CN113893700A - Rapid preparation method and application of dual-functionalized mixed matrix membrane with high carbon dioxide selectivity - Google Patents
Rapid preparation method and application of dual-functionalized mixed matrix membrane with high carbon dioxide selectivity Download PDFInfo
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Abstract
In order to solve the problems of low permeation selectivity, long preparation time and the like of the conventional mixed matrix membrane with a single functional group, the rapid preparation method of the dual-functionalized mixed matrix membrane with high carbon dioxide selectivity is provided2. The invention firstly utilizes quaternary ammonium salt to organically modify bentonite, then utilizes amino functional group to carry out amino functional modification on the organic bentonite as organic filler, then adopts mechanical stirring to disperse the amino functional bentonite into a membrane preparation mother agent while carrying out microwave radiation, and then sequentially adds a pore-forming agent and homogeneous polyvinylidene fluoride to quickly obtain the productTo homogeneous membrane casting solution. And (3) blade-coating the casting solution on a glass plate, and putting the glass plate into a solidification water bath to prepare the amino-fluorine-group dual-functional mixed matrix membrane. The preparation method of the dual-functionalized mixed matrix membrane is simple, short in used time, excellent in performance and suitable for CO2/N2、CO2/CH4And (5) separating.
Description
Technical Field
The invention belongs to the field of preparation of gas separation membrane materials; relates to a method for optimizing the preparation process of a gas separation membrane material by introducing a specific group, promoting the functional transformation of polymer molecules and the like to obtain a dual-functional mixed matrix membrane; in particular to a preparation method of a separating membrane material for capturing carbon dioxide.
Background
With the rapid development of modern industry and the acceleration of urbanization process, CO in the atmosphere2The data show that the CO in the atmosphere is gradually increased2The concentration is 280mL/m from 1800 years3Greatly increased to 410mL/m in 20203Global warming has been exacerbated by a rise in global air temperature of about 1.2 ℃. Global warming has become a major international concern, and at the 21 st united nations climate change convention, there is a concerted effort by countries in the world to limit the magnitude of temperature rise to within 1.5 ℃. To cope with climate change, CO is therefore2Capture, utilization and sequestration (CCUS) is becoming an increasingly important research focus in the scientific and industrial sectors, the key of which is the selective capture of CO from gas mixtures2. At present, CO2Trapping techniques include chemical absorption, cryogenic separation, adsorption, and membrane separation. Wherein, the membrane separation method has the characteristics of less fixed investment, simple operation, low energy consumption, small occupied area and the like, and CO is obtained2The method has good development prospect in the field of trapping.
Membrane technology for gas separation has been widely used, and although polymer matrix membranes have the characteristics of good mechanical stability, easy scale-up, and low cost, they are limited by the "trade-off" effect, which affects their efficient use. Therefore, the introduction of the filler with specific functional groups into the polymer matrix can increase the gas permeation flux and improve the gas selectivity. Materials currently used as fillers include zeolite, silica nanospheres, MOF, COF, graphene oxide, carbon nanotubes, etc., but these materials have problems of complicated preparation or high price, and the mixed matrix membrane having a single functional group has problems of low permselectivity, long preparation time, etc.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a method for efficiently capturing CO, which has the advantages of simple process, low cost, short time consumption, capability of greatly increasing gas permeation selectivity and capability of efficiently capturing CO2The preparation method of the membrane with the double-functionalized mixed matrix and the application of the membrane in gas separation.
In order to achieve the above purpose, we have conducted research and experiments to find that polyvinylidene fluoride (PVDF) has a structure that is easily transformed from an alpha phase to a beta phase under an external force stimulation, and the arrangement of the beta phase in a unit cell is a TTTT conformation, i.e., all F atoms are arranged outward. Can make more F atoms and CO2Contact with CO2The strong acting force is beneficial to improving the gas separation effect.
