CN108745004B - Preparation method and application of mixed matrix membrane with lamellar and cage-shaped synergistic screening effects - Google Patents

Preparation method and application of mixed matrix membrane with lamellar and cage-shaped synergistic screening effects Download PDF

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CN108745004B
CN108745004B CN201810587500.8A CN201810587500A CN108745004B CN 108745004 B CN108745004 B CN 108745004B CN 201810587500 A CN201810587500 A CN 201810587500A CN 108745004 B CN108745004 B CN 108745004B
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membrane
mixed matrix
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CN108745004A (en
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张新儒
王永洪
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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide

Abstract

The invention discloses a preparation method and application of a mixed matrix membrane with a lamellar and cage-shaped synergistic screening effect. The preparation method comprises the following steps: first graphitizing the carbonitride (g-C)3N4) Introducing a zeolite imidazole framework ester material ZIF-8 into the dispersion liquid in situ, then dispersing the composite material into the polyether block amide copolymer, and preparing the polyether block amide gas separation membrane with the lamellar and cage-shaped synergistic screening effect by adopting a solution casting method; the prepared film is a homogeneous compact film, and the thickness of a wet film is controlled to be 50-500 mu m. The preparation process of the inorganic material provided by the invention is easy to control, and g-C3N4Interlayer nanosheet and g-C of composite with ZIF-83N4The pores of the tris-s-triazine ring are CO2A channel is provided; the prepared membrane is acid-resistant and alkali-resistant, has good flexibility, and has excellent comprehensive performance when being used for gas separation; can effectively and selectively separate CO2Is CO2Provides a fast migration path.

Description

Preparation method and application of mixed matrix membrane with lamellar and cage-shaped synergistic screening effects
Technical Field
The invention relates to a preparation method and application of a mixed matrix membrane with a lamella and cage-shaped synergistic screening effect, and belongs to the technical field of gas separation membranes.
Background
The mixed matrix membrane is a composite membrane added with inorganic materials into organic polymers, and becomes a hotspot of current researches of researchers due to excellent separation performance, simple preparation, economy and practicality. On one hand, the introduction of the inorganic particles in the mixed matrix membrane 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. However, if the interfacial compatibility between the polymer and the filler in the MMMs is poor, non-selective voids may occur, hardening of the polymer and pore blocking may occur, resulting in deterioration of the membrane performance. Therefore, the choice of polymer and inorganic filler is critical to the development of MMMs.
The polyether copolyamide is a thermoplastic elastomer consisting of hard segments of polyamide PA and soft segments of polyether PE, the polyamide crystalline domains providing mechanical strength and the polyether amorphous domains providing high permeability. It is a typical commercialized rubbery block copolymer, has high thermal stability, mechanical stability, acid and alkali resistance and organic solvent resistance, and becomes one of the most promising materials.
Graphitized carbon nitride (g-C)3N4) Has good thermal and chemical stability and is proved to be the most stable carbon nitride allotrope under normal temperature and pressure. Constituting the graphite phase g-C3N4Is C6N7With an interlayer spacing of about 0.326nm, g-C3N4The lone pair electrons on the C and N atoms can interact to form a large pi bond similar to a benzene ring, thereby forming a highly delocalized conjugated system. In addition, in the thermal condensation process, the planar terminal has structural defects, and amino groups (-NH) exist2) And functional groups such as imino (-NH). g-C3N4All show that it is to CO2Very good affinity, but it is used for separating CO2Probably because of g-C3N4Is less than CO2Molecular size of (2) to CO2The resistance of (2) is large.
Disclosure of Invention
The invention aims to provide a preparation method and application of a mixed matrix membrane with a lamellar and cage-shaped synergistic screening effect, and particularly relates to a method for loading a zeolite imidazole ester framework material on the surface of graphitized carbonitride in situ, adding the material into a polyether block amide copolymer PEBA, and applying the material to CO2/N2Separation of (4). The mixed matrix membrane is found to have higher CO in application2Permeability coefficient and separation factor.
In the invention, ZIF-8 is loaded in the g-C in situ3N4Above, on the one hand, increase of g-C3N4On the other hand, ZIF-8 also provides a channel for gas diffusion(ii) a Overcome the defect of' g-C3N4Is less than CO2Molecular size of (2), to CO2The resistance of (2) is large; g-C in the invention3N4Is negatively charged with Zn2+The electrostatic interaction of (a) enables successful loading of ZIF-8 to g-C3N4On the sheet layer; by adjusting g-C3N4And the ratio of ZIF-8 to realize the regulation and control of the interlamellar spacing of the composite material, wherein the regulation and control range of the interlamellar spacing is 2-4 Å2/N2Is CO when separated2Providing a rapid passage and increasing CO2Permeability coefficient and separation factor.
