CN108744991B - Preparation method and application of organic-inorganic mixed matrix membrane doped with zeolite imidazole ester framework porous carbon nano material - Google Patents

Preparation method and application of organic-inorganic mixed matrix membrane doped with zeolite imidazole ester framework porous carbon nano material Download PDF

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CN108744991B
CN108744991B CN201810588579.6A CN201810588579A CN108744991B CN 108744991 B CN108744991 B CN 108744991B CN 201810588579 A CN201810588579 A CN 201810588579A CN 108744991 B CN108744991 B CN 108744991B
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porous carbon
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zeolite imidazole
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CN108744991A (en
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王永洪
张新儒
李龙
张桃
刘成岑
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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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • 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
    • 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 preparation method and application of an organic-inorganic mixed matrix membrane doped with zeolite imidazole ester framework porous carbon nano material, wherein the preparation method comprises the following steps: preparing a nickel-containing zeolite imidazole material by a solvothermal method by using zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole as raw materials; then, calcining the nickel-doped zeolite imidazole ester material serving as a precursor at high temperature of 700-1000 ℃ to prepare a zeolite imidazole ester framework porous carbon nano material; dispersing the porous carbon nano material in a polyether copolyamide solution to prepare a uniform membrane casting solution, wherein the wet membrane thickness is 50-500 mu m, and preparing the mixed matrix membrane doped with the zeolite imidazole ester skeleton porous carbon nano material by a solvent volatilization method. The inorganic material of the invention is simple and easy to obtain, the membrane preparation method is easy to operate, and the mixed matrix membrane is used for CO2The separated and added inorganic material can effectively improve the CO of the polyether copolyamide film2Permeability coefficient and CO2/N2A separation factor.

Description

Preparation method and application of organic-inorganic mixed matrix membrane doped with zeolite imidazole ester framework porous carbon nano material
Technical Field
The invention relates to a preparation method and application of an organic-inorganic mixed matrix membrane doped with zeolite imidazole ester skeleton porous carbon nano material, belonging to the technical field of gas separation membranes.
Background
With the development of industrial technology and the increase of population, global warming has attracted attention. Therefore, to reduce CO2Emission into the atmosphere, capture of CO before or after combustion of fossil fuels by an efficient method2Is in need of much attention. In general, CO is separated from a gas mixture2The method mainly comprises chemical adsorption, physical adsorption, cryogenic separation, membrane separation and the like. The membrane separation technology is often used for separating CO due to the advantages of high efficiency, strong adaptability, simple operation, low energy consumption, low investment, environmental protection and the like2. However, polymer membranes suffer from a trade-off effect between gas permeability and selectivity, i.e., an increase in permeability comes at the expense of selectivity and vice versa. The separation performance of inorganic membranes far exceeds the upper limit of Robeson. Therefore, the two materials are organically combinedAnd the preparation of composite membranes with excellent performance has become a trend. The organic-inorganic Mixed Matrix Membranes (MMMs) prepared by adding inorganic materials into organic macromolecules well combine the advantages of the organic materials and the inorganic mixed matrix membranes, overcome the defects of the organic materials and the inorganic mixed matrix membranes, and become a current research hotspot.
Disclosure of Invention
The invention aims to provide a preparation method and application of an organic-inorganic mixed matrix membrane doped with zeolite imidazole ester skeleton porous carbon nano material, wherein the preparation method is simple in process and is applied to CO2/N2Can effectively and selectively separate CO in a mixed system2Is CO2Provides a fast migration path.
In the mixed matrix membrane provided by the invention, the introduction of inorganic particles breaks the accumulation of molecular chains, accelerates the transfer of gas molecules and improves the permeability of gas. On the other hand, the inorganic particles not only increase the affinity for the target gas, but also provide diffusion channels matching the molecular kinetic diameters of the target gas, thereby increasing the selectivity of the gas. Thus, the mixed matrix membrane is able to break the trade-off effect even beyond the upper Robeson limit. The zeolite imidazole ester framework porous carbon nano material prepared by the invention is used for CO2Has strong adsorption capacity; the abundant nitrogen atoms can be used as Lewis base and react with acidic CO2Molecular reaction to promote CO2Is transmitted.