Therefore, the technical scheme adopted by the invention is as follows: PVDF is used as a polymer matrix, more alpha phase is promoted to be converted into beta phase in a microwave-assisted mode, more F atoms are exposed on the surface, cheap and easily-obtained bentonite is used as an inorganic filler, the bentonite is organized firstly, more amino groups can be crosslinked by the bentonite, so that the permeability of carbon dioxide and the gas selectivity are greatly increased, and the bentonite is dispersed in a mixed matrix membrane casting solution through microwave assistance to prepare the amino-containing and fluorine-based dual-functionalized mixed matrix membrane.
The method specifically comprises the following steps:
(1) preparing raw materials: the raw materials comprise bentonite powder, quaternary ammonium salt, a pore-making agent, PVDF, a membrane-making mother agent and a silane coupling agent solvent, and the bentonite powder, the pore-making agent and the PVDF are respectively and simultaneously placed in microwave vacuum drying equipment with the temperature of 65 +/-2 ℃ and the vacuum degree of not less than 20kPa for drying treatment;
(2) preparing organic bentonite: adding a proper amount of quaternary ammonium salt into deionized water by a massage concentration meter to form a quaternary ammonium salt solution with the concentration of 0.03-0.09mol/L, adding dried bentonite into the quaternary ammonium salt solution at a ratio of 2-3g/50mL, adjusting the pH to 6-6.5 by using hydrochloric acid, performing microwave stirring and dispersion for 10min, and performing centrifugation, washing, drying, grinding and sieving to obtain organic bentonite;
(3) amino functionalization: according to a molar concentration, amino functional group silane is placed in an ethanol solution, the mixture is fully stirred and dispersed to form a solution A with the concentration of 0.5-2mol/L, organic bentonite is added into ethanol according to 0.5g/100mL, the mixture is fully stirred and dispersed to form a dispersion liquid B, the solution A and the dispersion liquid B are mixed and then mechanically stirred for 20min in a microwave oven, the mixture is kept stand and centrifuged, and washed by ethanol, a washed product is placed in a blast drying oven to be dried, and the amino functional bentonite is obtained after grinding and sieving.
(4) Preparing a beta-phase casting solution: according to the weight parts, sequentially taking 1-7 parts of amino functionalized bentonite and 70-80 parts of film-making mother agent, stirring and mixing uniformly in a microwave oven, sequentially adding 1-3 parts of pore-forming agent and 15-20 parts of homogeneous PVDF, and mechanically stirring for 0.5-2 hours under the assistance of microwave radiation, on one hand, promoting the alpha phase in the PVDF to be converted into the beta phase, on the other hand, uniformly dispersing the amino functionalized bentonite in a casting solution, and then carrying out vacuum defoaming to obtain a homogeneous casting solution; and the method can greatly shorten the preparation method of the casting solution
Wherein the microwave radiation power is 200-350W, the radiation line is microwave, and the frequency range of the microwave is from 300MHz to 300 KMHz.
(5) Preparing and molding a film: and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and after 15-30s, performing heat treatment on the film in a vacuum oven at the temperature of 40-60 ℃ for 4-7h to obtain the dual-functionalized mixed matrix film after the film naturally falls off from the glass plate.
In the step (2), the quaternary ammonium salt is one of dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
Further, in the step (3), the amino functional group silane is one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane.
Further, the film-making mother agent in the step (4) is one or more of tetrahydrofuran, dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the pore-forming agent is one of polyvinylpyrrolidone, isopropanol or polyethylene glycol.
The invention also provides an application of the dual-functionalized mixed matrix membrane with high carbon dioxide selectivity in gas separation of different gas systems.
The application of the double-functionalized mixed matrix membrane with high carbon dioxide selectivity in the gas separation of different gas systems preferably comprises the following steps:
(1) cutting the dual-functionalized mixed matrix membrane, placing the cut dual-functionalized mixed matrix membrane in a membrane separation evaluation device, introducing feed gas, and keeping the temperature of a membrane pool at 25-55 ℃ and the pressure of the inlet gas at 0.15 MPa;
(2) and after the gas is stably transmitted, testing the gas flow and the pressure difference between the two sides of the membrane to obtain the permeation flux and the gas selection coefficient of the gas.