The invention provides a preparation method of a mixed matrix membrane with a lamellar and cage-shaped synergistic screening effect, which comprises the steps of firstly, preparing a mixed matrix membrane by using a solvent and a solvent in a solvent system in g-C3N4Introducing a zeolite imidazole framework ester material ZIF-8 into the dispersion liquid in situ, then dispersing the composite material into polyether block amide, and preparing the polyether block amide gas separation membrane with the lamellar and cage-shaped synergistic screening effect by adopting a solution casting method; the prepared film is a homogeneous compact film, and the thickness of a wet film is controlled to be 50-500 mu m.
In the preparation method, the polyamide chain segment of the polyether block amide is polyamide nylon-12, and the polyether chain segment is polytetrahydrofuran; in the preparation method, the composite material accounts for 0.5-5 wt% of the total mass of the mixed matrix membrane.
In the preparation method, the interlayer distance of the composite material is 2-4 Å.
The preparation method comprises the following steps:
step one, preparing graphitized carbon nitride g-C3N4：
Synthesis of g-C by thermal polymerization3N4: putting the dried urea into a flange type tubular heating furnace, and adjusting the flow speed of protective gas to be 10-200 mL/min-1At 1 to 10 ℃ per minute-1The temperature rising rate is increased to 350-850 ℃, the mixture is calcined at constant temperature for 2-10 hours, and then the temperature is naturally reduced to 25 ℃; the unpurified yellow g-C is obtained3N4Powder;
subjecting the obtainedUnpurified yellow g-C3N4Dispersing the powder in water, carrying out ultrasonic treatment for 1-3 h at the frequency of 10-50 MHz, centrifuging for 5-100 min by using a centrifuge with the rotating speed of 5000-15000 r/min, and then drying the lower layer precipitate in a vacuum drying oven at 80-110 ℃ for 4-72 h to obtain g-C3N4Powder is used for later use;
step two, preparation of g-C3N4And ZIF-8 composite (designated CNZ):
subjecting the g-C prepared in step one3N4Dispersing the powder in methanol to prepare a solution A of 10-150 g/L, and uniformly dispersing by ultrasonic for 1-5 h; then adding zinc nitrate hexahydrate into the solution A, and continuing to perform ultrasonic treatment for 0.5-3 hours to enable Zn to be obtained2+Fixed at g-C3N4Above, named solution B;
then pouring the solution B into a methanol solution of 2-methylimidazole with the concentration of 10-100 g/L, stirring the solution B on a magnetic stirrer with the rotation speed of 100-500 rpm and the temperature of 15-40 ℃ for 12-48 hours to react and synthesize g-C3N4And ZIF-8; standing for 12-48 h, removing supernatant, and washing the lower precipitate with methanol for three times to obtain CNZ-containing suspension C;
step three, preparing a casting solution:
dissolving the prepared CNZ suspension C in N, N-dimethylacetamide to prepare a solution D of 30-200 g/L, ultrasonically dispersing the solution D at the frequency of 10-50 MHz and the temperature of 20-70 ℃ for 0.5-4 h, adding a polyether block amide copolymer into the solution D, stirring the solution D 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 D is completely dissolved to form a uniform casting solution, and naming the uniform casting solution as a product E, and defoaming the uniform casting solution at the constant temperature of 25 ℃ for 12-24 h for later use;
adjusting the solid content of the polymer matrix to 3-25 wt% when preparing the casting solution;
step four, preparing a membrane:
casting the product E 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.
In the above preparation method, in the first step, the shielding gas is one of nitrogen gas and inert gas, and the inert gas includes one of argon gas and helium gas.
In the above preparation method, in step one, g-C3N4The mass ratio of the water to the water is 0.5-50: 300-5000; in step two, g-C3N4The mass ratio of the powder to the zinc nitrate hexahydrate is 1-20: 0.5-5, wherein the molar ratio of zinc nitrate hexahydrate to 2-methylimidazole is 1-10: 4 to 700.
The invention provides a mixed matrix membrane with a lamellar and cage-shaped synergistic screening effect, which is prepared by the method.
The invention provides the mixed matrix membrane with the lamella and cage-shaped synergistic screening effect for separating CO2The use of (1). The prepared membrane is used for separating CO2/N2The gas permeability is tested by adopting a constant pressure variable volume 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 testing temperature is room temperature, and the pressure difference is 0.1-0.5 MPa.