The invention provides an organic-inorganic mixed matrix membrane doped with zeolite imidazole ester skeleton porous carbon nano material, which consists of a polymer matrix and an additive, wherein the polymer matrix is polyether-polyamide block copolymer, the additive is zeolite imidazole ester skeleton porous carbon nano material, and the mass percentage of the additive in the mixed matrix membrane is 0.1-10 wt%.
The invention provides a preparation method of the organic-inorganic mixed matrix membrane doped with the zeolite imidazole ester skeleton porous carbon nano material, which comprises the following steps: firstly, zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole are selected as raw materials, and a nickel-doped zeolite imidazole ester material is synthesized by a solvothermal method; then, calcining the precursor at high temperature of 700-1000 ℃ to prepare the porous zeolite imidazole ester framework porous carbon nano material; dispersing the porous carbon nano material into a polyether-polyamide block polymer solution, and preparing an organic-inorganic mixed matrix membrane doped with the zeolite imidazole ester skeleton porous carbon nano material by adopting a solvent volatilization method; the film prepared is a homogeneous dense polymer film.
When the mixed matrix film is prepared, the thickness of the wet film is controlled to be 50-500 mu m.
The preparation method of the organic-inorganic mixed matrix membrane doped with the zeolite imidazole ester framework porous carbon nano material specifically comprises the following steps:
step one, preparing a nickel-doped zeolite imidazole ester material:
respectively dissolving zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole in a methanol solution to prepare solutions with the concentrations of 0.01-0.1 mol/L, 0.01-0.1 mol/L and 0.08-12 mol/L, and then respectively placing the solutions into a 4A molecular sieve to stand for 6-24 hours to remove redundant water, thus obtaining a solution A: methanol solution of zinc nitrate hexahydrate, solution B: methanol solution of nickel nitrate hexahydrate and solution C: a methanol solution of 2-methylimidazole; then, pouring the solution A, the solution B and the solution C into a three-neck flask, stirring for 12-48 hours at 20-80 ℃ to react, centrifuging the obtained solution for 10-120 minutes within the rotating speed range of 8000-12000 rpm, washing the lower-layer precipitate in a centrifugal tube for three times by using methanol, and drying in a vacuum oven at 60-100 ℃ for 12-24 hours to obtain purple powder, wherein the product is named as a product D;
wherein the particle size of the nickel-doped zeolite imidazole ester material is 30-48 nm.
Step two, preparing the zeolite imidazole ester framework porous carbon nano material:
putting the product D prepared in the step one into a flange type tubular heating furnace, and adjusting N2The flow rate is 10-500 mL/min-1At 1 to 10 ℃ per minute-1The rate of the calcination is increased to 700-1000 ℃, the calcination is carried out for 2-20 h at constant temperature, and then the calcination is naturally reduced to room temperature to obtain black powder which is named as a product E;
step three, preparing a casting solution:
dispersing the product E obtained in the step two in N, N-dimethylacetamide to prepare a solution F of 30-200G/L, ultrasonically dispersing the solution F at the frequency of 10-50 MHz and the temperature of 20-70 ℃ for 0.5-4 h, adding a polyether-polyamide block copolymer, stirring the solution F by using a magnetic stirrer at the rotating speed of 100-500 rpm and the temperature of 20-90 ℃ for 12-48 h until the solution is completely dissolved to form a uniform casting solution, namely a casting solution G, and defoaming the solution at the constant temperature of 25 ℃ for 12-24 h for later use;
the solid content of the polyether-polyamide block copolymer in the prepared casting solution is 3-25 wt%;
step four, preparing a membrane:
casting the casting solution G obtained in the third step on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet film to be 50-500 mu m, volatilizing the solvent for 24-48 h in a constant-temperature drying box with the temperature of 20-30 ℃ and the humidity of 40-60%, and drying for 24-48 h in a vacuum drying box with the temperature of 40-90 ℃; and further drying the obtained film in a blast drying oven at 30-90 ℃, and keeping the film properly for later use.