Wherein the resulting dual functionalized mixed matrix membrane is suitable for use with CO2/N2、CO2/CH4And (5) separating.
Compared with the prior art, the invention has the beneficial effects that:
(1) through the organic modification of the bentonite, cations in the quaternary ammonium salt exchange with cations in a bentonite layer, so that layered lattices are cracked, the spacing between crystal layers is enlarged, pore channels are dredged, the surface activity is increased, more amino groups are grafted to the bentonite during amination reaction, and the introduction of amino functional groups greatly improves the gas selectivity;
(2) because PVDF generally represents alpha phase, the invention adopts the microwave-assisted form, promote more alpha phases to turn into beta phase, and because the microwave radiation is more homogeneous, can form the homogeneous casting film liquid fast, greatly shorten the operating time, and is more favorable to the selective separation of carbon dioxide;
(3) the membrane prepared by the invention has more carbon dioxide active sites due to the coexistence of the bifunctional amino and fluorine groups, the carbon dioxide permeability is greatly increased, the preparation method is simple, the operation time is short, the implementation is easy, the cost is lower, the membrane forming property is excellent, and the prepared gas separation membrane has excellent permselectivity.
Drawings
FIG. 1 is a scanning electron micrograph of the surface structure of the dual functionalized mixed matrix membrane in example 1.
FIG. 2 shows CO in example 1 of the present invention2/N2The separation curve is compared to the Robeson curve.
FIG. 3 shows CO in example 1 of the present invention2/CH4The separation curve is compared to the Robeson curve.
FIG. 4 is a comparison of the compositions of the crystalline phases in example 1 of the present invention and comparative example 2.
Detailed Description
To further illustrate the technical solution of the present invention, the following specific examples are given. It should be understood that the present invention has been shown and described only by way of illustration and description, and it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention or exceeding the scope of the claims.
CO used in the following examples of the invention2、CH4、N2All are high purity gases.
Example 1
(1) Adding 1.275g of hexadecyl trimethyl ammonium bromide into 50mL of deionized water to form a quaternary ammonium salt solution with the concentration of 0.07mol/L, adding 2g of bentonite into the quaternary ammonium salt solution while stirring, adjusting the pH to 6-6.5 by using hydrochloric acid with the concentration of 2.5mol/L, transferring the solution into a microwave oven, stirring and dispersing for 10min by using a microwave with the power of 300W, washing for 3 times by using the deionized water, and then drying in an oven at 100 ℃ for 4h to obtain the organic bentonite; adding 5.525g of 3-aminopropyltriethoxysilane into 50mL of ethanol solution, fully stirring to form 0.5 mol/L3-aminopropyltriethoxysilane solution, adding 1g of organic bentonite into 50mL of ethanol, fully stirring and dispersing to form dispersion liquid B, mixing the solution A and the dispersion liquid B, transferring to a microwave oven, mechanically stirring for 20min under the assistance of 300W microwaves, standing, centrifuging, washing with ethanol, drying the washed product in a forced air drying oven, grinding, and sieving to obtain the amino functionalized bentonite.
(2) According to the weight portion, 2 portions of amino functionalized bentonite and 75 portions of N, N-dimethylformamide are stirred and mixed evenly in a microwave oven, 3 portions of polyvinylpyrrolidone and 20 portions of PVDF are added in sequence and stirred mechanically for 1 hour under the assistance of microwave radiation, the power is 270W, the mechanical stirring is not limited, and then homogeneous casting solution is obtained through vacuum defoaming; and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and after 30s, after the film naturally falls off from the glass plate, carrying out heat treatment for 5h in a vacuum oven at 50 ℃ to obtain the dual-functionalized mixed matrix film.
