CN113522040A - Method for preparing high-performance carbon dioxide separation composite membrane containing twisted structure through interfacial polymerization - Google Patents
Method for preparing high-performance carbon dioxide separation composite membrane containing twisted structure through interfacial polymerization Download PDFInfo
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- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 36
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- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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 relates to a method for preparing a high-performance carbon dioxide separation composite membrane containing a twisted structure by interfacial polymerization; dissolving trimesoyl chloride in an organic phase solvent n-heptane, and stirring to form a uniform oil phase solution; dissolving N-methyldiethanolamine and 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene in deionized water, uniformly stirring to form a solution, adding sodium carbonate to adjust the pH value of the solution to 10-11, and stirring to form an aqueous phase solution; fixing the ultrafiltration membrane coated with the middle layer on a plate frame, pouring an oil phase solution, pouring the oil phase solution out after the oil phase solution fully infiltrates the middle layer, drying the oil phase solution in the air, and then pouring a water phase solution into the middle layer to perform interfacial polymerization; finally pouring out the aqueous phase solution and washing with deionized water; and (5) putting the composite membrane into a constant temperature and humidity box, and drying to obtain the composite membrane. Composite membrane CO2The permeation rate is 250-480 GPU, CO2/N2The separation factor is 55-77.
Description
Technical Field
The invention relates to a method for preparing a composite material by adding a water-containing torsion into an oil phase or a water phaseMonomers of the bent unit are polymerized at the interface to prepare the high CO2Selectivity and high CO2A method for preparing a permeation rate composite membrane, which belongs to the field of preparation of gas separation membranes; high-performance CO is obtained by regulating and controlling the rigidity of a polymer skeleton chain segment and optimizing the monomer concentration and the reaction temperature2Separating the composite membrane.
Background
With the rapid development of the industry, CO2The discharge amount is increased year by year, the greenhouse effect is intensified, the global climate abnormity and natural disasters are frequent, the earth ecosystem is seriously damaged, and the serious influence is brought to the survival and sustainable development of human beings[1]. To CO2Capture and Sequestration (CCS) is currently performed to control and reduce CO2An effective means of venting. Common CO2The separation techniques mainly include absorption, adsorption, cryogenic rectification, membrane separation, and the like. Wherein, the membrane separation method has the advantages of simple process, small equipment investment, low energy consumption and unobvious amplification effect, and CO is obtained2Has significant advantages in separation[2]. Development of CO with high permeability and high selectivity2Separation membranes have been the focus of research. The polymer membrane for gas separation has received much attention from researchers due to its advantages of good mechanical stability, easy scale-up, low cost and ready availability[3]。
Currently, commercially available gas separation membranes include Cellulose Acetate (CA), Polysulfone (PSF), Polyethersulfone (PES), Polyimide (PI), polyphenylene oxide (PPO), Polydimethylsiloxane (PDMS), and the like. Existing commercial membrane CO2The permeation rate is generally not more than 100GPU, and CO is separated by a membrane method2Practical application of (C), CO2Permeation rates can reach hundreds to thousands of GPUs. The thin-layer composite membrane is a good choice for preparing the high-permeability selective membrane. The separation performance of the composite membrane is mainly determined by the material of the separation layer, and in order to fully exert the separation performance of the membrane material, the thickness of the separation layer is generally less than 200nm, and the separation layer is complete and has no defects[4]。
The interfacial polymerization method combines the development of membrane materials with the preparation of thin films, and can prepare membranes with the thickness less than 200 nm.Interfacial polymerization is a method for preparing high molecular weight polymers by following a step-growth polymerization mechanism, reaction occurs at the interface of a water phase and an oil phase, the development of membrane materials and the preparation of thin films can be simultaneously completed by preparing a separation membrane by the interfacial polymerization method, and the thickness of the prepared membrane is generally not more than 200nm because the interfacial polymerization has self-inhibition. The membrane material prepared by the interfacial polymerization method is of a cross-linked structure, has remarkable advantages in the aspect of preparing defect-free ultrathin membranes, and can prepare ultrathin separation membranes with the thickness of dozens of nanometers or even dozens of nanometers by optimizing interfacial polymerization process parameters[5]. Thus, interfacial polymerization processes are carried out on high performance CO2Great potential is shown in the preparation of separation composite membranes.