Further, in the first step, the molar ratio of zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole is 1-10: 1-10: 8-1200; 5-30 g of 4A molecular sieve is used per 100mL of methanol solution.
The invention provides an organic-inorganic mixed matrix membrane doped with zeolite imidazole ester skeleton porous carbon nano material for separating CO2Application in gas.
In the above applications, the membrane produced is used for separating CO2/N2The gas permeability is tested by adopting a constant pressure volume-variable method, and the effective area of membrane permeation is 1-12.56 cm2The scavenging gas is H2The scavenging flow rate is 10-60 mL/min-1The flow rate of the feed gas is 10-60 mL/min-1Measuring the flow of the raw material side and the flow of the permeation side by using a flowmeter, and measuring the component content of the permeation side by using gas chromatography; the test temperature is 20-80 ℃, and the pressure difference is 0.1-0.8 MPa.
The invention has the beneficial effects that:
1) nitrogen in the zeolite imidazole ester framework doped porous carbon nano material mainly exists in the forms of pyridine nitrogen, graphite nitrogen and pyrrole nitrogen, and the nitrogen atoms can be used as Lewis base to adsorb acidic CO2A molecule;
2) the zeolite imidazolate framework porous carbon nano material prepared by the method has smaller aperture than the nickel-doped zeolite imidazolate material, so that the diffusion of macromolecules is limited (N)23.6A), and to small molecules (CO)23.3A) diffusion resistance is small, thereby increasing CO2/N2Selectivity of (a);
3) zeolite imidazolate framework porous carbon nanomaterial on CO2Has strong adsorption capacity, and can enhance the CO content of the organic-inorganic mixed matrix membrane2The transfer function of (1);
4) the method has simple process, and can effectively and selectively separate CO2Is CO2Provides a fast migration path.
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 membrane with a solids content of 6wt% was prepared by the following steps:
dissolving polyether block amide in N, N-dimethylacetamide to prepare a 6wt% solution, stirring the solution at the frequency of 30MHz and the temperature of 70 ℃ for 48 hours until the solution is completely dissolved to form a uniform membrane casting solution, and defoaming at the constant temperature of 25 ℃ for 12 hours for later use. Casting the membrane casting solution on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet membrane to be 300 mu m, volatilizing the solvent in a constant-temperature drying box with the temperature of 25 ℃ and the humidity of 60 percent for 48h, and drying in a vacuum drying box with the temperature of 60 ℃ for 48 h; the obtained membrane is further dried in an air-blast drying box at the temperature of 80 ℃ and is properly stored for standby.
The prepared pure membrane is used for measuring CO under the dry condition of room temperature and the pressure difference of 0.1MPa2Has a permeability coefficient of 121Barrer (1 Barrer = 10)-10cm3(STP) cm·cm-2·s-1·cmHg-1），CO2/N2The selectivity was 24.
Example 1: a mixed matrix membrane with 1.5wt% nickel doped zeolite imidazolate material added was prepared as follows:
step one, preparing a nickel-doped zeolite imidazole ester material:
respectively dissolving zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole in a methanol solution to prepare solutions with the concentrations of 0.1mol/L, 0.1mol/L and 0.8mol/L respectively, then respectively placing the solutions into a 4A molecular sieve to stand for 12 hours to remove redundant water, and obtaining a methanol solution of zinc nitrate hexahydrate (named as solution A), a methanol solution of nickel nitrate hexahydrate (named as solution B) and a methanol solution of 2-methylimidazole (named as solution C); then, pouring the solution A, the solution B and the solution C into a three-neck flask, stirring for 48 hours at 30 ℃ to perform a chemical reaction, centrifuging the obtained solution for 20 minutes within the rotation speed range of 10000rpm, washing the lower-layer precipitate in a centrifugal tube for three times by using methanol, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain purple powder, wherein the product is named as a product D;
step two, preparing a casting solution:
dispersing the product D prepared in the first step in N, N-dimethylacetamide to prepare a 50g/L solution E, ultrasonically dispersing the solution E at the frequency of 30MHz and the temperature of 30 ℃ for 2h, and adding a polyether-polyamide block copolymer, wherein the nickel-doped zeolite imidazole ester material accounts for 1.5wt% of the polyether-polyamide block copolymer. Stirring for 12 hours at the rotating speed of 300rpm and the temperature of 60 ℃ by using a magnetic stirrer until the mixture is completely dissolved to form a uniform membrane casting solution, namely a membrane casting solution F, and defoaming at the constant temperature of 25 ℃ for 12-24 hours for later use;
step three, membrane preparation:
casting the product F obtained in the step two on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet film to be 300 mu m, volatilizing the solvent for 24h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 40%, and drying for 48h in a vacuum drying box with the temperature of 60 ℃; the obtained membrane is further dried in an air-blast drying box at the temperature of 80 ℃ and is properly stored for standby.