(3) Cutting the mixed matrix membrane into a circle with the diameter of 1.5cm, pasting the circle on a non-woven fabric support net, clamping two sides of the non-woven fabric support net respectively by using silica gel gaskets, integrally placing the non-woven fabric support net into a membrane pool, controlling the temperature to be 25 ℃, and sealing the membrane pool. Introduction of N2Or CO2，CH4The gas pressure at the gas inlet side reaches 0.15MPa, and the soap film flowmeter is connected to the outlet of the permeation side to calculate the gas permeation flux. CO 22The permeability is 3.68 multiplied by 10-6mol/m2·s·Pa，CO2/N2And CO2/CH4The highest separation selectivity of (a) was 34.94 and 30.54, respectively.
From fig. 2 and fig. 3, it can be seen that the performance of the prepared dual-functionalized mixed matrix membrane is superior to that of the separation membranes.
From FIG. 4, it can be seen that the microwave radiation is located at 800cm and 500--1The diffraction peaks of the alpha phase at most of the positions disappeared and turned into the beta phase.
Example 2
(1) Adding 0.73g of hexadecyl trimethyl ammonium bromide into 50mL of deionized water to form a quaternary ammonium salt solution with the concentration of 0.04mol/L, adding 1g of bentonite into the quaternary ammonium salt solution while stirring, adjusting the pH to 6-6.5 by using hydrochloric acid with the concentration of 2.5mol/L, transferring the solution into a microwave oven, stirring and dispersing for 10min by using microwaves at the power of 300W, washing the solution for 3 times by using the deionized water, and then drying the solution in an oven at the temperature of 100 ℃ for 4 hours to obtain the organic bentonite; adding 11.05g of 3-aminopropyltriethoxysilane into 50mL of ethanol solution, fully stirring to form 1 mol/L3-aminopropyltriethoxysilane solution, adding 1g of organic bentonite into 50mL of ethanol, fully stirring and dispersing to form dispersion liquid B, mixing the solution A and the dispersion liquid B, transferring the mixture into a microwave oven, mechanically stirring for 20min under the assistance of 300W microwaves, standing, centrifuging, washing with ethanol, drying the washed product in a forced air drying oven, grinding, and sieving to obtain the amino functionalized bentonite.
(2) Taking 4 parts of amino functionalized bentonite and 80 parts of N, N dimethylformamide, stirring and mixing uniformly in a microwave oven, sequentially adding 1 part of polyvinylpyrrolidone and 15 parts of PVDF, mechanically stirring for 1h under the assistance of microwave radiation, wherein the power is 260W, the mechanical stirring is not limited, and then carrying out vacuum defoaming to obtain a homogeneous casting solution; and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and after 30s, after the film naturally falls off from the glass plate, carrying out heat treatment for 4h in a vacuum oven at the temperature of 60 ℃ to obtain the dual-functionalized mixed matrix film.
(3) Cutting the mixed matrix membrane into a circle with the diameter of 1.5cm, pasting the circle on a non-woven fabric support net, clamping two sides of the non-woven fabric support net respectively by using silica gel gaskets, integrally placing the non-woven fabric support net into a membrane pool, controlling the temperature to be 35 ℃, and sealing the membrane pool. Introduction of CH4Or CO2And enabling the gas pressure at the gas inlet side to reach 0.15MPa, connecting a soap film flowmeter at the outlet of the permeation side, and calculating the gas permeation flux. CO 22Permeability of 2.57X 10-6mol/m2·s·Pa，CO2/N2And CO2/CH4The separation selectivity of (a) is highest at 30.45 and 28.59, respectively.