The invention has the beneficial effects that:
（1）g-C3N4and interlayer nanosheet of ZIF-8 composite CNZ and C3N4The hole on the upper tris-triazine ring is CO2A channel is provided;
(2) ZIF-8 with flexible backbone and high porosity for CO2Diffusion of (2);
（3）g-C3N4the large pi bond formed by the interaction of the lone pair of electrons on the carbon can be bonded with CO2The pi-pi complexation interaction occurs, and CO is promoted2The transfer of (2);
(4) the preparation process of the inorganic material provided by the invention is simple and easy to control, the preparation process of the mixed matrix membrane is convenient to operate, the prepared membrane is acid-resistant and alkali-resistant, the flexibility is good,the catalyst is used for gas separation and has excellent comprehensive performance; 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 27.
Example 1: preparation of 1.5wt% addition of g-C3N4The mixed matrix membrane of (1), the steps are as follows:
step one, g-C3N4The preparation of (1):
synthesis of g-C by thermal polymerization3N4. Putting the dried urea into a flange type tubular heating furnace, and adjusting the flow rate of protective gas to be 100 mL/min-1At 10 ℃ min-1The temperature rising rate is increased to 850 ℃, the mixture is calcined for 10 hours at constant temperature and then naturally reduced to 25 ℃. The resulting unpurified yellow g-C3N4The powder is dispersed in water (g-C)3N4The mass ratio of the water to the water is 30: 5000), ultrasonic treatment is carried out for 3h under the frequency of 50MHz, a centrifuge with the rotating speed of 12000r/min is used for centrifuging for 60min, and then the lower layer is depositedDrying at 100 deg.C in vacuum drying oven for 24 hr to obtain g-C3N4Powder is used for later use;
step two, preparing a casting solution:
subjecting the g-C prepared in step one3N4Dissolving the powder in N, N-dimethylacetamide to obtain 100g/L solution A, ultrasonically dispersing the solution A at 50MHz and 60 deg.C for 4 hr, adding polyether block amide copolymer, wherein g-C3N4And the polyether block amide copolymer in a mass ratio of 1.5: 100. Stirring for 48 hours at the rotating speed of 500rpm and the temperature of 80 ℃ by using a magnetic stirrer until the uniform membrane casting solution is completely dissolved, namely a product B, and defoaming at the constant temperature of 25 ℃ for 24 hours for later use;
step three, membrane preparation:
casting the product B of the second 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 48h in a constant-temperature drying box with the temperature of 25 ℃ and the humidity of 60%, 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 221Barrer, CO2/N2The selectivity was 28. Addition of g-C in comparison with comparative example 13N4The mixed matrix membrane has greatly raised permeability coefficient without lowering the selectivity of the pure polyether block amide membrane.
Example 2: a mixed matrix membrane with 1.5wt% CNZ added was prepared by the following steps:
step one, g-C3N4The preparation of (1):
synthesis of g-C by thermal polymerization3N4. Putting the dried urea into a flange type tubular heating furnace, and adjusting the flow rate of protective gas to be 100 mL/min-1At 5 ℃ min-1The temperature rising rate is increased to 850 ℃, the mixture is calcined for 6 hours at constant temperature, and then the temperature is naturally reduced to 25 ℃. The resulting unpurified yellow g-C3N4The powder is dispersed in water (g-C)3N4The mass ratio of the water to the water is 20: 3000), performing ultrasonic treatment for 2h at the frequency of 30MHz, centrifuging for 20min by a centrifuge with the rotation speed of 10000r/min, and drying the lower layer in a vacuum drying oven at 80 ℃ for 24h to obtain g-C3N4Powder is used for later use;
step two, g-C3N4And preparation of ZIF-8 composite (designated CNZ):
subjecting the g-C prepared in step one3N4The powder is dispersed in methanol to prepare a solution A with the concentration of 50g/L, and the solution A is uniformly dispersed by ultrasonic treatment for 3 hours. An amount of zinc nitrate hexahydrate was then added to the solution a, designated as solution B. Continuing to perform ultrasonic treatment for 2h to enable Zn2+Fixed at g-C3N4The above. Then pouring the solution B into a methanol solution of 2-methylimidazole with the concentration of 30g/L, stirring the solution B on a magnetic stirrer with the rotation speed of 300rpm and the temperature of 30 ℃ for 48 hours to react and synthesize ZIF-8, standing the mixture for 12 hours, removing supernatant, washing the lower-layer precipitate with methanol for three times to obtain CNZ-containing suspension C, wherein g-C is3N4And ZIF-8 in a mass ratio of 10: 1;
step three, preparing a casting solution:
dissolving the prepared CNZ suspension C in N, N-dimethylacetamide to prepare 50g/L solution D, ultrasonically dispersing the solution D at 20 ℃ at the frequency of 20MHz for 2h, and adding polyether block amide, wherein g-C3N4And the polyether block amide copolymer in a mass ratio of 1.5: 100. Stirring for 24 hours at the rotation speed of 300rpm and the temperature of 70 ℃ by adopting a magnetic stirrer until the mixture is completely dissolved to form a uniform membrane casting solution, namely a product E, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product E obtained in the step three 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 24h 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 at room temperature and the pressure difference is 0.1MPaMeasurement of CO under Dry conditions2Has a permeability coefficient of 238Barrer, CO2/N2The selectivity was 34.