The prepared mixed matrix membrane is used for measuring CO under the dry condition of room temperature and the pressure difference of 0.1MPa2Has a permeability coefficient of 180Barrer, CO2/N2The selectivity was 30.
Example 2: the preparation method of the mixed matrix membrane added with 1.5wt% of zeolite imidazole ester framework porous carbon nano material comprises the following steps:
step one, preparing a nickel-doped zeolite imidazole ester material:
respectively dissolving zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole in a methanol solution to prepare solutions with the concentrations of 0.1mol/L, 0.1mol/L and 0.8mol/L respectively, then respectively placing the solutions into a 4A molecular sieve to stand for 12 hours to remove redundant water, and obtaining a methanol solution of zinc nitrate hexahydrate (named as solution A), a methanol solution of nickel nitrate hexahydrate (named as solution B) and a methanol solution of 2-methylimidazole (named as solution C); then, pouring the solution A, the solution B and the solution C into a three-neck flask, stirring for 48 hours at 30 ℃ to perform a chemical reaction, centrifuging the obtained solution for 20 minutes within the rotation speed range of 10000rpm, washing the lower-layer precipitate in a centrifuge tube for three times by using methanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain purple powder, wherein the product is named as a product D;
step two, preparing the zeolite imidazole ester framework porous carbon nano material:
putting the product D prepared in the step one into a flange type tubular heating furnace, and adjusting N2The flow rate is 100 mL/min-1At 5 ℃ min-1The rate of the reaction is increased to 800 ℃, the mixture is calcined for 3 hours at constant temperature, and then the temperature is naturally reduced to room temperature, so that black powder is obtained, and the product is named as a product E.
Step three, preparing a casting solution:
dispersing the product E prepared in the second step in N, N-dimethylacetamide to prepare a 50g/L solution F, ultrasonically dispersing the solution F at the frequency of 30MHz and the temperature of 30 ℃ for 2h, and adding a polyether-polyamide block copolymer into the solution F, wherein the mass ratio of the zeolite imidazole ester framework porous carbon nano material to the polyether-polyamide block copolymer is 1.5 wt%. Stirring for 24 hours at the rotating speed of 300rpm and the temperature of 70 ℃ by using a magnetic stirrer until the mixture is completely dissolved to form a uniform membrane casting solution, namely a membrane casting solution G, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product G obtained in the third step on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet film to be 300 mu m, volatilizing the solvent for 24h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 50%, and drying for 48h in a vacuum drying box with the temperature of 60 ℃; the obtained membrane is further dried in a forced air drying box at 60 ℃ and is properly stored for standby.
The prepared mixed matrix membrane is used for measuring CO under the dry condition of room temperature and the pressure difference of 0.1MPa2Has a permeability coefficient of 326Barrer, CO2/N2The selectivity was 36.