Example 3
(1) Adding 0.924g of dodecyl trimethyl ammonium chloride into 50mL of deionized water to form a quaternary ammonium salt solution with the concentration of 0.07mol/L, adding 2g of bentonite into the quaternary ammonium salt solution while stirring, adjusting the pH to 6-6.5 by using hydrochloric acid with the concentration of 2.5mol/L, transferring the solution into a microwave oven, stirring and dispersing for 10min by using microwave with the power of 300W, washing for 3 times by using the deionized water, and then drying in an oven at 100 ℃ for 4h to obtain the organic bentonite; adding 4.482g of 3-aminopropyltrimethoxysilane into 50mL of ethanol solution, fully stirring to form 0.5 mol/L3-aminopropyltrimethoxysilane solution, adding 1g of organic bentonite into 50mL of ethanol, fully stirring and dispersing to form dispersion liquid B, mixing the solution A and the dispersion liquid B, transferring the mixture into a microwave oven, mechanically stirring for 20min under the assistance of 300W microwaves, standing, centrifuging, washing with ethanol, placing the washed product in a blast drying oven for drying, grinding and sieving to obtain the amino functionalized bentonite.
(2) According to the weight portion, 2 portions of amino functionalized bentonite and 75 portions of tetrahydrofuran are stirred and mixed evenly in a microwave oven, 3 portions of polyethylene glycol and 20 portions of PVDF are added in sequence and stirred mechanically for 1 hour under the assistance of microwave radiation, the power is 250W, the mechanical stirring is not limited, and then homogeneous casting solution is obtained through vacuum defoaming; and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and after 30s, after the film naturally falls off from the glass plate, carrying out heat treatment for 5h in a vacuum oven at 50 ℃ to obtain the dual-functionalized mixed matrix film.
(3) Cutting the mixed matrix membrane into a circle with the diameter of 1.5cm, pasting the circle on a non-woven fabric support net, clamping two sides of the non-woven fabric support net respectively by using silica gel gaskets, integrally placing the non-woven fabric support net into a membrane pool, controlling the temperature to be 25 ℃, and sealing the membrane pool. Introduction of N2Or CO2And enabling the gas pressure at the gas inlet side to reach 0.15MPa, connecting a soap film flowmeter at the outlet of the permeation side, and calculating the gas permeation flux. CO 22The permeability is 2.68 multiplied by 10-6mol/m2·s·Pa，CO2/N2And CO2/CH4The separation selectivity of (a) is highest at 29.75 and 26.13, respectively.
Example 4
(1) Adding 0.924g of dodecyl trimethyl ammonium chloride into 50mL of deionized water to form a quaternary ammonium salt solution with the concentration of 0.07mol/L, adding 2g of bentonite into the quaternary ammonium salt solution while stirring, adjusting the pH to 6-6.5 by using hydrochloric acid with the concentration of 2.5mol/L, transferring the solution into a microwave oven, stirring and dispersing for 10min by using microwave with the power of 300W, washing for 3 times by using the deionized water, and then drying in an oven at 100 ℃ for 4h to obtain the organic bentonite; adding 4.482g of 3-aminopropyltrimethoxysilane into 50mL of ethanol solution, fully stirring to form 0.5 mol/L3-aminopropyltrimethoxysilane solution, adding 1g of organic bentonite into 50mL of ethanol, fully stirring and dispersing to form dispersion liquid B, mixing the solution A and the dispersion liquid B, transferring the mixture into a microwave oven, mechanically stirring for 20min under the assistance of 300W microwaves, standing, centrifuging, washing with ethanol, placing the washed product in a blast drying oven for drying, grinding and sieving to obtain the amino functionalized bentonite.
(2) According to the weight portion, 2 portions of amino functionalized bentonite and 75 portions of N, N dimethylacetamide are stirred and mixed evenly in a microwave oven, 3 portions of polyethylene glycol and 20 portions of PVDF are added in sequence and stirred mechanically for 1h under the assistance of microwave radiation, the power is 260W, the mechanical stirring is not limited, and then homogeneous casting solution is obtained through vacuum defoaming; and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and after 30s, after the film naturally falls off from the glass plate, carrying out heat treatment for 5h in a vacuum oven at 50 ℃ to obtain the dual-functionalized mixed matrix film.