The separation membrane produced by the interfacial polymerization method has a problem that the gas separation performance is not sufficiently high. At 5atm, CO2/N2Is generally less than 40[6]. Therefore, there is a need to further improve the separation factor of the composite membrane. While increasing the separation factor, the permeation rate tends to decrease. For the separation layer, its high permeability is generally required to ensure that the membrane material has a large free volume or a high degree of swelling during use, and a sufficiently thin thickness. The existing gas separation membrane prepared by interfacial polymerization is generally compact in structure and is not beneficial to gas transmission in the membrane. Therefore, it is necessary to prepare a separation layer having a relatively loose structure and a relatively large free volume in order to obtain high gas permeability. High selectivity usually needs to be optimized from three aspects of dissolution, diffusion and reaction[7]。
In order to obtain CO with high permeability and high selectivity2The invention discloses a method for preparing a composite membrane by introducing a twisted structure on a polymer framework. CO proposed by the invention2The preparation method of the separation composite membrane can ensure that the polymer frameworks are not on the same plane, improve the free volume of the polymer of the separation layer and facilitate the promotion of CO2Rapid diffusion within the membrane. Simultaneously introduces reactive groups, is favorable for realizing CO2Preferential fast adsorption of CO at membrane surface2Rapid transfer within the membrane. The introduction of a twisted structure increases the hydroxyl content in the film, which is beneficial to improving CO2Dissolution on the membrane surface. The introduction of the twisted structure can optimize the pore structure in the membrane, and the micropores formed by the prepared membrane can block N2And CH4Transport of the larger molecules within the membrane, while for smaller sized CO2The molecular influence is not great, and the structural characteristics of the pore channel are favorable for CO2/N2、CO2/CH4Increase the separation factor of the system. To summarize. The preparation method of the composite membrane provided by the invention can realize the comprehensive regulation and control of membrane reaction selectivity, dissolution selectivity and diffusion selectivity, and can prepare CO2High performance CO with sufficiently high permeation rate and greatly improved separation factor2Separating the composite membrane.
Reference to the literature
[1]Schwartzman A,Keeling R.Achieving atmospheric verification of CO2emissions[J].Nature Climate Change,2020,10(5):1-2.
[2]Qiao Z,Zhao S,Sheng M,et al.Metal-induced ordered microporous polymers for fabricating large-area gas separation membranes[J].Nature Materials,2019,18(2):163-168.
[3]On the grounds of CO2Isolated high Performance Polyvinylamine Membrane development [ D]Tianjin, Tianjin university, 2019.
[4]M.Galizia,W.S.Chi,Z.P.Smith,T.C.Merkel,R.W.Baker,B.D.Freeman,50th Anniversary Perspective:Polymers and Mixed Matrix Membranes for Gas and Vapor Separation:A Review and Prospective Opportunities,Macromolecules,2017,50:7809-7843.
[5]Wang M,Wang Z,Li S,et al.Ahigh performance antioxidative and acid resistant membrane prepared by interfacial polymerization for CO2 separation from flue gas[J].Energy&Environmental Science,2013,6(2):539-551.
[6]Yuan S,Wang Z,Qiao Z,Wang M,et al.Improvement of CO2/N2 separation characteristics of polyvinylamine by modifying with ethylenediamine,Journal of Membrane Science,2011,378:425-437.
[7]Li S,Wang Z,Yu X,et al.High-performance membranes with multi-permselectivity for CO2 separation[J].Advanced Materials,2012,24(24):3196-3200.
Disclosure of Invention
The invention aims to improve the CO content of the composite membrane by introducing a twisted structural unit into a polymer skeleton to improve the free volume in the membrane2Ensures that the composite membrane still has enough high CO while ensuring the selectivity2The permeation rate.
The conventional method for preparing the composite membrane by the interfacial polymerization method is divided into two steps at present. Firstly, preparing an intermediate layer, namely coating a layer of silicon rubber on a polysulfone ultrafiltration membrane to prepare the intermediate layer; and then preparing a separation layer, namely putting the membrane coated with the middle layer into the oil phase solution for a period of time, taking out and drying the membrane, putting the membrane into the water phase solution for reaction, washing the membrane with deionized water after the reaction is finished, and drying the membrane to obtain the composite membrane. Two different reaction monomers are added into the water phase, and the two monomers can participate in interfacial polymerization reaction at the same time. A schematic of the interfacial polymerization process is shown in FIG. 1. To obtain CO with better performance2Separating membrane, the content of flexible chain segment, the number of amino groups and the microporous structure in the membrane must be optimized. Therefore, the invention obtains the CO by regulating and controlling the reaction conditions2An isolated thin film composite membrane. For the prepared CO2Separating the composite membrane to obtain mixed gas (CO)2/N2、CO2/CH4) And (6) testing. The results show that the membranes produced all have good CO2Permeation rate and separation factor.