Example 3: the preparation method of the mixed matrix membrane added with 0.5wt% of zeolite imidazole ester framework porous carbon nano material comprises the following steps:
step one, preparing a nickel-doped zeolite imidazole ester material:
respectively dissolving zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole in a methanol solution to prepare solutions with the concentrations of 0.1mol/L, 0.1mol/L and 0.8mol/L respectively, then respectively placing the solutions into a 4A molecular sieve to stand for 12 hours to remove redundant water, and obtaining a methanol solution of zinc nitrate hexahydrate (named as solution A), a methanol solution of nickel nitrate hexahydrate (named as solution B) and a methanol solution of 2-methylimidazole (named as solution C); then, pouring the solution A, the solution B and the solution C into a three-neck flask, stirring for 48 hours at 30 ℃ to perform a chemical reaction, centrifuging the obtained solution for 20 minutes within the rotation speed range of 10000rpm, washing the lower-layer precipitate in a centrifuge tube for three times by using methanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain purple powder, wherein the product is named as a product D;
step two, preparing the zeolite imidazole ester framework porous carbon nano material:
putting the product D prepared in the step one into a flange type tubular heating furnace, and adjusting N2The flow rate is 100 mL/min-1At 5 ℃ min-1The rate of the reaction is increased to 800 ℃, the mixture is calcined for 3 hours at constant temperature, and then the temperature is naturally reduced to room temperature, so that black powder is obtained, and the product is named as a product E.
Step three, preparing a casting solution:
dispersing the product E prepared in the second step in N, N-dimethylacetamide to prepare a 15g/L solution F, ultrasonically dispersing the solution F at the frequency of 30MHz and the temperature of 30 ℃ for 2h, and adding a polyether-polyamide block copolymer into the solution F, wherein the mass ratio of the zeolite imidazole ester framework porous carbon nano material to the polyether-polyamide block copolymer is 0.5 wt%. Stirring for 24 hours at the rotating speed of 300rpm and the temperature of 70 ℃ by using a magnetic stirrer until the mixture is completely dissolved to form a uniform membrane casting solution, namely a membrane casting solution G, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product G obtained in the third step on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet film to be 300 mu m, volatilizing the solvent for 24h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 50%, and drying for 48h in a vacuum drying box with the temperature of 60 ℃; the obtained membrane is further dried in a forced air drying box at 60 ℃ and is properly stored for standby.
The prepared mixed matrix membrane is used for measuring CO under the dry condition of room temperature and the pressure difference of 0.1MPa2Has a permeability coefficient of 231Barrer, CO2/N2The selectivity was 29.
Example 4: the preparation method of the mixed matrix membrane added with 1wt% of zeolite imidazole ester skeleton porous carbon nano material comprises the following steps:
step one, preparing a nickel-doped zeolite imidazole ester material:
respectively dissolving zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole in a methanol solution to prepare solutions with the concentrations of 0.1mol/L, 0.1mol/L and 0.8mol/L respectively, then respectively placing the solutions into a 4A molecular sieve to stand for 12 hours to remove redundant water, and obtaining a methanol solution of zinc nitrate hexahydrate (named as solution A), a methanol solution of nickel nitrate hexahydrate (named as solution B) and a methanol solution of 2-methylimidazole (named as solution C); then, pouring the solution A, the solution B and the solution C into a three-neck flask, stirring for 48 hours at 30 ℃ to perform a chemical reaction, centrifuging the obtained solution for 20 minutes within the rotation speed range of 10000rpm, washing the lower-layer precipitate in a centrifuge tube for three times by using methanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain purple powder, wherein the product is named as a product D;
step two, preparing the zeolite imidazole ester framework porous carbon nano material:
putting the product D prepared in the step one into a flange type tubular heating furnace, and adjusting N2The flow rate is 100 mL/min-1At 5 ℃ ·min-1The rate of the reaction is increased to 800 ℃, the mixture is calcined for 3 hours at constant temperature, and then the temperature is naturally reduced to room temperature, so that black powder is obtained, and the product is named as a product E.
Step three, preparing a casting solution:
dispersing the product E prepared in the second step in N, N-dimethylacetamide to prepare a 30g/L solution F, ultrasonically dispersing the solution F at the frequency of 30MHz and the temperature of 30 ℃ for 2h, and adding a polyether-polyamide block copolymer into the solution F, wherein the mass ratio of the zeolite imidazole ester skeleton porous carbon nano material to the polyether-polyamide block copolymer is 1 wt%. Stirring for 24 hours at the rotating speed of 300rpm and the temperature of 70 ℃ by using a magnetic stirrer until the mixture is completely dissolved to form a uniform membrane casting solution, namely a membrane casting solution G, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product G obtained in the third step on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet film to be 300 mu m, volatilizing the solvent for 24h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 50%, and drying for 48h in a vacuum drying box with the temperature of 60 ℃; the obtained membrane is further dried in a forced air drying box at 60 ℃ and is properly stored for standby.