(3) Cutting the mixed matrix membrane into a circle with the diameter of 1.5cm, pasting the circle on a non-woven fabric support net, clamping two sides of the non-woven fabric support net respectively by using silica gel gaskets, integrally placing the non-woven fabric support net into a membrane pool, controlling the temperature to be 25 ℃, and sealing the membrane pool. Introduction of CH4Or CO2And enabling the gas pressure at the gas inlet side to reach 0.15MPa, connecting a soap film flowmeter at the outlet of the permeation side, and calculating the gas permeation flux. CO 22Permeability of 3.01X 10-6mol/m2·s·Pa，CO2/N2And CO2/CH4The separation selectivity of (a) is highest at 28.06 and 26.45, respectively.
Example 5
(1) Adding 1.275g of hexadecyl trimethyl ammonium bromide into 50mL of deionized water to form a quaternary ammonium salt solution with the concentration of 0.07mol/L, adding 2g of bentonite into the quaternary ammonium salt solution while stirring, adjusting the pH to 6-6.5 by using hydrochloric acid with the concentration of 2.5mol/L, transferring the solution into a microwave oven, stirring and dispersing for 10min by using a microwave with the power of 300W, washing for 3 times by using the deionized water, and then drying in an oven at 100 ℃ for 4h to obtain the organic bentonite; adding 5.525g of 3-aminopropyltriethoxysilane into 50mL of ethanol solution, fully stirring to form 0.5 mol/L3-aminopropyltriethoxysilane solution, adding 1g of organic bentonite into 50mL of ethanol, fully stirring and dispersing to form dispersion liquid B, mixing the solution A and the dispersion liquid B, transferring to a microwave oven, mechanically stirring for 20min under the assistance of 300W microwaves, standing, centrifuging, washing with ethanol, drying the washed product in a forced air drying oven, grinding, and sieving to obtain the amino functionalized bentonite.
(2) According to the weight portion, 2 portions of amino functionalized bentonite and 75 portions of N-methyl pyrrolidone are stirred and mixed evenly in a microwave oven, 3 portions of isopropanol and 20 portions of PVDF are added in sequence and stirred mechanically for 1 hour under the assistance of microwave radiation, the power is 260W, the mechanical stirring is not limited, and then homogeneous casting solution is obtained through vacuum defoaming; and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and after 30s, after the film naturally falls off from the glass plate, carrying out heat treatment for 5h in a vacuum oven at 50 ℃ to obtain the dual-functionalized mixed matrix film.
(3) Cutting the mixed matrix membrane into a circle with the diameter of 1.5cm, pasting the circle on a non-woven fabric support net, clamping two sides of the non-woven fabric support net respectively by using silica gel gaskets, integrally placing the non-woven fabric support net into a membrane pool, controlling the temperature to be 25 ℃, and sealing the membrane pool. Introduction of N2Or CO2And enabling the gas pressure at the gas inlet side to reach 0.15MPa, connecting a soap film flowmeter at the outlet of the permeation side, and calculating the gas permeation flux. CO 22The permeability is 2.83 multiplied by 10-6mol/m2·s·Pa，CO2/N2And CO2/CH4The separation selectivity of (a) was highest at 29.14 and 26.05, respectively.
Comparative example 1
(1) According to the weight portion, 2 portions of bentonite and 75 portions of N-methyl pyrrolidone are stirred and mixed evenly in a microwave oven, 3 portions of isopropanol and 20 portions of PVDF are added in sequence and stirred mechanically for 1 hour under the assistance of microwave radiation, the power is 270W, the mechanical stirring is not limited, and then homogeneous casting solution is obtained through vacuum defoaming; and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and after 30s, performing heat treatment for 5h in a vacuum oven at 50 ℃ after the film naturally falls off from the glass plate to obtain a mixed matrix film.
(2) Cutting the mixed matrix membrane into a circle with the diameter of 1.5cm, pasting the circle on a non-woven fabric support net, clamping two sides of the non-woven fabric support net respectively by using silica gel gaskets, integrally placing the non-woven fabric support net into a membrane pool, controlling the temperature to be 25 ℃, and sealing the membrane pool. Introduction of N2Or CO2And enabling the gas pressure at the gas inlet side to reach 0.15MPa, connecting a soap film flowmeter at the outlet of the permeation side, and calculating the gas permeation flux. CO 22Permeability of 1.33X 10-7mol/m2·s·Pa，CO2/N2And CO2/CH4The separation selectivity of (a) is highest at 15.82 and 13.37, respectively.