Example 3: a mixed matrix membrane with 1.5wt% CNZ added was prepared by the following steps:
step one, g-C3N4The preparation of (1):
synthesis of g-C by thermal polymerization3N4. Putting the dried urea into a flange type tubular heating furnace, and adjusting the flow rate of protective gas to 120 mL/min-1At 8 ℃ min-1The temperature rising rate is increased to 850 ℃, the mixture is calcined for 7 hours at constant temperature and then naturally reduced to 25 ℃. The resulting unpurified yellow g-C3N4The powder is dispersed in water (g-C)3N4The mass ratio of the water to the water is 10: 3000), performing ultrasonic treatment for 3h at the frequency of 20MHz, centrifuging for 30min by a centrifuge with the rotating speed of 12000r/min, and drying the lower layer in a vacuum drying oven at 90 ℃ for 48h to obtain the g-C3N4Powder is used for later use;
step two, g-C3N4And preparation of ZIF-8 composite (designated CNZ):
subjecting the g-C prepared in step one3N4The powder is dispersed in methanol to prepare a solution A of 80g/L, and the solution A is uniformly dispersed by ultrasonic treatment for 4 hours. An amount of zinc nitrate hexahydrate was then added to the solution a, designated as solution B. Continuing to perform ultrasonic treatment for 3h to enable Zn2+Fixed at g-C3N4The above. Then pouring the solution B into a methanol solution of 2-methylimidazole with the concentration of 30g/L, stirring the solution B on a magnetic stirrer with the rotation speed of 500rpm and the temperature of 40 ℃ for 48 hours to react and synthesize ZIF-8, standing the mixture for 48 hours, removing supernatant, washing the lower-layer precipitate with methanol for three times to obtain CNZ-containing suspension C, wherein g-C is3N4And ZIF-8 in a mass ratio of 5: 1;
step three, preparing a casting solution:
dissolving the prepared CNZ suspension C in N, N-dimethylacetamide to prepare 80g/L solution D, ultrasonically dispersing the solution D at the frequency of 30MHz and the temperature of 50 ℃ for 3h, and adding polyether block amide, wherein g-C3N4And polyether block amidesThe mass ratio of the amine copolymer was 1.5: 100. Stirring for 24 hours at the rotation speed of 500rpm and the temperature of 80 ℃ by using a magnetic stirrer until the uniform membrane casting solution is completely dissolved, namely a product E, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product E obtained in the step three on a clean glass plate or a polytetrafluoroethylene plate, controlling the thickness of a wet film to be 200 mu m, volatilizing the solvent for 24h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 30%, and drying for 24h in a vacuum drying box with the temperature of 80 ℃; 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 248Barrer, CO2/N2The selectivity was 36.