The prepared mixed matrix membrane is used for measuring CO under the dry condition of room temperature and the pressure difference of 0.1MPa2Has a permeability coefficient of 265Barrer, CO2/N2The selectivity was 33.
Example 5: the preparation method of the mixed matrix membrane added with 2wt% of zeolite imidazole ester skeleton porous carbon nano material comprises the following steps:
step one, preparing a nickel-doped zeolite imidazole ester material:
respectively dissolving zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole in a methanol solution to prepare solutions with the concentrations of 0.1mol/L, 0.1mol/L and 0.8mol/L respectively, then respectively placing the solutions into a 4A molecular sieve to stand for 12 hours to remove redundant water, and obtaining a methanol solution of zinc nitrate hexahydrate (named as solution A), a methanol solution of nickel nitrate hexahydrate (named as solution B) and a methanol solution of 2-methylimidazole (named as solution C); then, pouring the solution A, the solution B and the solution C into a three-neck flask, stirring for 48 hours at 30 ℃ to perform a chemical reaction, centrifuging the obtained solution for 20 minutes within the rotation speed range of 10000rpm, washing the lower-layer precipitate in a centrifuge tube for three times by using methanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain purple powder, wherein the product is named as a product D;
step two, preparing the zeolite imidazole ester framework porous carbon nano material:
putting the product D prepared in the step one into a flange type tubular heating furnace, and adjusting N2The flow rate is 100 mL/min-1At 5 ℃ min-1The rate of the reaction is increased to 800 ℃, the mixture is calcined for 3 hours at constant temperature, and then the temperature is naturally reduced to room temperature, so that black powder is obtained, and the product is named as a product E.
Step three, preparing a casting solution:
dispersing the product E prepared in the second step in N, N-dimethylacetamide to prepare a 60g/L solution F, ultrasonically dispersing the solution F at the frequency of 30MHz and the temperature of 30 ℃ for 2h, and adding a polyether-polyamide block copolymer into the solution F, wherein the mass ratio of the zeolite imidazole ester skeleton porous carbon nano material to the polyether-polyamide block copolymer is 2 wt%. Stirring for 24 hours at the rotating speed of 300rpm and the temperature of 70 ℃ by using a magnetic stirrer until the mixture is completely dissolved to form a uniform membrane casting solution, namely a membrane casting solution G, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product G obtained in the third step on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet film to be 300 mu m, volatilizing the solvent for 24h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 50%, and drying for 48h in a vacuum drying box with the temperature of 60 ℃; the obtained membrane is further dried in a forced air drying box at 60 ℃ and is properly stored for standby.
The prepared mixed matrix membrane is used for measuring CO under the dry condition of room temperature and the pressure difference of 0.1MPa2Has a permeability coefficient of 474Barrer, CO2/N2The selectivity was 34.
Example 6: the preparation method of the mixed matrix membrane added with 2.5wt% of zeolite imidazole ester framework porous carbon nano material comprises the following steps:
step one, preparing a nickel-doped zeolite imidazole ester material:
respectively dissolving zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole in a methanol solution to prepare solutions with the concentrations of 0.1mol/L, 0.1mol/L and 0.8mol/L respectively, then respectively placing the solutions into a 4A molecular sieve to stand for 12 hours to remove redundant water, and obtaining a methanol solution of zinc nitrate hexahydrate (named as solution A), a methanol solution of nickel nitrate hexahydrate (named as solution B) and a methanol solution of 2-methylimidazole (named as solution C); then, pouring the solution A, the solution B and the solution C into a three-neck flask, stirring for 48 hours at 30 ℃ to perform a chemical reaction, centrifuging the obtained solution for 20 minutes within the rotation speed range of 10000rpm, washing the lower-layer precipitate in a centrifuge tube for three times by using methanol, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain purple powder, wherein the product is named as a product D;
step two, preparing the zeolite imidazole ester framework porous carbon nano material:
putting the product D prepared in the step one into a flange type tubular heating furnace, and adjusting N2The flow rate is 100 mL/min-1At 5 ℃ min-1The rate of the reaction is increased to 800 ℃, the mixture is calcined for 3 hours at constant temperature, and then the temperature is naturally reduced to room temperature, so that black powder is obtained, and the product is named as a product E.