Comparative example 2
(1) Taking 2 parts of bentonite and 75 parts of N-methylpyrrolidone, stirring and mixing uniformly in a water bath, sequentially adding 3 parts of isopropanol and 20 parts of PVDF, mechanically stirring for 5 hours, and then performing vacuum defoaming to obtain a homogeneous casting solution; and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and after 30s, after the film naturally falls off from the glass plate, carrying out heat treatment for 5h in a vacuum oven at 50 ℃ to obtain the dual-functionalized mixed matrix film.
(2) Cutting the mixed matrix membrane into a circle with the diameter of 1.5cm, pasting the circle on a non-woven fabric support net, clamping two sides of the non-woven fabric support net respectively by using silica gel gaskets, integrally placing the non-woven fabric support net into a membrane pool, controlling the temperature to be 25 ℃, and sealing the membrane pool. Introduction of N2Or CO2And enabling the gas pressure at the gas inlet side to reach 0.15MPa, connecting a soap film flowmeter at the outlet of the permeation side, and calculating the gas permeation flux. CO 22Permeability of 8.33X 10-8mol/m2·s·Pa，CO2/N2And CO2/CH4The separation selectivity of (a) was highest at 13.27 and 10.41, respectively.
Comparative example 3
(1) Adding 1.275g of hexadecyl trimethyl ammonium bromide into 50mL of deionized water to form a quaternary ammonium salt solution with the concentration of 0.07mol/L, adding 2g of bentonite into the quaternary ammonium salt solution while stirring, adjusting the pH to 6-6.5 by using hydrochloric acid with the concentration of 2.5mol/L, transferring the solution into a microwave oven, stirring and dispersing for 10min by using a microwave with the power of 300W, washing for 3 times by using the deionized water, and then drying in an oven at 100 ℃ for 4h to obtain the organic bentonite; adding 5.525g of 3-aminopropyltriethoxysilane into 50mL of ethanol solution, fully stirring to form 0.5 mol/L3-aminopropyltriethoxysilane solution, adding 1g of organic bentonite into 50mL of ethanol, fully stirring and dispersing to form dispersion liquid B, mixing the solution A and the dispersion liquid B, transferring to a microwave oven, mechanically stirring for 20min under the assistance of 300W microwaves, standing, centrifuging, washing with ethanol, drying the washed product in a forced air drying oven, grinding, and sieving to obtain the amino functionalized bentonite.
(2) According to the weight portion, 2 portions of amino functionalized bentonite and 75 portions of N-methyl pyrrolidone are taken to be stirred and mixed evenly in a water bath, 3 portions of isopropanol and 20 portions of PVDF are sequentially added to be mechanically stirred for 5 hours, and then homogeneous casting solution is obtained through vacuum defoaming; and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and after 30s, after the film naturally falls off from the glass plate, carrying out heat treatment for 5h in a vacuum oven at 50 ℃ to obtain the dual-functionalized mixed matrix film.
(3) Cutting the mixed matrix membrane into a circle with the diameter of 1.5cm, pasting the circle on a non-woven fabric support net, clamping two sides of the non-woven fabric support net respectively by using silica gel gaskets, integrally placing the non-woven fabric support net into a membrane pool, controlling the temperature to be 25 ℃, and sealing the membrane pool. Introduction of N2Or CO2And enabling the gas pressure at the gas inlet side to reach 0.15MPa, connecting a soap film flowmeter at the outlet of the permeation side, and calculating the gas permeation flux. CO 22Permeability of 6.91X 10-7mol/m2·s·Pa，CO2/N2And CO2/CH4The separation selectivity of (a) was the highest at 21.36 and 18.62, respectively.
