Azos polymer mixed matrix membrane as well as preparation method and application thereof

Abstract

The invention discloses an Azos polymer mixed matrix membrane and a preparation method and application thereof, and the method comprises the following steps: dissolving one or more aniline compounds in an organic solvent, and carrying out a coupling reaction under the action of a catalyst and a catalyst auxiliary agent; after the reaction is finished, filtering, washing and drying in sequence to obtain Azos particles with azo functional groups; ultrasonically dispersing Azos particles in an organic solvent, adding the Azos particles into the dissolved polymer matrix solution, blending, and uniformly stirring to obtain a membrane casting solution; and carrying out ultrasonic defoaming treatment on the obtained membrane casting solution, preparing a membrane by adopting a vacuum-assisted membrane forming method or a high-pressure and vacuum coupling membrane forming method or a solution pouring method, and finally drying the membrane in a drying oven at 70-90 DEG C for 10-15 hours to obtain the Azos / polymer mixed matrix membrane. The method has the advantages of being easy to operate, environmentally friendly, low in cost and the like, and a new choice is provided for the fields of bioethanol preparation, gas adsorption / separation and the like.

Description

Technical Field

[0001] The present invention relates to a preparation method and application of Azos / polymer mixed matrix membranes, belonging to the fields of mixed matrix membrane preparation technology, membrane application, and environmental protection technology, and particularly belonging to the field of CO 2 gas separation. Background Art

[0002] Since the Industrial Revolution, the global economy has been rising rapidly, and the world's demand for energy, especially traditional fossil fuels (natural gas, oil, and coal), has increased. The large amount of CO 2 emissions not only cause environmental problems such as global warming and ocean acidification, but also result in a large waste of carbon resources. Therefore, it is urgent to develop separation technologies for CO 2 . Compared with traditional separation technologies, membrane separation has the advantages of simple operation, low energy consumption, low cost, small floor area, and no secondary pollution. It combines the high efficiency and economy of separation and has great potential.

[0003] The trade-off between permeability and selectivity remains the main problem restricting the development of membranes. To break this restriction, many methods for improving performance have been proposed. Mixed matrix membranes (MMMs) prepared by dispersing highly adsorptive and selective fillers in a continuous phase are one of the most effective methods to overcome the Robeson upper limit [W. Zhu, Y. Qin, Z. Wang, J. Zhang, R. Guo, X. Li, Incorporating the magnetic alignment of GO composites into Pebax matrix for gas separation, Journal of Energy Chemistry 31 (2019) 1-10.]. However, most current traditional mixed matrix membranes are inorganic fillers, and there are problems of compatibility and dispersibility with organic polymer matrices. In view of this, developing mixed matrix membranes prepared with organic fillers has great potential for CO 2 separation. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for preparing a mixed matrix membrane filled with Azos particles. Starting from the filler material, the present invention improves the specific surface area of polymer particles by introducing three-dimensional space and network structure monomers to provide sufficient adsorption sites for CO 2 . At the same time, groups such as azo bonds and tertiary amino groups are used to increase the affinity for CO 2 . In addition, the membrane preparation method is further improved to make the membrane layer more dense, reduce the permeability of the mixed matrix membrane to N 2 and thus enhance the CO 2 / N 2Separation performance.

[0005] The object of the present invention can be achieved by the following measures:

[0006] A method for preparing a mixed matrix membrane, the method comprising the following steps:

[0007] (1) Dissolve one or more aniline compounds in an organic solvent and carry out a coupling reaction under the action of a catalyst and its catalyst adjuvant; after the reaction is completed, filter, wash and dry in sequence to obtain Azos particles with azo functional groups;

[0008] (2) Ultrasonically disperse the Azos particles in an organic solvent, add them to the dissolved polymer matrix solution for blending, and obtain a casting solution after stirring evenly; after the obtained casting solution is ultrasonically degassed, then use a vacuum-assisted film-forming method or a high-pressure and vacuum coupling film-forming method or a solution casting method to form a film, and finally place it in an oven at 70-90 °C for drying for 10-15 h to obtain an Azos / polymer mixed matrix membrane.