The preparation of the separating layer is realized by the following technical scheme:
a method for preparing a high-performance carbon dioxide separation composite membrane containing a twisted structure by interfacial polymerization; the middle layer of the composite membrane mainly plays a role in preventing the material of the separation layer from permeating pores, and the separation layer is the key for determining the gas separation effect. Therefore, to obtain a catalyst having good CO2The method optimizes and regulates the structure of the separation layer, and specifically comprises the following steps:
a method for preparing a high-performance carbon dioxide separation composite membrane containing a twisted structure by interfacial polymerization; the method is characterized by comprising the following steps:
(1) preparing a separation layer solution: dissolving trimesoyl chloride in an organic phase solvent n-heptane, and stirring to form a uniform oil phase solution; dissolving N-methyldiethanolamine and 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene in deionized water, uniformly stirring to form a solution, adding sodium carbonate to adjust the pH value of the solution to 10-11, and stirring to form an aqueous phase solution;
(2) preparing a composite membrane: fixing the ultrafiltration membrane coated with the middle layer on a plate frame, pouring an oil phase solution, pouring the oil phase solution out after the oil phase solution fully infiltrates the middle layer, drying the oil phase solution in the air, and then pouring a water phase solution into the middle layer to perform interfacial polymerization; finally pouring out the aqueous phase solution and washing with deionized water; and (5) putting the composite membrane into a constant temperature and humidity box, and drying to obtain the composite membrane.
In the step (1), the concentration of the trimesoyl chloride solution is 0.01-0.02 mol/L.
In the step (1), the concentration of N-methyldiethanolamine is 0.03-0.12 mol/L, and the molar ratio of 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spirobisindane to N-methyldiethanolamine is 0.05-0.5: 1.
In the step (2), the ultrafiltration membrane comprises a polysulfone ultrafiltration membrane, a polyacrylonitrile ultrafiltration membrane, a polyether sulfone ultrafiltration membrane, a polyether ether ketone ultrafiltration membrane, a polyvinylidene fluoride ultrafiltration membrane or a polycarbonate ultrafiltration membrane material.
And (3) in the step (2), reacting in the aqueous phase solution for 3-15 minutes.
In the step (2), the reaction temperature control range of the interfacial polymerization is 30-50 ℃.
The invention utilizes the method to obtain high-performance CO2The separation composite membrane is mainly for the following reasons. Firstly, the separation layer generated by the interfacial polymerization method is of a cross-linked structure, and is compact, so that a thin and defect-free separation membrane can be prepared more easily. The invention can prepare a defect-free separation layer with the thickness of about 40nm by an interface polymerization method, and the thinner the separation layer is, the CO of the prepared separation membrane2The higher the permeation rate. Secondly, the chain of the polymer in the membrane can be increased by adding 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spirobiindan having a twisted structure to the aqueous monomerThe space increases the free volume in the membrane, accelerates the diffusion of gas in the membrane, and further increases the permeation rate of the membrane. Finally, the segment rigidity of 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene is stronger than that of the N-methyldiethanolamine segment, and molecules with larger size are difficult to extrude the molecular segment to permeate through the membrane, but have little influence on molecules with smaller size. Thus, in CO2Greatly improves the permeability rate of the membrane to CO under the condition of basically unchanged permeability rate2/N2And CO2/CH4And (4) selectivity of mixed gas. For combining the three reasons, the prepared composite membrane has excellent CO finally2/N2And CO2/CH4Selectivity, with sufficiently high CO2The permeation rate.
The invention can simultaneously optimize the membrane material and the separation membrane structure, has simple preparation process and is easy to amplify. By regulating and controlling the reaction conditions, the obtained composite membrane has CO under the condition that the pressure of the feed gas is 0.5MPa2Permeation rate is between 250GPU and 480GPU, CO2/N2The separation factor is between 55 and 77.
Drawings
FIG. 1 is a schematic view of an interfacial polymerization process.
FIG. 2 shows CO2Scanning electron microscope image of the surface appearance of the separation composite membrane.
FIG. 3 is CO2And (3) a scanning electron microscope image of the section morphology of the separation composite membrane.