Table 1 compares the gas separation performance of the dual functionalized mixed matrix membrane.
As can be seen from the comparative data on gas separation performance of the dual functionalized mixed matrix membrane in Table 1, the mode adopted by the invention greatly increases CO2Permeability, and CO2/N2And CO2/CH4The separation selectivity of the method and the time required for the formation of the casting solution is greatly shortened.
The sample of example 1 is the best sample of all examples at this time.
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the content of the embodiment. It will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and any changes and modifications made are within the protective scope of the present invention.
Claims (7)
1. A method for rapidly preparing a dual-functionalized mixed matrix membrane with high carbon dioxide selectivity is characterized by comprising the following steps:
(1) preparing amino functionalized bentonite;
(2) preparing a beta-phase casting solution: taking 1-7 parts by weight of amino functionalized bentonite and 70-80 parts by weight of membrane preparation mother agent, stirring and mixing uniformly in a microwave oven, sequentially adding 1-3 parts by weight of pore-forming agent and 15-20 parts by weight of homogeneous PVDF, mechanically stirring for 0.5-2h under the assistance of microwave radiation, and defoaming in vacuum to obtain a homogeneous membrane casting solution;
(3) preparing and molding a film: and uniformly coating the obtained casting solution on a clean glass plate, putting the glass plate into a solidification water bath for solidification and molding, and performing heat treatment in a vacuum oven after the film naturally falls off from the glass plate to obtain the amino/fluorine-based dual-functionalized mixed matrix film.
2. The method for rapidly preparing the dual-functionalized mixed matrix membrane with high carbon dioxide selectivity according to claim 1, wherein the method comprises the following steps: the preparation method of the amino functionalized bentonite comprises the following steps: according to the molar concentration, amino functional group silane is placed in an ethanol solution, and the solution A is formed after full stirring and dispersion, wherein the concentration is 0.5-2 mol/L; adding organic bentonite into ethanol, fully stirring and dispersing to form a dispersion liquid B, mixing the solution A and the dispersion liquid B, mechanically stirring for a certain time, standing, centrifuging, washing with ethanol, and drying the washed product in a forced air drying oven to obtain amino functionalized bentonite; the amino functional group silane is one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane.
3. The method for rapidly preparing the dual-functionalized mixed matrix membrane with high carbon dioxide selectivity according to claim 1, wherein the method comprises the following steps: the power of the microwave oven in the mechanical stirring under the assistance of the microwave radiation is 200-350W; the frequency of the microwave ranges from 300MHz to 300 KMHz.
4. The method for rapidly preparing the dual-functionalized mixed matrix membrane with high carbon dioxide selectivity according to claim 1, wherein the method comprises the following steps: the film-making mother agent is one or more of tetrahydrofuran, dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide.
5. The method for rapidly preparing the dual-functionalized mixed matrix membrane with high carbon dioxide selectivity according to claim 1, wherein the method comprises the following steps: the pore-forming agent is one of polyvinylpyrrolidone, isopropanol or polyethylene glycol.
6. The method for rapidly preparing the dual-functionalized mixed matrix membrane with high carbon dioxide selectivity according to claim 1, wherein the method comprises the following steps: the heat treatment temperature of the mixed matrix membrane in a vacuum oven is 40-60 ℃, and the treatment time is 4-7 h.
7. Use of a bi-functionalized mixed matrix membrane with high carbon dioxide selectivity prepared according to the process of claims 1-6, characterized in that: the dual functionalized mixed matrix membrane is used as a separation membrane for CO2/N2、CO2/CH4And (5) gas separation.
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| US20180304193A1 (en) * | 2017-04-21 | 2018-10-25 | King Fahd University Of Petroleum And Minerals | Mixed matrix membrane, a method of making thereof, and a method for gas separation |
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| CN110227349A (en) * | 2019-06-12 | 2019-09-13 | 常州大学 | Based on the nano-silicon dioxide modified blended ultrafiltration membrane and preparation method thereof of functionalization sodium base bentonite and amination |
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