[0009] In the technical solution of the present invention: in step (1), the aniline compound is selected from any one or more of 2,6,14-triaminotriphenylene, N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, tris(4-aminophenyl)amine, 1,4-benzenediamine, 4,4'-(4,4'-isopropylidenediphenyl-1,1'-dioxy)diphenylamine, 4-aminophenyl sulfone, o-phenylenediamine, m-phenylenediamine, 1,4-benzenediamine, benzidine, 4-propoxy-1,2-diaminobenzene, 3-(2,4-diaminophenoxy)propane-1,2-diol, 4-(2-methoxyethoxy)-5-methylbenzene-1,3-diamine, 2,7-diaminobenzo-9,10-dione, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 4-[2-(4-aminophenyl)ethynyl]aniline, 4-(4-amino-2-methylphenyl)-2,3,6-trimethylaniline, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 2,5-diamino-4-nitro-4'-dimethylaminostilbene, 2,4-diaminophenol, 2,5-diaminophenol, 2,3-diaminophenol, 4-fluoro-1,3-diaminobenzene, 4,4'-diaminobiphenyl-2,2-dicarboxylic acid, 4,4''-diaminoterphenyl, 3,5-diamino-1,2,4-triazole, 2-chloro-4,6-diamino-1,3,5-triazine, 1,4-diamino-2,3-dicyano-9,10-anthraquinone, 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,2'-diaminoethylene diphenyl ether, 4,4'-diaminobenzanilide, 2,4-diaminoanisole, 2,7-diaminodiphenyl sulfone, 3,6-thioanthracenediamine, o-tolidine sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, 3,3'-diaminodiphenyl sulfone, diaminodiphenyl methane, 3,3'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 3,3'-oxybis[5-(trifluoromethyl)aniline], 5,5'-(hexafluoroisopropylidene)di-o-toluidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 3,4,4'-triaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 2-aminophenyl ether, 2,4,5,6-tetrafluoro-1,3-benzenediamine;

[0010] Preferably: the aniline compound monomer is one or more of 2,6,14-triaminotriphenylene, N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, 4-propoxy-1,2-diaminobenzene, 1,4-benzenediamine, benzidine;

[0011] Further preferably, the aniline compound monomer is 2,6,14-triaminotriphenylene and N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine with a molar ratio of 1 to 3:1 to 3.

[0012] In the technical solution of the present invention: in step (1), the organic solvent is one or two of tetrahydrofuran, toluene, ethanol, carbon tetrachloride, dimethyl sulfoxide, chloroform, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, dichloroethane, ether, acetonitrile, xylene, benzene, bromobenzene, trichloromethane, acetone, isopropanol, tert-butanol, and carbon tetrachloride;

[0013] The catalyst is any one of cuprous chloride, cuprous bromide, cuprous iodide, sodium nitrite, and potassium nitrite;

[0014] The catalyst assistant is one of pyridine, furan, and thiophene;

[0015] Preferably, the organic solvents are one or two of tetrahydrofuran, toluene, carbon tetrachloride, and dimethyl sulfoxide; the catalyst is cuprous chloride or cuprous bromide, and the catalyst assistant is pyridine;

[0016] The molar ratio between the aniline compound, the catalyst, and the catalyst assistant is 0.1 to 2:0.1 to 2:0.1 to 10;

[0017] Preferably, the molar ratio between the aniline compound, the catalyst, and the catalyst assistant is 1 to 2:1 to 2:3 to 8.

[0018] In the technical solution of the present invention: in step (1), the coupling reaction temperature ranges from 10 to 100 °C, and the reaction time is 80 to 120 h;

[0019] Preferably, the reaction is heated from the initial temperature (10 °C) at a rate of 5 to 8 °C / min. When the temperature is raised to 25 to 30 °C, the reaction is carried out for 45 to 50 h; then, it is heated at a rate of 5 to 8 °C / min until the temperature reaches 55 to 65 °C, and the reaction is carried out for 20 to 25 h. Finally, it is heated at a rate of 5 to 8 °C / min until the temperature reaches 75 to 85 °C, and the reaction is carried out for 20 to 25 h.

[0020] In the technical solution of the present invention: in step (1), the support for filtration is polyamide, and the pore size distribution of the support is in the range of 0.1 to 1000 nm; the drying condition is drying in an oven at 60 to 100 °C for 3 to 48 h.

[0021] Preferably, the pore size distribution of the support is 1 to 500 nm, and the drying condition is drying in an oven at 70 to 90 °C for 10 to 30 h.

[0022] In the technical solution of the present invention: in step (2), the Azos particles are dispersed in an organic solvent, and the organic solvent is one or two of toluene, ethanol, carbon tetrachloride, dimethyl sulfoxide, chloroform, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, dichloroethane, ether, acetonitrile, xylene, benzene, bromobenzene, trichloromethane, acetone, isopropanol, tert-butanol, carbon tetrachloride;

[0023] Preferably: the organic solvent is any one or two of dimethylformamide, ethanol, N-methylpyrrolidone and dimethyl sulfoxide.

[0024] In the technical solution of the present invention, in step (2), the polymer matrix is any one of polydimethylsiloxane (PDMS), polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyether copolyamide (Pebax), polyamide (PA), polyimide (PI), polymer of intrinsic microporosity (PIMs), cellulose acetate (AT);

[0025] Preferably: the polymer matrix is polyether copolyamide (Pebax); More preferably: any one of Pebax-1074, Pebax-1657, Pebax-2533.