Example 4: a mixed matrix membrane with 1.5wt% CNZ added was prepared by the following steps:
step one, g-C3N4The preparation of (1):
synthesis of g-C by thermal polymerization3N4. Putting the dried urea into a flange type tubular heating furnace, and adjusting the flow rate of protective gas to 150 mL/min-1At 10 ℃ min-1The temperature rising rate is increased to 550 ℃, the mixture is calcined for 5 hours at constant temperature and then naturally reduced to 25 ℃. The resulting unpurified yellow g-C3N4The powder is dispersed in water (g-C)3N4The mass ratio of the water to the water is 5: 2000), ultrasonic processing is carried out for 3h under the frequency of 30MHz, a centrifuge with the rotating speed of 15000r/min is used for centrifuging for 50min, the lower layer is precipitated in a vacuum drying oven at 100 ℃ for drying for 48h, and g-C is prepared3N4Powder is used for later use;
step two, g-C3N4And preparation of ZIF-8 composite (designated CNZ):
subjecting the g-C prepared in step one3N4The powder is dispersed in methanol to prepare a solution A of 100g/L, and the solution A is uniformly dispersed by ultrasonic for 3 h. An amount of zinc nitrate hexahydrate was then added to the solution a, designated as solution B. Continuing to perform ultrasonic treatment for 2h to enable Zn2+Fixed at g-C3N4The above. Then pouring the solution B into a methanol solution of 2-methylimidazole with the concentration of 30g/L, stirring the solution B on a magnetic stirrer with the rotation speed of 500rpm and the temperature of 30 ℃ for 48 hours to react and synthesize ZIF-8, standing the mixture for 48 hours, removing supernatant, washing the lower-layer precipitate with methanol for three times to obtain CNZ-containing suspension C, wherein g-C is3N4And ZIF-8 in a mass ratio of 2: 1;
step three, preparing a casting solution:
dissolving the prepared CNZ suspension C in N, N-dimethylacetamide to prepare 80g/L solution D, ultrasonically dispersing the solution D at the frequency of 50MHz and the temperature of 60 ℃ for 4h, and adding polyether block amide, wherein g-C3N4And the polyether block amide copolymer in a mass ratio of 1.5: 100. Stirring for 24 hours at the rotating speed of 300rpm and the temperature of 60 ℃ by using a magnetic stirrer until the uniform membrane casting solution is completely dissolved, namely a product E, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product E obtained in the step three 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 48h 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 253Barrer, CO2/N2The selectivity was 36.
Example 5: a mixed matrix membrane with 1.5wt% CNZ added was prepared by the following steps:
step one, g-C3N4The preparation of (1):
synthesis of g-C by thermal polymerization3N4. Putting the dried urea into a flange type tubular heating furnace, and adjusting the flow rate of protective gas to be 100 mL/min-1At 5 ℃ min-1The temperature rising rate is increased to 650 ℃, the mixture is calcined for 5 hours at constant temperature and then naturally reduced to 25 ℃. The resulting unpurified yellow g-C3N4The powder is dispersed in water (g-C)3N4The mass ratio of the water to the water is 5: 2000), performing ultrasonic treatment for 3h at the frequency of 30MHz, centrifuging for 60min by a centrifuge with the rotation speed of 15000r/min, and drying the lower layer in a vacuum drying oven at 110 ℃ for 48h to obtain g-C3N4Powder is used for later use;
step two, g-C3N4And preparation of ZIF-8 composite (designated CNZ):
subjecting the g-C prepared in step one3N4The powder is dispersed in methanol to prepare a solution A of 120g/L, and the solution A is uniformly dispersed by ultrasonic for 5 hours. An amount of zinc nitrate hexahydrate was then added to the solution a, designated as solution B. Continuing to perform ultrasonic treatment for 3h to enable Zn2+Fixed at g-C3N4The above. Then pouring the solution B into a methanol solution of 2-methylimidazole with the concentration of 30g/L, stirring the solution B on a magnetic stirrer with the rotation speed of 500rpm and the temperature of 40 ℃ for 48 hours to react and synthesize ZIF-8, standing the mixture for 48 hours, removing supernatant, washing the lower-layer precipitate with methanol for three times to obtain CNZ-containing suspension C, wherein g-C is3N4And ZIF-8 in a mass ratio of 1: 1;
step three, preparing a casting solution:
dissolving the prepared CNZ suspension C in N, N-dimethylacetamide to prepare 80g/L solution D, ultrasonically dispersing the solution D at the frequency of 50MHz and the temperature of 70 ℃ for 4h, and adding polyether block amide, wherein g-C3N4And the polyether block amide copolymer in a mass ratio of 1.5: 100. Stirring for 24 hours at the rotation speed of 500rpm and the temperature of 80 ℃ by using a magnetic stirrer until the uniform membrane casting solution is completely dissolved, namely a product E, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product E obtained in the step three 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 48h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 60%, and drying for 48h in a vacuum drying box with the temperature of 80 ℃; 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 281Barrer, CO2/N2The selectivity was 43.