Detailed Description
Example 1
(1) Preparing a separation layer solution: dissolving trimesoyl chloride in n-heptane, and stirring to form a uniform oil phase solution, wherein the concentration of the trimesoyl chloride solution is 0.01 mol/L; dissolving N-methyldiethanolamine and 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene in deionized water, adding sodium carbonate, stirring to form an aqueous solution, wherein the concentration of the N-methyldiethanolamine is 0.03mol/L, the molar ratio of the 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene to the methyldiethanolamine is 0.05:1, and the pH of the solution is adjusted to 10.5 by using the sodium carbonate.
(2) Preparing a composite membrane: to be coated with intermediate layersFixing polysulfone ultrafiltration membrane on plate frame, pouring oil phase solution, soaking middle layer with oil phase solution, pouring oil phase solution, air drying, pouring water phase solution, reacting at 40 deg.C for 10 min by interfacial polymerization, washing with deionized water, and drying to obtain CO2Separating the composite membrane. The surface and cross-sectional profile of the prepared composite membrane are shown in fig. 2 and 3. As can be seen from the figure, the surface of the composite film is rough and has no defects, and the thickness of the separation layer of the prepared composite film is about 40 nm.
Testing CO at 0.5MPa and 25 deg.C respectively2/N2(15/85) and CO2/CH4(10/90) the composite film performance of the mixed gas, the test results are shown in Table 1.
Example 2
(1) Preparing a separation layer solution: dissolving trimesoyl chloride in n-heptane, and stirring to form a uniform oil phase solution, wherein the concentration of the trimesoyl chloride solution is 0.015 mol/L; dissolving N-methyldiethanolamine and 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene in deionized water, adding sodium carbonate, stirring to form an aqueous solution, wherein the concentration of the N-methyldiethanolamine is 0.06mol/L, the molar ratio of the 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene to the N-methyldiethanolamine is 0.05:1, and the pH value of the solution is adjusted to 10 by using the sodium carbonate.
(2) Preparing a composite membrane: fixing the polyacrylonitrile ultrafiltration membrane coated with the middle layer on a plate frame, pouring an oil phase solution, fully soaking the middle layer with the oil phase solution, pouring the oil phase solution, drying in the air, pouring a water phase solution, reacting at 40 ℃ for 15 minutes through interfacial polymerization, washing with deionized water after the reaction is finished, and drying to obtain CO2Separating the composite membrane.
Testing CO at 0.5MPa and 25 deg.C respectively2/N2(15/85) and CO2/CH4(10/90) the composite film performance of the mixed gas, the test results are shown in Table 1.
Example 3
(1) Preparing a separation layer solution: dissolving trimesoyl chloride in n-heptane, and stirring to form a uniform oil phase solution, wherein the concentration of the trimesoyl chloride solution is 0.015 mol/L; dissolving N-methyldiethanolamine and 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene in deionized water, adding sodium carbonate, stirring to form an aqueous solution, wherein the concentration of the N-methyldiethanolamine is 0.12mol/L, the molar ratio of the 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene to the N-methyldiethanolamine is 0.5:1, and the pH of the solution is adjusted to 10.5 by using the sodium carbonate.
(2) Preparing a composite membrane: fixing the polyethersulfone ultrafiltration membrane coated with the middle layer on a plate frame, pouring an oil phase solution, fully infiltrating the middle layer with the oil phase solution, pouring the oil phase solution out, drying in the air, pouring an aqueous phase solution, reacting at 30 ℃ for 3 minutes through interfacial polymerization, washing with deionized water after the reaction is finished, and drying to obtain CO2Separating the composite membrane.
Testing CO at 0.5MPa and 25 deg.C respectively2/N2(15/85) and CO2/CH4(10/90) the composite film performance of the mixed gas, the test results are shown in Table 1.
Example 4
(1) Preparing a separation layer solution: dissolving trimesoyl chloride in n-heptane, and stirring to form a uniform oil phase solution, wherein the concentration of the trimesoyl chloride solution is 0.01 mol/L; dissolving N-methyldiethanolamine and 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene in deionized water, adding sodium carbonate, stirring to form an aqueous solution, wherein the concentration of the N-methyldiethanolamine is 0.06mol/L, the molar ratio of the 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene to the N-methyldiethanolamine is 0.1:1, and the pH value of the solution is adjusted to 10-11 by using the sodium carbonate.
(2) Preparing a composite membrane: fixing the polyvinylidene fluoride ultrafiltration membrane coated with the middle layer on a plate frame, pouring an oil phase solution, fully soaking the middle layer with the oil phase solution, pouring the oil phase and drying in the air, then pouring an aqueous phase solution, reacting at 50 ℃ for 10 minutes through interfacial polymerization, washing with deionized water after the reaction is finished, and drying to obtain CO2Separating the composite membrane.