[0026] In the technical solution of the present invention, in step (2), the solvent for dissolving the polymer matrix is one or two or more mixed solvents with different proportions of distilled water, ethanol, methanol, n-hexane, n-heptane, toluene, tetrahydrofuran, chloroform, methanol, acetone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, carbon tetrachloride, n-butanol; the condition for dissolving the polymer matrix is refluxing at 60-95 °C for 1-3 h;

[0027] The concentration of the polymer matrix solution is 0.1-80 wt.%; the mass ratio of the Azos particles to the polymer matrix is 1:10-300;

[0028] Preferably: the solvent for dissolving the polymer matrix is a mixed solution of distilled water and ethanol with a mass ratio of 1-5:1-10; the concentration of the matrix polymer solution is 0.1-10 wt.%; the mass ratio of the Azos particles to the polymer matrix is 1:20-200.

[0029] The condition for blending is stirring at 20-30 °C for 1-20 h; preferably: the blending stirring time is 3-10 h.

[0030] In step (2) of the technical solution of the present invention, the vacuum-assisted film formation method or the high-pressure and vacuum coupled film formation method uses a support for filtration, and the support material is one or more of polytetrafluoroethylene, polyamide, cellulose acetate, ceramic, silicon carbide, alumina, polyvinylidene fluoride and polyacrylonitrile, and the pore size is 50-200 nm;

[0031] In the vacuum-assisted film formation method, the pressure on the lower surface of the support is 100 - 10,000 PaA; the upper surface is at atmospheric pressure;

[0032] In the high-pressure and vacuum coupling film formation method, the pressure on the lower surface of the support is 100 - 10,000 PaA; the upper surface is pressurized, and the pressurizing pressure is 20 - 1,000 kPaG.

[0033] In the solution casting method, the casting solution of the mixed matrix membrane is directly poured into a petri dish and dried in an oven at 60 - 100 °C for 12 - 24 h;

[0034] Preferably: In the vacuum-assisted film formation method, the pressure on the lower surface of the support is 100 - 5,000 PaA; Further preferably: In the vacuum-assisted film formation method, the pressure on the lower surface of the support is 500 - 3,000 PaA;

[0035] Preferably: In the high-pressure and vacuum coupling film formation method, the pressure on the lower surface of the support is 100 - 5,000 PaA, and the upper surface is pressurized, and the pressurizing pressure is 50 - 800 kPaG. Further preferably: In the high-pressure and vacuum coupling film formation method, the pressure on the lower surface of the support is 500 - 3,000 PaA, and the upper surface is pressurized, and the pressurizing pressure is 50 - 600 kPaG.

[0036] In the technical solution of the present invention, the mixed matrix membrane prepared by the method is used in the application of CO 2 gas separation; Preferably: Applied to CO 2 / N 2 、H 2 / CO 2 、CO 2 / CH 4 gas separation applications;

[0037] Preferably: The pressure on the feed side is 10 - 1,000 kPaG, and the test temperature is 0 - 100 °C;

[0038] Further preferably: The pressure on the feed side is 30 - 500 kPaG, and the test temperature is 10 - 50 °C.

[0039] In the technical solution of the present invention: paA or kpaA is absolute pressure, and paG or kpaG is gauge pressure.

[0040] The beneficial effect of the present invention is: The present invention prepares a mixed matrix membrane by synthesizing a new type of Azos filling. The core lies in preparing a mixed matrix membrane by the vacuum-assisted film formation method and the high-pressure and vacuum coupling film formation method for separating CO 2 / N 2System. Compared with the solution casting method, this method can improve the separation selectivity without changing the permeation rate. The matrix polymer membrane material has good ductility, thermal stability and chemical stability. However, there is a trade-off between permeability and selectivity in the matrix polymer membrane material itself. Therefore, the microporous organic polymer particles introduced in the present invention can improve the separation selectivity of the prepared homogeneous membrane. In addition, the membrane material is prepared by the suction filtration method, and the membrane layer thickness is accurately controlled by adjusting the mass of the casting solution, reducing the accidental error caused by manual methods. Some studies have shown that the denser the mixed matrix membrane structure, the higher the separation selectivity of the membrane layer, which is beneficial to CO 2 / N 2 efficient separation [CN118356812A]. Brief Description of the Drawings

[0041] Figure 1 It is the electron micrograph of Azo-3 particles in Example 3.

[0042] Figure 2 It is the infrared spectrum of Azos particles in Examples 1-5.

[0043] Figure 3 It is the electron micrograph of the surface and cross-section of the mixed matrix membrane in Example 3.

[0044] Figure 4 It is the CO 2 / N 2 adsorption selectivity diagram of polymer particles in Example 3. Detailed Description of the Invention

[0045] The present invention will be further described in detail below with reference to specific examples, but the present invention is not limited to specific examples.