Example 6: a mixed matrix membrane with 1.5wt% CNZ added was prepared by the following steps:
step one, g-C3N4The preparation of (1):
synthesis of g-C by thermal polymerization3N4. Putting the dried urea into a flange type tubular heating furnace, and adjusting the flow rate of protective gas to 150 mL/min-1At 5 ℃ min-1The temperature rising rate is increased to 550 ℃, the mixture is calcined for 8 hours at constant temperature and then naturally reduced to 25 ℃. The resulting unpurified yellow g-C3N4The powder is dispersed in water (g-C)3N4The mass ratio of the water to the water is 3: 1000), ultrasonic treatment is carried out for 3h under the frequency of 50MHz, a centrifuge with the rotating speed of 12000r/min is used for centrifuging for 30min, the lower layer is precipitated in a vacuum drying oven at 80 ℃ for drying for 72h, and g-C is prepared3N4Powder is used for later use;
step two, g-C3N4And preparation of ZIF-8 composite (designated CNZ):
subjecting the g-C prepared in step one3N4The powder is dispersed in methanol to prepare a solution A of 100g/L, and the solution A is uniformly dispersed by ultrasonic for 5 hours. An amount of zinc nitrate hexahydrate was then added to the solution a, designated as solution B. Continuing to perform ultrasonic treatment for 2h to enable Zn2+Fixed at g-C3N4The above. Then pouring the solution B into a methanol solution of 2-methylimidazole with the concentration of 30g/L, stirring the solution B on a magnetic stirrer with the rotation speed of 500rpm and the temperature of 30 ℃ for 48 hours to react and synthesize ZIF-8, standing the mixture for 48 hours, removing supernatant, washing the lower-layer precipitate with methanol for three times to obtain CNZ-containing suspension C, wherein g-C is3N4And ZIF-8 in a mass ratio of 1: 2;
step three, preparing a casting solution:
dissolving the prepared CNZ suspension C in N, N-dimethylacetamide to prepare 80g/L solution D, ultrasonically dispersing the solution D at the frequency of 30MHz and the temperature of 50 ℃ for 3h, and adding polyether block amideWherein g-C3N4And the polyether block amide copolymer in a mass ratio of 1.5: 100. Stirring for 24 hours at the rotating speed of 300rpm and the temperature of 60 ℃ by using a magnetic stirrer until the uniform membrane casting solution is completely dissolved, namely a product E, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product E obtained in the step three 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 48h 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 242Barrer, CO2/N2The selectivity was 41.
Example 7: a mixed matrix membrane with 0.5wt% CNZ added was prepared by the following steps:
step one, g-C3N4The preparation of (1):
synthesis of g-C by thermal polymerization3N4. Putting the dried urea into a flange type tubular heating furnace, and adjusting the flow rate of protective gas to be 20 mL/min-1At 3 ℃ min-1The temperature rising rate is increased to 550 ℃, the mixture is calcined for 5 hours at constant temperature and then naturally reduced to 25 ℃. The resulting unpurified yellow g-C3N4The powder is dispersed in water (g-C)3N4The mass ratio of the water to the water is 3: 5000), ultrasonic treatment is carried out for 3h under the frequency of 20MHz, a centrifuge with the rotating speed of 8000r/min is used for centrifuging for 30min, the lower layer is precipitated in a vacuum drying oven at 80 ℃ for drying for 48h, and g-C is prepared3N4Powder is used for later use;
step two, g-C3N4And preparation of ZIF-8 composite (designated CNZ):
subjecting the g-C prepared in step one3N4The powder is dispersed in methanol to prepare a solution A with the concentration of 50g/L, and the solution A is uniformly dispersed by ultrasonic treatment for 3 hours. Then adding a certain amount of zinc nitrate hexahydrate into the solution A, named as solutionAnd (B) liquid. Continuing to perform ultrasonic treatment for 3h to enable Zn2+Fixed at g-C3N4The above. Then pouring the solution B into a methanol solution of 2-methylimidazole with the concentration of 30g/L, stirring the solution B on a magnetic stirrer with the rotation speed of 300rpm and the temperature of 40 ℃ for 48 hours to react and synthesize ZIF-8, standing the mixture for 48 hours, removing supernatant, washing the lower-layer precipitate with methanol for three times to obtain CNZ-containing suspension C, wherein g-C is3N4And ZIF-8 in a mass ratio of 1: 1;
step three, preparing a casting solution:
dissolving the prepared CNZ suspension C in N, N-dimethylacetamide to prepare 80g/L solution D, ultrasonically dispersing the solution D at the frequency of 50MHz and the temperature of 70 ℃ for 4h, and adding polyether block amide, wherein g-C3N4And the polyether block amide copolymer in a mass ratio of 0.5: 100. Stirring for 24 hours at the rotation speed of 500rpm and the temperature of 80 ℃ by using a magnetic stirrer until the uniform membrane casting solution is completely dissolved, namely a product E, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product E obtained in the step three 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 48h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 60%, and drying for 48h in a vacuum drying box with the temperature of 80 ℃; 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 241Barrer, CO2/N2The selectivity was 39.