Step three, preparing a casting solution:
dispersing the product E prepared in the second step in N, N-dimethylacetamide to prepare 80g/L solution F, ultrasonically dispersing the solution F at the frequency of 30MHz and the temperature of 30 ℃ for 2h, and adding a polyether-polyamide block copolymer into the solution F, wherein the mass ratio of the zeolite imidazole ester framework porous carbon nano material to the polyether-polyamide block copolymer is 2.5 wt%. Stirring for 24 hours at the rotating speed of 300rpm and the temperature of 70 ℃ by using a magnetic stirrer until the mixture is completely dissolved to form a uniform membrane casting solution, namely a membrane casting solution G, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product G obtained in the third step on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet film to be 300 mu m, volatilizing the solvent for 24h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 50%, and drying for 48h in a vacuum drying box with the temperature of 60 ℃; the obtained membrane is further dried in a forced air drying box at 60 ℃ and is properly stored for standby.
The prepared mixed matrix membrane is used for measuring CO under the dry condition of room temperature and the pressure difference of 0.1MPa2Has a permeability coefficient of 527Barrer, CO2/N2The selectivity was 33.
Compared with comparative example 1, the CO of the mixed matrix membrane prepared in the examples 1 to 62Permeability coefficient and CO2/N2The selectivity is obviously improved. Obviously, active metal sites and doped nitrogen in zeolite imidazole ester framework porous carbon nano-materials are CO2The transmission of (a) plays a synergistic role. In comparative examples 1 to 2, it was found that CO in a zeolite imidazole ester skeleton porous carbon nanomaterial-mixed matrix film was doped under the same conditions2Permeability coefficient and CO2/N2The selectivity is higher than that of the nickel-doped zeolite imidazate material mixed matrix membrane. In comparative examples 3 to 6, it was found that CO in the mixed matrix membrane was increased with the increase in the content of the porous carbon nanomaterial of the zeolite imidazolate framework2Permeability coefficient is increased, and CO2/N2The selectivity of the zeolite imidazole ester framework porous carbon nano material is increased and then reduced, and when the content of the zeolite imidazole ester framework porous carbon nano material reaches 1.5wt%, the selectivity reaches the maximum value.
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 many modifications without departing from the spirit of the present invention, which falls within the protection of the present invention.

Claims (7)

1. The organic-inorganic mixed matrix membrane is composed of a polymer matrix and an additive, wherein the polymer matrix is polyether-polyamide block copolymer, the additive is zeolite imidazole ester framework porous carbon nano material, and the additive accounts for 0.1-10 wt% of the mixed matrix membrane; the method is characterized in that:
firstly, zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole are selected as raw materials, and a nickel-doped zeolite imidazole ester material is synthesized by a solvothermal method; then, calcining the precursor at high temperature of 700-1000 ℃ to prepare the porous zeolite imidazole ester framework porous carbon nano material; dispersing the porous carbon nano material into a polyether-polyamide block polymer solution, and preparing an organic-inorganic mixed matrix membrane doped with the zeolite imidazole ester skeleton porous carbon nano material by adopting a solvent volatilization method; the prepared film is a homogeneous compact polymer film;
the preparation method specifically comprises the following steps:
step one, preparing a nickel-doped zeolite imidazole ester material:
respectively dissolving zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole in a methanol solution to prepare solutions with the concentrations of 0.01-0.1 mol/L, 0.01-0.1 mol/L and 0.08-12 mol/L, and then respectively placing the solutions into a 4A molecular sieve to stand for 6-24 hours to remove redundant water, thus obtaining a solution A: methanol solution of zinc nitrate hexahydrate, solution B: methanol solution of nickel nitrate hexahydrate and solution C: a methanol solution of 2-methylimidazole; then, pouring the solution A, the solution B and the solution C into a three-neck flask, stirring for 12-48 hours at 20-80 ℃ to react, centrifuging the obtained solution for 10-120 minutes within the rotating speed range of 8000-12000 rpm, washing the lower-layer precipitate in a centrifugal tube for three times by using methanol, and drying in a vacuum oven at 60-100 ℃ for 12-24 hours to obtain purple powder, wherein the product is named as a product D;
step two, preparing the zeolite imidazole ester framework porous carbon nano material:
putting the product D prepared in the step one into a flange type tubular heating furnace, and adjusting N2The flow rate is 10-500 mL/min-1At 1 to 10 ℃ per minute-1The rate of the calcination is increased to 700-1000 ℃, the calcination is carried out for 2-20 h at constant temperature, and then the calcination is naturally reduced to room temperature to obtain black powder which is named as a product E;
step three, preparing a casting solution:
dispersing the product E obtained in the step two in N, N-dimethylacetamide to prepare a solution F of 30-200G/L, ultrasonically dispersing the solution F at the frequency of 10-50 MHz and the temperature of 20-70 ℃ for 0.5-4 h, adding a polyether-polyamide block copolymer, stirring the solution F by using a magnetic stirrer at the rotating speed of 100-500 rpm and the temperature of 20-90 ℃ for 12-48 h until the solution is completely dissolved to form a uniform casting solution, namely a casting solution G, and defoaming the solution at the constant temperature of 25 ℃ for 12-24 h for later use;
the solid content of the polyether-polyamide block copolymer in the prepared casting solution is 3-25 wt%;
step four, preparing a membrane:
casting the casting solution G obtained in the third step on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet film to be 50-500 mu m, volatilizing the solvent for 24-48 h in a constant-temperature drying box with the temperature of 20-30 ℃ and the humidity of 40-60%, and drying for 24-48 h in a vacuum drying box with the temperature of 40-90 ℃; and further drying the obtained film in a blast drying oven at 30-90 ℃, and keeping the film properly for later use.
2. The method for preparing an organic-inorganic mixed matrix membrane doped with zeolite imidazolate framework porous carbon nanomaterial according to claim 1, wherein: when preparing the mixed matrix membrane, the thickness of the wet membrane is controlled to be 50-500 mu m.
3. The method for preparing an organic-inorganic mixed matrix membrane doped with zeolite imidazolate framework porous carbon nanomaterial according to claim 1, wherein: in the first step, the molar ratio of zinc nitrate hexahydrate, nickel nitrate hexahydrate and 2-methylimidazole is 1-10: 1-10: 8 to 1200.
4. The method for preparing an organic-inorganic mixed matrix membrane doped with zeolite imidazolate framework porous carbon nanomaterial according to claim 1, wherein: in the first step, 5-30 g of 4A molecular sieve is used per 100mL of methanol solution.
5. The method for preparing an organic-inorganic mixed matrix membrane doped with zeolite imidazolate framework porous carbon nanomaterial according to claim 1, wherein: the particle size of the nickel-doped zeolite imidazole ester material is 30-48 nm.
6. Prepared by the preparation method of claim 1Organic-inorganic mixed matrix membrane doped with zeolite imidazole ester framework porous carbon nanomaterial for separating CO2Application in gas.
7. Use according to claim 6, characterized in that: the prepared membrane is used for separating CO2/N2The gas permeability is tested by adopting a constant pressure volume-variable method, and the effective area of membrane permeation is 1-12.56 cm2The scavenging gas is H2The scavenging flow rate is 10-60 mL/min-1The flow rate of the feed gas is 10-60 mL/min-1Measuring the flow of the raw material side and the flow of the permeation side by using a flowmeter, and measuring the component content of the permeation side by using gas chromatography; the test temperature is 20-80 ℃, and the pressure difference is 0.1-0.8 MPa.
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