[0046] The present invention uses the constant volume variable pressure method to measure the permeability coefficient P (Barrer) of the prepared mixed matrix membrane, 1 Barrer = 10 -10 cm 3 (STP) cm / (cm 2 ·s·cmHg), and its calculation formula is as follows:

[0047]

[0048] Among them, l is the membrane thickness (cm), A is the membrane area (cm 2 ), T is the test temperature (K), p is the atmospheric pressure (cmHg), V is the volume of the soap bubble flowing through (cm 3 ), t is the time (s), ΔP i is the transmembrane pressure (cmHg), x i and y i respectively represent the volume fractions of component i on the feed side and the permeate side, and P 0and P 1 represent the pressures on the feed side and the permeate side, respectively.

[0049] The selectivity calculation formula for the Azos / polymer mixed matrix membrane is as follows:

[0050]

[0051] where P CO2 and P N2 correspond to the permeability coefficients of CO 2 and N 2 respectively.

[0052] Example 1

[0053] Take 0.38 g (1.26 mmol) of 2,6,14-triaminotriphenylene and add it to a mixed solution of 50 ml of THF and 50 ml of toluene, stir to dissolve, add 0.234 g (1.63 mmol) of cuprous bromide, and then add 0.5 ml (6.21 mmol) of pyridine. The initial temperature is 10 °C, set the heating rate to 5 °C / min and heat up to 25 °C, stir for 48 h, then heat up to 60 °C at a heating rate of 5 °C / min and react for 24 h, and finally heat up to 80 °C at a heating rate of 5 °C / min and react for 24 h. After completion, wash the reactant solution three times with tetrahydrofuran, hydrochloric acid solution and water respectively, and then filter it through a polyamide support with a pore size of 100 nm. Place the obtained polymer in a blast drying oven at 80 °C and dry for 12 h to obtain Azo-1 particles.

[0054] Weigh 0.003 g of Azo-1 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Then weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a Pebax polymer solution. Then add the Azo-1 particle dispersion to the Pebax polymer solution, stir evenly at 25 °C for 8 h to obtain a casting solution.

[0055] First, ultrasonically degas the casting solution for 5 min, and then vacuum filter (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on the polyamide support (pore size: 100 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then bake it in a blast drying oven at 80 °C for 12 h to obtain the Azo-1 / Pebax mixed matrix membrane.

[0056] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm2 , the pressure on the membrane raw material side is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 55.69 Barrer, and the N 2 permeation coefficient is 0.81 Barrer. The ideal selectivity is 68.75.

[0057] Example 2

[0058] Weigh 0.25 g (0.84 mmol) of 2,6,14-triaminotriphenylene and 0.19 g (0.42 mmol) of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, add them to a mixed solution of 50 ml of THF and 50 ml of toluene and stir. Then add 0.23 g (1.63 mmol) of cuprous bromide, and then add 0.5 ml (6.21 mmol) of pyridine. The initial temperature is 10 °C. Set the heating rate to 5 °C / min and heat up to 25 °C, stir for 48 h, then heat up to 60 °C at a heating rate of 5 °C / min and react for 24 h, and finally heat up to 80 °C at a heating rate of 5 °C / min and react for 24 h. After completion, wash the reaction solution with tetrahydrofuran, hydrochloric acid solution and water three times respectively, and then filter it through a polyamide support with a pore size of 100 nm. Place the obtained polymer in a blast drying oven at 80 °C and dry for 12 h to obtain Azo-2 particles.

[0059] Weigh 0.003 g of Azo-2 particles, add them to 0.597 g of DMF solution, and disperse them ultrasonically to prepare a polymer particle dispersion. Then weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-2 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0060] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then vacuum filter (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on the polyamide support (pore size: 100 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then bake it in a blast drying oven at 80 °C for 12 h to obtain an Azo-2 / Pebax mixed matrix membrane.

[0061] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the membrane raw material side is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the CO 2The permeability coefficient is 49.23 Barrer, N 2 The permeability coefficient is 0.66 Barrer. The ideal selectivity is 71.09.

[0062] Example 3

[0063] Weigh 0.19 g (0.63 mmol) of 2,6,14-triaminotriphenylene and 0.29 g (0.63 mmol) of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, add them to a mixed solution of 50 ml of THF and 50 ml of toluene and stir. Then add 0.23 g (1.63 mmol) of cuprous bromide, and then add 0.5 ml (6.21 mmol) of pyridine. The initial temperature is 10 °C, and the temperature is raised to 25 °C at a heating rate of 5 °C / min and stirred for 48 h. Then the temperature is raised to 60 °C at a heating rate of 5 °C / min and reacted for 24 h. Finally, the temperature is raised to 80 °C at a heating rate of 5 °C / min and reacted for 24 h. After completion, the reaction solution is washed three times with tetrahydrofuran, hydrochloric acid solution and water respectively, and then filtered through a polyamide support with a pore size of 100 nm. The obtained polymer is placed in a blast drying oven at 80 °C and dried for 12 h to obtain Azo-3 particles.