Example 8: a mixed matrix membrane with 2.5wt% CNZ added was prepared by the following steps:
step one, g-C3N4The preparation of (1):
synthesis of g-C by thermal polymerization3N4. Putting the dried urea into a flange type tubular heating furnace, and adjusting the flow rate of protective gas to be 50 mL/min-1At 8 ℃ min-1The temperature rising rate is increased to 850 ℃, the mixture is calcined for 5 hours at constant temperature, and then the temperature is naturally reduced to 25 ℃.The resulting unpurified yellow g-C3N4The powder is dispersed in water (g-C)3N4The mass ratio of the water to the water is 3: 5000), performing ultrasonic treatment for 3h at the frequency of 50MHz, centrifuging for 50min by a centrifuge with the rotation speed of 12000r/min, and drying the lower layer in a vacuum drying oven at 80 ℃ for 48h to obtain g-C3N4Powder is used for later use;
step two, g-C3N4And preparation of ZIF-8 composite (designated CNZ):
subjecting the g-C prepared in step one3N4The powder is dispersed in methanol to prepare a solution A of 100g/L, and the solution A is uniformly dispersed by ultrasonic for 5 hours. An amount of zinc nitrate hexahydrate was then added to the solution a, designated as solution B. Continuing to perform ultrasonic treatment for 3h to enable Zn2+Fixed at g-C3N4The above. Then pouring the solution B into a methanol solution of 2-methylimidazole with the concentration of 30g/L, stirring the solution B on a magnetic stirrer with the rotation speed of 500rpm and the temperature of 40 ℃ for 48 hours to react and synthesize ZIF-8, standing the mixture for 48 hours, removing supernatant, washing the lower-layer precipitate with methanol for three times to obtain CNZ-containing suspension C, wherein g-C is3N4And ZIF-8 in a mass ratio of 1: 1;
step three, preparing a casting solution:
dissolving the prepared CNZ suspension C in N, N-dimethylacetamide to prepare 150g/L solution D, ultrasonically dispersing the solution D at the frequency of 50MHz and the temperature of 70 ℃ for 4h, and adding polyether block amide, wherein g-C3N4And the polyether block amide copolymer in a mass ratio of 2.5: 100. Stirring for 24 hours at the rotation speed of 500rpm and the temperature of 80 ℃ by using a magnetic stirrer until the uniform membrane casting solution is completely dissolved, namely a product E, and defoaming for 24 hours at the constant temperature of 25 ℃ for later use;
step four, membrane preparation:
casting the product E obtained in the step three 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 48h in a constant-temperature drying box with the temperature of 30 ℃ and the humidity of 60%, and drying for 48h in a vacuum drying box with the temperature of 80 ℃; 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 310Barrer, CO2/N2The selectivity was 46.
Compared with comparative example 1, the CO of the mixed matrix membrane prepared in the examples 1 to 82Permeability coefficient and CO2/N2The selectivity is obviously improved. It is clear that the synergistic sieving effect of the lamella and the cage is CO2Provides a channel. Comparative examples 1 to 6, found to follow C3N4: increase in ZIF-8 mass ratio, CO2Permeability coefficient and CO2/N2All selectivity increases and then decreases at C3N4: ZIF-8=1:1, CO2Permeability coefficient and CO2/N2The selectivity reaches a maximum. Comparing examples 5, 7 and 8, it was found that with increasing CNZ content, CO of the mixed matrix membrane was increased2Permeability coefficient is increased, and CO2/N2The selectivity of (a) increases and then decreases, and reaches a maximum when the content of CNZ reaches 1.5 wt%.
