of the glycerol to the ethanol is 0.33: 1, refluxing at 90 ℃ for 6 h. Then, the powder was washed with ethanol 3 times and dried in a forced air drying oven at 60 ℃ for 12 hours to prepare porous small layer g-C3N4Is marked as product D.
(2) Embedded porous few layer g-C3N4Preparation of ZIF-8: and taking a product D to disperse in methanol, wherein the concentration of the product D in the methanol is 0.033 g/mL, and carrying out ultrasonic treatment for 2h at the frequency of 30 KHz and the temperature of 25 ℃ to ensure that the product D is uniformly dispersed. Adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4In the methanol solution, Zn (NO) was mechanically stirred at 100rpm for 4 hours3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.01 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 4, mechanically stirring at 25 ℃ for 24h to allow Zn (NO)3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4Crude ZIF-8 product. The product was washed 3 times with methanol and dried in an oven at 40 ℃ for 12 h. The resulting composite was designated product E.
(3) Based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: adding the product E into a solvent N, N-dimethylacetamide, and carrying out ultrasonic treatment for 0.5 h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse the product E, namely, obtaining a solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring for 8 hours by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, standing and defoaming for 24 hours to obtain a 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 in the casting solution to the polyether block amide is 0.01: 1. uniformly coating the casting solution H on a clean glass plate by using a 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 for 24H, and then drying in a vacuum oven at 80 ℃ for 12H; and removing the film after the solvent is removed from the surface of the glass plate, and keeping the film properly for later use.
Prepared embedded porous-based few-layer g-C3N4the/ZIF-8 mixed matrix membrane 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 membrane is 0.2 MPa, and CO is measured2Permeability coefficient of 315 Barrer, CO2/N2The separation factor is 76.
Example 3:
based on embedded porous few-layer g-C3N4The preparation method of the/ZIF-8 mixed matrix membrane comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, 10 g of melamine is weighed and placed in a tube furnace, and the temperature is raised by 2.5 ℃/minThe rate is heated to 550 ℃ and then the temperature is kept constant in the air for 12 h. The yellow product was collected and ground to a powder in a mortar and designated product a. Then adding the product A into a mixture of ethylene glycol and ethanol, wherein the concentration of the product A in the ethylene glycol is 0.12 g/mL, and the volume ratio of the ethylene glycol to the ethanol is 0.33: 1, refluxing at 80 ℃ for 6 h. Then, the powder was washed with ethanol 3 times and dried in a forced air drying oven at 80 ℃ for 8 hours to prepare porous small layer g-C3N4Is marked as product D.
(2) Embedded porous few layer g-C3N4Preparation of ZIF-8: and taking a product D to disperse in methanol, wherein the concentration of the product D in the methanol is 0.0167 g/mL, and carrying out ultrasonic treatment for 1h at the frequency of 40 KHz and the temperature of 30 ℃ to ensure that the dispersion is uniform. Adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4In the methanol solution, Zn (NO) was mechanically stirred at 200 rpm for 4 hours3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.01 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 4, mechanically stirring at 25 ℃ for 24h to allow Zn (NO)3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4Crude ZIF-8 product. 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) Based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: adding the product E into a solvent N, N-dimethylacetamide, and carrying out ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse the product E, namely, obtaining a solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring for 8 hours by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, standing and defoaming for 24 hours to obtain a uniform casting solution H. Wherein, the mass percentage of the polyether block amide in the casting solution is 6%, and the product E in the casting solution and the mass percentage of the polyether block amideThe quantity ratio is 0.02: 1. uniformly coating the casting solution H on a clean glass plate by using a 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 for 24H, and then drying in a vacuum oven at 80 ℃ for 12H; and removing the film after the solvent is removed from the surface of the glass plate, and keeping the film properly for later use.
Prepared embedded porous-based few-layer g-C3N4the/ZIF-8 mixed matrix membrane 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 membrane is 0.2 MPa, and CO is measured2Permeability coefficient of 366 Barrer, CO2/N2The separation factor was 82.
Example 4:
based on embedded porous few-layer g-C3N4The preparation method of the/ZIF-8 mixed matrix membrane comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, 10 g of melamine is weighed and placed in a tube furnace, heated to 600 ℃ at the heating rate of 2 ℃/min and then kept at the constant temperature in the air for 18 h. The yellow product was collected and ground to a powder in a mortar and 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 volume ratio of the glycerol to the ethanol is 0.33: 1, refluxing at 80 ℃ for 6 h. Then, the powder was washed with ethanol 3 times and dried in a forced air drying oven at 80 ℃ for 8 hours to prepare porous small layer g-C3N4Is marked as product D.