[0064] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Then weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0065] First, the casting solution is subjected to ultrasonic degassing treatment for 5 min, and then vacuum filtered (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on the polyamide support (pore size: 100 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then bake it in a blast drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0066] Test the separation performance of the mixed matrix membrane obtained in this example for CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 ², the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeability coefficient of CO 2 is 47.33 Barrer, N 2 The permeability coefficient is 0.5 Barrer. The ideal selectivity is 94.66.

[0067] Example 4

[0068] Weigh 0.25 g (0.42 mmol) of 2,6,14-triaminotriphenylene and 0.39 g (0.84 mmol) of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, add them to a mixed solution of 50 ml of THF and 50 ml of toluene, stir, then add 0.23 g (1.63 mmol) of cuprous bromide, and then add 0.5 ml (6.21 mmol) of pyridine. The initial temperature is 10 °C, and the temperature is raised to 25 °C at a heating rate of 5 °C / min, stir for 48 h, then raise the temperature to 60 °C at a heating rate of 5 °C / min and react for 24 h, and finally raise the temperature to 80 °C at a heating rate of 5 °C / min and react for 24 h. After completion, the reaction solution is washed three times with tetrahydrofuran, hydrochloric acid solution and water respectively, and then filtered through a polyamide support with a pore size of 100 nm. The obtained polymer is placed in a blast drying oven at 80 °C and dried for 12 h to obtain Azo-4 particles.

[0069] Weigh 0.003 g of Azo-4 particles, add them to 0.597 g of DMF solution, and disperse them ultrasonically to prepare a polymer particle dispersion. Then weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-4 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0070] First, the casting solution is ultrasonically degassed for 5 min, and then vacuum filtered (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on a polyamide support (pore size: 100 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then bake it in a blast drying oven at 80 °C for 12 h to obtain an Azo-4 / Pebax mixed matrix membrane.

[0071] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 45.5 Barrer, and the permeation coefficient of N 2 is 0.58 Barrer. The ideal selectivity is 78.44.

[0072] Example 5

[0073] Take 0.59 g (1.26 mmol) of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, add it to a mixed solution of 50 ml of THF and 50 ml of toluene, stir, then add 0.23 g (1.63 mmol) of cuprous bromide, and then add 0.5 ml (6.21 mmol) of pyridine. The initial temperature is 10 °C, and the temperature is raised to 25 °C at a heating rate of 5 °C / min, stir for 48 h, then raise the temperature to 60 °C at a heating rate of 5 °C / min and react for 24 h, and finally raise the temperature to 80 °C at a heating rate of 5 °C / min and react for 24 h. After completion, wash the reactant solution three times with tetrahydrofuran, hydrochloric acid solution and water respectively, and then filter it through a polyamide support with a pore size of 100 nm. Place the obtained polymer in a blast drying oven at 80 °C and dry for 12 h to obtain Azo-5 particles.

[0074] Weigh 0.003 g of Azo-5 particles, add them to 0.597 g of DMF solution, and disperse them ultrasonically to prepare a polymer particle dispersion. Then weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-5 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0075] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then vacuum filter (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on a polyamide support (pore size: 100 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then bake it in a blast drying oven at 80 °C for 12 h to obtain an Azo-5 / Pebax mixed matrix membrane.

[0076] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 41.97 Barrer, and the permeation coefficient of N 2 is 0.57 Barrer. The ideal selectivity is 73.63.

[0077] Example 6

[0078] Weigh 0.0008 g of Azo-3 particles, add them to 0.1492 g of DMF solution, and ultrasonically disperse to prepare a polymer particle dispersion. Subsequently, weigh 0.146 g of Pebax polymer, dissolve it in 4.704 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0079] First, ultrasonically degas the casting solution for 5 min, and then perform vacuum filtration (the lower surface pressure is 1000 PaA) to evenly cover the casting solution on a polyamide support (pore size: 100 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then dry it in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0080] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 27.78 Barrer, and the permeation coefficient of N 2 is 0.46 Barrer. The ideal selectivity is 60.

[0081] Example 7

[0082] Weigh 0.0015 g of Azo-3 particles, add them to 0.2985 g of DMF solution, and ultrasonically disperse to prepare a polymer particle dispersion. Subsequently, weigh 0.141 g of Pebax polymer, dissolve it in 4.559 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0083] First, ultrasonically degas the casting solution for 5 min, and then perform vacuum filtration (the lower surface pressure is 1000 PaA) to evenly cover the casting solution on a polyamide support (pore size: 100 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then dry it in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0084] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2For the separation performance of the system, the effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 30.31 Barrer, and the N 2 permeation coefficient is 0.41 Barrer. The ideal selectivity is 74.68.