Testing CO at 0.5MPa and 25 deg.C respectively2/N2(15/85) and CO2/CH4(10/90) the composite film performance of the mixed gas, the test results are shown in Table 1.
Example 5
(1) Preparing a separation layer solution: dissolving trimesoyl chloride in n-heptane, and stirring to form a uniform oil phase solution, wherein the concentration of the trimesoyl chloride solution is 0.02 mol/L; dissolving N-methyldiethanolamine and 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene in deionized water, adding sodium carbonate, stirring to form an aqueous solution, wherein the concentration of the N-methyldiethanolamine is 0.06mol/L, the molar ratio of the 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene to the N-methyldiethanolamine is 0.25:1, and the pH value of the solution is adjusted to be 11 by using the sodium carbonate.
(2) Preparing a composite membrane: fixing the polysulfone ultrafiltration membrane coated with the middle layer on a plate frame, pouring an oil phase solution, fully soaking the middle layer with the oil phase solution, pouring the oil phase solution out, drying in the air, pouring a water phase solution, reacting at 30 ℃ for 10 minutes through interfacial polymerization, washing with deionized water after the reaction is finished, and drying to obtain CO2Separating the composite membrane.
Testing CO at 0.5MPa and 25 deg.C respectively2/N2(15/85) and CO2/CH4(10/90) the composite film performance of the mixed gas, the test results are shown in Table 1.
TABLE 1 CO of the membranes prepared in the examples under different separation systems2Separation Performance
As can be seen from Table 1, in CO2/N2And CO2/CH4Under the system, the CO prepared by the invention2The separation composite membrane exhibits good separation performance. CO of the membranes prepared in the examples at 0.11MPa2/N2Separation factor is between 125 and 370, CO2/CH4The separation factor is between 55 and 61; at 0.20MPa, of the films produced in the examplesCO2/N2Separation factor between 82 and 142, CO2/CH4A separation factor between 35 and 45; CO of the membranes prepared in the examples at 0.50MPa2/N2Separation factor between 55 and 77, CO2/CH4The separation factor is between 24 and 32. By adjusting the conditions of reaction temperature, monomer concentration and the like, composite membranes with different permeation rates and different separation factors can be obtained.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (6)
1. A method for preparing a high-performance carbon dioxide separation composite membrane containing a twisted structure by interfacial polymerization; the method is characterized by comprising the following steps:
(1) preparing a separation layer solution: dissolving trimesoyl chloride in an organic phase solvent n-heptane, and stirring to form a uniform oil phase solution; dissolving N-methyldiethanolamine and 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spiral bisindene in deionized water, uniformly stirring to form a solution, adding sodium carbonate to adjust the pH value of the solution to 10-11, and stirring to form an aqueous phase solution;
(2) preparing a composite membrane: fixing the ultrafiltration membrane coated with the middle layer on a plate frame, pouring an oil phase solution, pouring the oil phase solution out after the oil phase solution fully infiltrates the middle layer, drying the oil phase solution in the air, and then pouring a water phase solution into the middle layer to perform interfacial polymerization; finally pouring out the aqueous phase solution and washing with deionized water; and (5) putting the composite membrane into a constant temperature and humidity box, and drying to obtain the composite membrane.
2. The method as set forth in claim 1, wherein in the step (1), the concentration of the trimesoyl chloride solution is 0.01mol/L to 0.02 mol/L.
3. The method according to claim 1, wherein in the step (1), the concentration of N-methyldiethanolamine is 0.03-0.12 mol/L, and the molar ratio of 5,5 ', 6, 6' -tetrahydroxy-3, 3,3 ', 3' -tetramethyl-spirobisindane to methyldiethanolamine is 0.05-0.5: 1.
4. The method of claim 1, wherein in the step (2), the ultrafiltration membrane comprises a polysulfone ultrafiltration membrane, a polyacrylonitrile ultrafiltration membrane, a polyethersulfone ultrafiltration membrane, a polyetheretherketone ultrafiltration membrane, a polyvinylidene fluoride ultrafiltration membrane or a polycarbonate ultrafiltration membrane material.
5. The method according to claim 1, wherein in the step (2), the reaction is carried out in the aqueous solution for 3 to 15 minutes.
6. The method as set forth in claim 1, wherein in the step (2), the reaction temperature of the interfacial polymerization is controlled in the range of 30 ℃ to 50 ℃.
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