(2) Embedded porous few layer g-C3N4Preparation of ZIF-8: and taking a product D to disperse in methanol, wherein the concentration of the product D in the methanol is 0.0167 g/mL, and carrying out ultrasonic treatment for 1h at the frequency of 40 KHz and the temperature of 30 ℃ to ensure that the dispersion is uniform. Adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4In the methanol solution, Zn (NO) was mechanically stirred at 200 rpm for 4 hours3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.01 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 6, mechanically stirring at 30 ℃ for 24h to make Zn (NO)3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4Crude ZIF-8 product. The product was washed 3 times with methanol and dried in an oven at 50 ℃ for 24 h. The resulting composite was designated product E.
(3) Based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: adding the product E into a solvent N, N-dimethylformamide, and carrying out ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse the product E, namely, obtaining a solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring for 8 hours by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, standing and defoaming for 24 hours to obtain a 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 in the casting solution to the polyether block amide is 0.005: 1. uniformly coating the casting solution H on a clean glass plate by using a 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 for 24H, and then drying in a vacuum oven at 80 ℃ for 12H; and removing the film after the solvent is removed from the surface of the glass plate, and keeping the film properly for later use.
Prepared embedded porous-based few-layer g-C3N4the/ZIF-8 mixed matrix membrane 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 membrane is 0.2 MPa, and CO is measured2Permeability coefficient 269 Barrer, CO2/N2The separation factor was 71.
Example 5:
based on embedded porous few-layer g-C3N4The preparation method of the/ZIF-8 mixed matrix membrane comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, 10 g of melamine is weighed and placed in a tube furnace, heated to 550 ℃ at the heating rate of 3 ℃/min, and then kept at the constant temperature in the air for 12 hours. The yellow product was collected and ground to a powder in a mortar and designated product a. Then will produceAdding the product A into a mixture of ethylene glycol and ethanol, wherein the concentration of the product A in the ethylene glycol is 0.15 g/mL, and the volume ratio of the ethylene glycol to the ethanol is 0.33: 1, refluxing at 80 ℃ for 12 h. Then, the powder was washed with ethanol 3 times and dried in a forced air drying oven at 80 ℃ for 8 hours to prepare porous small layer g-C3N4Is marked as product D.
(2) Embedded porous few layer g-C3N4Preparation of ZIF-8: and taking a product D to disperse in methanol, wherein the concentration of the product D in the methanol is 0.0167 g/mL, and carrying out ultrasonic treatment for 1h at the frequency of 40 KHz and the temperature of 30 ℃ to ensure that the dispersion is uniform. Adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4Mechanically stirring the methanol solution at 200 rpm for 8h to obtain Zn (NO)3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.01 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 4, mechanically stirring at 25 ℃ for 24h to allow Zn (NO)3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4Crude ZIF-8 product. The product was washed 5 times with methanol and dried in an oven at 50 ℃ for 24 h. The resulting composite was designated product E.
(3) Based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: adding the product E into a solvent N, N-dimethylacetamide, and carrying out ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse the product E, namely, obtaining a solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring for 8 hours by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, standing and defoaming for 24 hours to obtain a 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 in the casting solution to the polyether block amide is 0.01: 1. uniformly coating the casting solution H on a clean glass plate by using a coater, controlling the thickness of a wet film to be 300 mu m, and then coatingPlacing the filmed glass plate in a vacuum oven at 45 ℃ for vacuum drying for 24 hours, and then drying in a vacuum oven at 80 ℃ for 12 hours; and removing the film after the solvent is removed from the surface of the glass plate, and keeping the film properly for later use.
Prepared embedded porous-based few-layer g-C3N4the/ZIF-8 mixed matrix membrane 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 membrane is 0.5 MPa, and CO is measured2Permeability coefficient 471Barrer, CO2/N2The separation factor is 110.