[0085] Example 8

[0086] Weigh 0.0023 g of Azo-3 particles, add them to 0.4477 g of DMF solution, and disperse them ultrasonically to prepare a polymer particle dispersion. Subsequently, weigh 0.1365 g of Pebax polymer, dissolve it in 4.4135 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0087] First, ultrasonically degas the casting solution for 5 min, and then perform vacuum filtration (the pressure on the lower surface is 1000 PaA) to evenly cover the casting solution on the polyamide support (pore size: 100 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then dry it in a blast drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0088] Test the separation performance of the mixed matrix membrane obtained in this example for CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 34.72 Barrer, and the N 2 permeation coefficient is 0.39 Barrer. The ideal selectivity is 89.72.

[0089] Example 9

[0090] Weigh 0.0038 g of Azo-3 particles, add them to 0.7462 g of DMF solution, and disperse them ultrasonically to prepare a polymer particle dispersion. Subsequently, weigh 0.1275 g of Pebax polymer, dissolve it in 4.1225 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0091] First, the casting solution was ultrasonically degassed for 5 min, and then vacuum filtered (the pressure on the lower surface was 1000 PaA) to uniformly cover the polyamide support (pore size: 100 nm) with the casting solution. After the surface was free of liquid, filtration was continued for 1 h. After filtration, it was left standing at room temperature for 2 h, and then dried in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0092] The separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system was tested. The effective area of the polymer membrane was 10 cm 2 , the pressure on the feed side of the membrane was 200 kPaG, and the test temperature was 25 °C. The permeation results showed that the permeation coefficient of CO 2 was 59.57 Barrer, and the permeation coefficient of N 2 was 0.72 Barrer. The ideal selectivity was 82.3.

[0093] Example 10

[0094] 0.0045 g of Azo-3 particles were weighed and added to 0.8955 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Subsequently, 0.123 g of Pebax polymer was weighed and dissolved in 3.977 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. Then the Azo-3 particle dispersion was added to the Pebax matrix polymer solution, and stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0095] First, the casting solution was ultrasonically degassed for 5 min, and then vacuum filtered (the pressure on the lower surface was 1000 PaA) to uniformly cover the polyamide support (pore size: 100 nm) with the casting solution. After the surface was free of liquid, filtration was continued for 1 h. After filtration, it was left standing at room temperature for 2 h, and then dried in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0096] The separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system was tested. The effective area of the polymer membrane was 10 cm 2 , the pressure on the feed side of the membrane was 200 kPaG, and the test temperature was 25 °C. The permeation results showed that the permeation coefficient of CO 2 was 86.45 Barrer, and the permeation coefficient of N 2 was 1.72 Barrer. The ideal selectivity was 50.34.

[0097] Example 11

[0098] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0099] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then perform vacuum filtration (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on a polyamide support (pore size: 100 nm). After the surface has no liquid, the filtration ends. Let it stand at room temperature for 2 h, and then dry it in a forced-air drying oven at 80 °C for 12 h to obtain an Azo-3 / Pebax mixed matrix membrane.

[0100] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 72 Barrer, and the permeation coefficient of N 2 is 1.1 Barrer. The ideal selectivity is 65.47.

[0101] Example 12

[0102] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0103] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then perform vacuum filtration (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on a polyamide support (pore size: 100 nm). After the surface has no liquid, filter for another 10 min. After the filtration ends, let it stand at room temperature for 2 h, and then dry it in a forced-air drying oven at 80 °C for 12 h to obtain an Azo-3 / Pebax mixed matrix membrane.

[0104] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2For the separation performance of the system, the effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 64.48 Barrer, and the N 2 permeation coefficient is 0.93 Barrer. The ideal selectivity is 68.97.

[0105] Example 13

[0106] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0107] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then perform vacuum filtration (the pressure on the lower surface is 1000 PaA) to uniformly cover the casting solution on the polyamide support (pore size: 100 nm). After there is no liquid on the surface, pump for another 30 min. After the filtration is completed, let it stand at room temperature for 2 h, and then dry it in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0108] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 58.73 Barrer, and the N 2 permeation coefficient is 0.75 Barrer. The ideal selectivity is 78.72.

[0109] Example 14

[0110] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0111] First, the casting solution was subjected to ultrasonic degassing treatment for 5 min, and then vacuum filtration was carried out (the pressure on the lower surface was 1000 PaA) to uniformly cover the polyamide support (pore size: 100 nm) with the casting solution. After there was no liquid on the surface, filtration was continued for 2 h. After the filtration was completed, it was left standing at room temperature for 2 h, and then dried in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0112] The separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system was tested. The effective area of the polymer membrane was 10 cm 2 , the pressure on the feed side of the membrane was 200 kPaG, and the test temperature was 25 °C. The permeation results showed that the permeation coefficient of CO 2 was 44.99 Barrer, and the N 2 permeation coefficient was 0.46 Barrer. The ideal selectivity was 96.72.