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 (9)

1. A preparation method of a mixed matrix membrane with a lamellar and cage-shaped synergistic screening effect is characterized by comprising the following steps: firstly, introducing a zeolite imidazole ester framework material ZIF-8 in situ in a graphitized nitrogen carbide dispersion liquid to form a composite material CNZ, then dispersing the composite material into a polyether block amide copolymer, and preparing a polyether block amide gas separation membrane with a lamellar and cage-shaped synergistic screening effect by adopting a solution casting method; the prepared film is a homogeneous compact film, and the thickness of a wet film is controlled to be 50-500 mu m;
the preparation method of the mixed matrix membrane with the lamellar and cage-shaped synergistic screening effect specifically comprises the following steps:
step one, preparing graphitized carbon nitride g-C3N4：
Synthesis of g-C by thermal polymerization3N4: putting the dried urea into a flange type tubular heating furnace, and adjusting the flow speed of protective gas to be 10-200 mL/min-1At 1 to 10 ℃ per minute-1The temperature rising rate is increased to 350-850 ℃, the mixture is calcined at constant temperature for 2-10 hours, and then the temperature is naturally reduced to 25 ℃; the unpurified yellow g-C is obtained3N4Powder;
the unpurified yellow g-C3N4Dispersing the powder in water, carrying out ultrasonic treatment for 1-3 h at the frequency of 10-50 MHz, centrifuging for 5-100 min by using a centrifuge with the rotating speed of 5000-15000 r/min, and then drying the lower layer precipitate in a vacuum drying oven at 80-110 ℃ for 4-72 h to obtain g-C3N4Powder is used for later use;
step two, preparation of g-C3N4And ZIF-8 composite CNZ:
subjecting the g-C prepared in step one3N4Dispersing the powder in methanol to prepare a solution A of 10-150 g/L, and uniformly dispersing by ultrasonic for 1-5 h; then adding zinc nitrate hexahydrate into the solution A, and continuing to perform ultrasonic treatment for 0.5-3 hours to enable Zn to be obtained2+Fixed at g-C3N4Above, named solution B;
then pouring the solution B into a methanol solution of 2-methylimidazole with the concentration of 10-100 g/L, stirring the solution B on a magnetic stirrer with the rotation speed of 100-500 rpm and the temperature of 15-40 ℃ for 12-48 hours to react and synthesize g-C3N4And ZIF-8; standing for 12-48 h, removing supernatant, and washing the lower precipitate with methanol for three times to obtain CNZ-containing suspension C;
step three, preparing a casting solution:
dissolving the prepared CNZ suspension C in N, N-dimethylacetamide to prepare a solution D of 30-200 g/L, ultrasonically dispersing the solution D at the frequency of 10-50 MHz and the temperature of 20-70 ℃ for 0.5-4 h, adding a polyether block amide copolymer into the solution D, stirring the solution D for 12-48 h at the rotation speed of 100-500 rpm and the temperature of 20-90 ℃ by using a magnetic stirrer until the solution D is completely dissolved to form a uniform casting solution, namely a product E, and defoaming the solution at the constant temperature of 25 ℃ for 12-24 h for later use;
adjusting the solid content of the polymer matrix to 3-25 wt% when preparing the casting solution;
step four, preparing a membrane:
casting the product E 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 a mixed matrix membrane with a lamellar and caged cooperative sieving function as claimed in claim 1, wherein: the polyamide chain segment of the polyether block amide copolymer is polyamide nylon-12, and the polyether chain segment is polytetrahydrofuran.
3. The method for preparing a mixed matrix membrane with a lamellar and caged cooperative sieving function as claimed in claim 1, wherein: the mass ratio of the composite material to the total mass of the mixed matrix membrane is 0.5-5 wt%.
4. The method for preparing a mixed matrix membrane with a lamellar and caged cooperative sieving function as claimed in claim 1, wherein: by adjusting g-C3N4And ZIF-8, so that the interlamellar spacing of the composite material is regulated and controlled, and is 2-4 Å.
5. The method for preparing a mixed matrix membrane with a lamellar and caged cooperative sieving function as claimed in claim 1, wherein: in the first step, the protective gas is one of nitrogen or inert gas, and the inert gas includes one of argon and helium.
6. The method for preparing a mixed matrix membrane with a lamellar and caged cooperative sieving function according to claim 1,the method is characterized in that: in step one, g-C3N4The mass ratio of the water to the water is 0.5-50: 300-5000; in step two, g-C3N4The mass ratio of the powder to the zinc nitrate hexahydrate is 1-20: 0.5-5, wherein the molar ratio of zinc nitrate hexahydrate to 2-methylimidazole is 1-10: 4 to 700.
7. A mixed matrix membrane with a lamellar and cage-shaped synergistic screening effect, which is prepared by the preparation method of any one of claims 1 to 6.
8. Use of the mixed matrix membrane with lamellar and caged cooperative sieving as claimed in claim 7 in separating CO2The use of (1).
9. Use according to claim 8, characterized in that: the prepared mixed matrix membrane with the lamellar and cage-shaped synergistic screening function is used for separating CO2/N2The gas permeability is tested by adopting a constant pressure variable volume 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 testing temperature is room temperature, and the pressure difference is 0.1-0.5 MPa.
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