Example 6:
based on embedded porous few-layer g-C3N4The preparation method of the/ZIF-8 mixed matrix membrane comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, 10 g of melamine is weighed and placed in a tube furnace, heated to 550 ℃ at the heating rate of 2.5 ℃/min, and then kept at the constant temperature in the air for 12 hours. The yellow product was collected and ground to a powder in a mortar and designated product a. Then adding the product A into a mixture of ethylene glycol and ethanol, wherein the concentration of the product A in the ethylene glycol is 0.12 g/mL, and the volume ratio of the ethylene glycol to the ethanol is 0.33: 1, refluxing at 80 ℃ for 6 h. Then, the powder was washed with ethanol 3 times and dried in a forced air drying oven at 80 ℃ for 8 hours to prepare porous small layer g-C3N4Is marked as product D.
(2) Embedded porous few layer g-C3N4Preparation of ZIF-8: and taking a product D to disperse in methanol, wherein the concentration of the product D in the methanol is 0.0167 g/mL, and carrying out ultrasonic treatment for 1h at the frequency of 40 KHz and the temperature of 30 ℃ to ensure that the dispersion is uniform. Adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4In the methanol solution, Zn (NO) was mechanically stirred at 200 rpm for 4 hours3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.01 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 4, mechanically stirring at 30 ℃ for 24h to allow Zn (NO)3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4Crude ZIF-8 product. The product was washed 3 times with methanol and dried in an oven at 80 ℃ for 8 h. The resulting composite was designated product E.
(3) Based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: adding the product E into a solvent N, N-dimethylacetamide, and carrying out ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse the product E, namely, obtaining a solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring for 8 hours by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, standing and defoaming for 24 hours to obtain a 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 in the casting solution to the polyether block amide is 0.03: 1. uniformly coating the casting solution H on a clean glass plate by using a 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 for 24H, and then drying in a vacuum oven at 80 ℃ for 12H; and removing the film after the solvent is removed from the surface of the glass plate, and keeping the film properly for later use.
Prepared embedded porous-based few-layer g-C3N4the/ZIF-8 mixed matrix membrane 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 membrane is 0.3 MPa, and CO is measured2Permeability coefficient of 410 Barrer, CO2/N2The separation factor was 91.
Example 7:
based on embedded porous few-layer g-C3N4The preparation method of the/ZIF-8 mixed matrix membrane comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, 10 g of melamine is weighed and placed in a tube furnace, heated to 550 ℃ at the heating rate of 2.5 ℃/min, and then kept at the constant temperature in the air for 12 hours. The yellow product was collected and ground to a powder in a mortar and designated product a. Then adding the product A into a mixture of ethylene glycol and ethanol, wherein the concentration of the product A in the ethylene glycol is 0.12 g/mL, and the volumes of the ethylene glycol and the ethanolThe ratio is 0.33: 1, refluxing at 80 ℃ for 6 h. Then, the powder was washed with ethanol 3 times and dried in a forced air drying oven at 80 ℃ for 8 hours to prepare porous small layer g-C3N4Is marked as product D.
(2) Embedded porous few layer g-C3N4Preparation of ZIF-8: and taking a product D to disperse in methanol, wherein the concentration of the product D in the methanol is 0.0167 g/mL, and carrying out ultrasonic treatment for 1h at the frequency of 40 KHz and the temperature of 30 ℃ to ensure that the dispersion is uniform. Adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4In the methanol solution, Zn (NO) was mechanically stirred at 200 rpm for 4 hours3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.01 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 4, mechanically stirring at 25 ℃ for 24h to allow Zn (NO)3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4Crude ZIF-8 product. 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) Based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: adding the product E into dimethyl sulfoxide as a solvent, and carrying out ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse the product E, namely, obtaining a solution G. And then adding the polymer matrix polyether block amide into the solution G, stirring for 8 hours by using a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, standing and defoaming for 24 hours to obtain a 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 in the casting solution to the polyether block amide is 0.04: 1. uniformly coating the casting solution H on a clean glass plate by using a 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 for 24H, and then drying in a vacuum oven at 80 ℃ for 12H; removing the solvent from the filmTaken off from the surface of the glass plate and stored properly for standby.
Prepared embedded porous-based few-layer g-C3N4the/ZIF-8 mixed matrix membrane is tested under the conditions that the temperature is 70 ℃ and the pressure difference between the raw material side and the permeation side of the membrane is 0.2 MPa, and CO is measured2Permeability coefficient of 459 Barrer, CO2/N2The separation factor was 78.