[0113] Example 15

[0114] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonic dispersion was carried out to prepare a polymer particle dispersion. Subsequently, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), and refluxed and continuously stirred at 80 °C for 2 h to obtain a matrix polymer solution. Then, the Azo-3 particle dispersion was added to the Pebax matrix polymer solution, and stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0115] First, the casting solution was subjected to ultrasonic degassing treatment for 5 min, and then vacuum filtration was carried out (the pressure on the lower surface was 1000 PaA) to uniformly cover the polyamide support (pore size: 100 nm) with the casting solution. After there was no liquid on the surface, filtration was continued and placed under the condition of 100 kPaG pressure (upper surface) for 1 h to assist in the preparation. It was left standing at room temperature for 2 h, and finally dried in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0116] The separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system was tested. The effective area of the polymer membrane was 10 cm 2 , the pressure on the feed side of the membrane was 200 kPaG, and the test temperature was 25 °C. The permeation results showed that the permeation coefficient of CO 2 was 42.57 Barrer, and the N 2 permeation coefficient was 0.45 Barrer. The ideal selectivity was 95.03.

[0117] Example 16

[0118] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0119] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then perform vacuum filtration (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on a polyamide support (pore size: 100 nm). After the surface has no liquid, continue filtration and place it under the condition of 200 kPaG pressure (upper surface) for auxiliary preparation for 1 h, let it stand at room temperature for 2 h, and finally dry it in a blast drying oven at 80 °C for 12 h to obtain an Azo-3 / Pebax mixed matrix membrane.

[0120] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 40.34 Barrer, and the permeation coefficient of N 2 is 0.42 Barrer. The ideal selectivity is 95.47.

[0121] Example 17

[0122] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0123] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then perform vacuum filtration (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on a polyamide support (pore size: 100 nm). After the surface has no liquid, continue filtration and place it under the condition of 400 kPaG pressure (upper surface) for auxiliary preparation for 1 h, let it stand at room temperature for 2 h, and finally dry it in a blast drying oven at 80 °C for 12 h to obtain an Azo-3 / Pebax mixed matrix membrane.

[0124] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 . The pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 37.48 Barrer, and the permeation coefficient of N 2 is 0.39 Barrer. The ideal selectivity is 95.73.

[0125] Example 18

[0126] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer and dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30). Reflux and continuously stir at 80 °C for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0127] First, ultrasonically degas the casting solution for 5 min, and then perform vacuum filtration (the pressure on the lower surface is 1000 PaA) to uniformly cover the casting solution on the polyamide support (pore size: 100 nm). After there is no liquid on the surface, continue the filtration and place it under the condition of 600 kPaG pressure (upper surface) for 1 h of auxiliary preparation, let it stand at room temperature for 2 h, and finally dry it in a blast drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0128] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 . The pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 35.48 Barrer, and the permeation coefficient of N 2 is 0.36 Barrer. The ideal selectivity is 97.53.

[0129] Example 19

[0130] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and ultrasonically disperse to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0131] First, ultrasonically degas the casting solution for 5 min, and then vacuum filter (the lower surface pressure is 1000 PaA) to evenly cover the casting solution on the polyamide support (pore size: 100 nm). After the surface has no liquid, continue to filter and place it under the condition of 400 kPaG pressure (upper surface) to assist in preparation for 30 min, let it stand at room temperature for 2 h, and finally dry it in a blast drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0132] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 40.21 Barrer, and the permeation coefficient of N 2 is 0.42 Barrer. The ideal selectivity is 95.52.

[0133] Example 20

[0134] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and ultrasonically disperse to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0135] First, ultrasonically degas the casting solution for 5 min, and then vacuum filter (the lower surface pressure is 1000 PaA) to evenly cover the casting solution on the polyamide support (pore size: 100 nm). After the surface has no liquid, continue to filter and place it under the condition of 400 kPaG pressure (upper surface) to assist in preparation for 2 h, let it stand at room temperature for 2 h, and finally dry it in a blast drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0136] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 36.45 Barrer, and the permeation coefficient of N 2 is 0.38 Barrer. The ideal selectivity is 96.65.

[0137] Example 21

[0138] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer and dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0139] First, ultrasonically degas the casting solution for 5 min, and then perform vacuum filtration (the pressure on the lower surface is 1000 PaA) to uniformly cover the casting solution on a polytetrafluoroethylene support (pore size: 150 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then dry it in a forced-air drying oven at 80 °C for 12 h to obtain an Azo-3 / Pebax mixed matrix membrane.

[0140] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 50.64 Barrer, and the permeation coefficient of N 2 is 0.61 Barrer. The ideal selectivity is 82.65.

[0141] Example 22

[0142] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0143] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then perform vacuum filtration (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on a polyacrylonitrile support (pore size: 50 nm). After the surface has no liquid, continue filtration for 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then dry it in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0144] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 45.64 Barrer, and the permeation coefficient of N 2 is 0.49 Barrer. The ideal selectivity is 92.65.