Example 8:
based on embedded porous few-layer g-C3N4The preparation method of the/ZIF-8 mixed matrix membrane comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, 10 g of melamine is weighed and placed in a tube furnace, heated to 550 ℃ at the heating rate of 2.5 ℃/min, and then kept at the constant temperature in the air for 12 hours. The yellow product was collected and ground to a powder in a mortar and designated product a. Then adding the product A into a mixture of ethylene glycol and ethanol, wherein the concentration of the product A in the ethylene glycol is 0.12 g/mL, and the volume ratio of the ethylene glycol to the ethanol is 0.33: 1, refluxing at 80 ℃ for 6 h. Then, the powder was washed with ethanol 3 times and dried in a forced air drying oven at 80 ℃ for 8 hours to prepare porous small layer g-C3N4Is marked as product D.
(2) Embedded porous few layer g-C3N4Preparation of ZIF-8: and taking a product D to disperse in methanol, wherein the concentration of the product D in the methanol is 0.0167 g/mL, and carrying out ultrasonic treatment for 1h at the frequency of 40 KHz and the temperature of 30 ℃ to ensure that the dispersion is uniform. Adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4In the methanol solution, Zn (NO) was mechanically stirred at 200 rpm for 4 hours3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.01 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 4, mechanically stirring at 30 ℃ for 24h to allow Zn (NO)3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4Crude ZIF-8 product. The product was washed with methanol3 times and dried in an oven at 80 ℃ for 8 h. The resulting composite was designated product E.
(3) Based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: adding the product E into a solvent N, N-dimethylacetamide, and carrying out ultrasonic treatment for 1h at the temperature of 30 ℃ and the frequency of 40 KHz to uniformly disperse the product E, namely, obtaining a solution G. And then adding the polymer matrix sulfonated polyether ether ketone into the solution G, stirring for 8 hours by adopting a magnetic stirrer at the temperature of 30 ℃ and the rotating speed of 200 rpm to completely dissolve the polymer, standing and defoaming for 24 hours to obtain uniform casting solution H. Wherein the mass percentage of the sulfonated polyether ether ketone in the membrane casting solution is 10%, and the mass ratio of the product E in the membrane casting solution to the sulfonated polyether ether ketone is 0.03: 1. uniformly coating the casting solution H on a clean glass plate by using a 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 for 24H, and then drying in a vacuum oven at 80 ℃ for 12H; and removing the film after the solvent is removed from the surface of the glass plate, and keeping the film properly for later use.
Prepared embedded porous-based few-layer g-C3N4the/ZIF-8 mixed matrix membrane 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 membrane is 0.2 MPa, and CO is measured2Permeability coefficient of 610 Barrer, CO2/N2The separation factor was 39.
From comparative studies of comparative example 1 and examples 1 to 7, it was found that the prepared embedded porous-based sublayer g-C3N4CO of/ZIF-8 mixed matrix membranes compared to polyether block amide homogeneous Polymer membranes2Permeability coefficient and CO2/N2The separation factors are greatly improved. Especially CO in comparative example 52The permeability coefficient reaches 471Barrer, CO2/N2The separation factor reaches 110. CO with polyether Block amide homogeneous Polymer films2Permeability coefficient of 162 Barrer ratio, CO2The permeability coefficient is improved by 191 percent; CO over polyether block amide homogeneous polymer films2/N2The separation factor 26 increased by 323%. From comparative studies of comparative example 2 and example 8, it was found that the prepared embedded-based polypeptidesLess porous layer g-C3N4Compared with a sulfonated polyether ether ketone homogeneous polymer membrane, the CO of the/ZIF-8 mixed matrix membrane is CO2Permeability coefficient and CO2/N2The separation factor is also obviously improved.
Although the present invention has been described above, the present invention is not limited to the above-mentioned embodiments, which are only illustrative and not restrictive, and those skilled in the art can make various modifications without departing from the spirit of the present invention, which fall within the scope of the present invention.

Claims (9)

1. Embedded porous few-layer g-C3N4The preparation method of the/ZIF-8 mixed matrix membrane is characterized by comprising the following steps: firstly preparing g-C3N4Stripping by hot reflux in alcohol, and stripping the porous layer g-C3N4Preparation of embedded porous few-layer g-C by in-situ growth of ZIF-83N4ZIF-8, and mixing the embedded porous small layer g-C3N4the/ZIF-8 is introduced into a polymer matrix, and the embedded porous few-layer g-C is prepared by using a solution casting method3N4Mixed matrix membranes of/ZIF-8.
2. The embedded porous few layer g-C of claim 13N4The preparation method of the/ZIF-8 mixed matrix membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) porous less layer g-C3N4The preparation of (1): firstly, weighing 1-200 g of melamine, placing the melamine in a tube furnace, heating the melamine to 400-600 ℃ at a heating rate of 1-10 ℃/min, and then keeping the temperature in the air for 2-24 hours; the yellow product was collected and ground to a powder in a mortar and designated product a; and then adding the product A into a mixture of a solvent B and a 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 for 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 DEG CDrying for 8-24 h to obtain the porous few-layer g-C3N4Marking as a product D;
(2) embedded porous few layer g-C3N4Preparation of ZIF-8: dispersing the product D in methanol, wherein the concentration of the product D in the methanol is 0.01-0.5 g/mL, and performing ultrasonic treatment at the frequency of 20-50 KHz and the temperature of 20-70 ℃ for 0.5-24 h to uniformly disperse the product D; adding Zn (NO)3)2·6H2O is added to the porous small layer g-C3N4Mechanically stirring the solution in methanol at a rotation speed of 100 to 500rpm for 0.5 to 12 hours to allow Zn (NO) to be present3)2·6H2O is uniformly dispersed and named as solution E, wherein Zn (NO)3)2·6H2The concentration of O in the methanol solution is 0.001-0.1 g/mL; adding 2-methylimidazole in which Zn (NO) is added to the solution E3)2·6H2The molar ratio of O to 2-methylimidazole is 1: (4-10), mechanically stirring at 20-90 ℃ for 12-48 h to enable Zn (NO)3)2·6H2Reaction of O and 2-methylimidazole to generate embedded porous few-layer g-C3N4A crude ZIF-8 product; washing the product with methanol for 3-5 times, and drying in an oven at 30-80 ℃ for 6-24 h; marking the obtained composite material as a product E;
(3) based on embedded porous few-layer g-C3N4Preparation of/ZIF-8 Mixed matrix Membrane: adding the product E into a solvent F required by film preparation, and carrying out ultrasonic treatment for 0.5-6 h at the temperature of 20-70 ℃ and the frequency of 20-50 KHz to uniformly disperse, namely named as solution G; adding the polymer matrix into the solution G, stirring for 2-24 hours by using a magnetic stirrer at the temperature of 20-80 ℃ and the rotating speed of 100-2000 rpm to completely dissolve the polymer, standing and defoaming for 12-48 hours to obtain a uniform casting solution H; wherein the polymer matrix accounts for (2-15)% of the mass of the membrane casting solution, and the mass ratio of the product E in the membrane casting solution to the polymer matrix is (0.01-0.1): 1; uniformly coating the casting solution H on a clean glass plate or a polytetrafluoroethylene plate by using a 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 for 12-48H, and then placing the coated glass plate or polytetrafluoroethylene plate in a vacuum oven at 80-150 DEG CDrying for 8-48 h; and (4) removing the film after the solvent is removed from the glass plate or the polytetrafluoroethylene plate, and keeping the film properly for later use.
3. The embedded porous few layer g-C of claim 23N4The preparation method of the/ZIF-8 mixed matrix membrane is characterized by comprising the following steps: in the step (1), the solvent B is one of ethylene glycol and glycerol.
4. The embedded porous few layer g-C of claim 23N4The preparation method of the/ZIF-8 mixed matrix membrane is characterized by comprising the following steps: in the step (1), the solvent C is one of methanol, ethanol, n-propanol and n-butanol.
5. The embedded porous few layer g-C of claim 23N4The preparation method of the/ZIF-8 mixed matrix membrane is characterized by comprising the following steps: in the step (3), the solvent F required for membrane preparation is one of N, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran.
6. The embedded porous few layer g-C of claim 23N4The 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.
7. The embedded porous few layer g-C of claim 23N4The preparation method of the/ZIF-8 mixed matrix membrane is characterized by comprising the following steps: the thickness of the prepared mixed matrix membrane is 20-200 mu m.
8. Embedded porous few-layer based g-C prepared by the method of any one of claims 1 to 73N4ZIF-8 mixed matrix membrane for separating CO2The use of (1).
9. Use according to claim 8, 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 cm2The scavenging gas is H2The scavenging flow rate is 10-100 mL/min, the feeding flow rate is 10-60 mL/min, the flow of the raw material side and the flow of the permeation side are measured by flow meters, and the component content of the permeation side is measured by gas chromatography; the testing temperature is 20-100 ℃, and the pressure difference is 0.1-1.5 MPa.
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