[0145] Example 23

[0146] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0147] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then perform vacuum filtration (the lower surface pressure is 1000 PaA) to uniformly cover the casting solution on a polyvinylidene fluoride support (pore size: 200 nm). After the surface has no liquid, continue filtration for 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then dry it in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0148] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2For the separation performance of the system, the effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 60.64 Barrer, and the N 2 permeation coefficient is 0.77 Barrer. The ideal selectivity is 78.85.

[0149] Example 24

[0150] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0151] First, subject the casting solution to ultrasonic degassing treatment for 5 min, and then perform vacuum filtration (the pressure on the lower surface is 500 PaA) to uniformly cover the casting solution on a polyamide support (pore size: 100 nm). After there is no liquid on the surface, filter for another 1 h. After the filtration is completed, let it stand at room temperature for 2 h, and then dry it in a forced-air drying oven at 80 °C for 12 h to obtain an Azo-3 / Pebax mixed matrix membrane.

[0152] Test the separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 45.32 Barrer, and the N 2 permeation coefficient is 0.47 Barrer. The ideal selectivity is 97.32.

[0153] Example 25

[0154] Weigh 0.003 g of Azo-3 particles, add them to 0.597 g of DMF solution, and disperse them by ultrasonic treatment to prepare a polymer particle dispersion. Subsequently, weigh 0.132 g of Pebax polymer, dissolve it in 4.268 g of ethanol / water mixed solution (ethanol / water mass ratio = 70 / 30), reflux at 80 °C and continuously stir for 2 h to obtain a matrix polymer solution. Then add the Azo-3 particle dispersion to the Pebax matrix polymer solution, and stir evenly at 25 °C for 8 h to obtain a casting solution.

[0155] First, the casting solution was ultrasonically degassed for 5 min, and then vacuum filtered (the pressure on the lower surface was 3000 PaA) to uniformly cover the polyamide support (pore size: 100 nm) with the casting solution. After there was no liquid on the surface, it was further evacuated for 1 h. After the filtration was completed, it was left standing at room temperature for 2 h, and then dried in a forced-air drying oven at 80 °C for 12 h to obtain the Azo-3 / Pebax mixed matrix membrane.

[0156] The separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system was tested. The effective area of the polymer membrane was 10 cm 2 , the pressure on the feed side of the membrane was 200 kPaG, and the test temperature was 25 °C. The permeation results showed that the permeation coefficient of CO 2 was 54.32 Barrer, and the permeation coefficient of N 2 was 0.6 Barrer. The ideal selectivity was 90.62.

[0157] Comparative Example 1

[0158] 0.15 g of Pebax polymer was weighed and dissolved in 4.85 g of an ethanol-water mixed solution (ethanol / water mass ratio = 70 / 30). It was refluxed and continuously stirred at 80 °C for 2 h to obtain a Pebax polymer solution. Then it was vacuum filtered (the absolute pressure on the lower surface was 1000 Pa) to uniformly cover the polyamide support (pore size: 100 nm) with the Pebax polymer solution. After there was no liquid on the surface, it was further evacuated for 1 h. After the filtration was completed, it was left standing at room temperature for 2 h, and then dried in a forced-air drying oven at 80 °C for 12 h to obtain the Pebax mixed matrix membrane.

[0159] The separation performance of the mixed matrix membrane obtained in this example for the CO 2 / N 2 system was tested. The effective area of the polymer membrane was 10 cm 2 , the pressure on the feed side of the membrane was 200 kPaG, and the test temperature was 25 °C. The permeation results showed that the permeation coefficient of CO 2 was 22.26 Barrer, and the permeation coefficient of N 2 was 0.4 Barrer. The ideal selectivity was 55.65.

[0160] Comparative Example 2

[0161] 0.15 g of Pebax polymer was weighed and dissolved in 4.85 g of an ethanol-water mixed solution (ethanol / water mass ratio = 70 / 30). It was refluxed and continuously stirred at 80 °C for 2 h to obtain a Pebax polymer solution. First, the Pebax polymer solution was ultrasonically degassed for 5 min, and then poured into a polytetrafluoroethylene petri dish and dried in a forced-air drying oven at 80 °C for 12 h to obtain a Pebax homogeneous membrane.

[0162] Test the separation performance of the Pebax homogeneous membrane obtained in this example for CO 2 / N 2 system. The effective area of the polymer membrane is 10 cm 2 , the pressure on the feed side of the membrane is 200 kPaG, and the test temperature is 25 °C. The permeation results show that the permeation coefficient of CO 2 is 90.36 Barrer, and the permeation coefficient of N 2 is 1.87 Barrer. The ideal selectivity is 48.43.

Claims

1. A method for preparing a mixed matrix membrane, characterized in that: The method comprises the following steps: (1) dissolving one or more aniline compounds in an organic solvent, and performing a coupling reaction in the presence of a catalyst and a catalyst auxiliary agent; after the reaction is completed, filtering, washing and drying are performed in sequence to obtain Azos particles with a coupling functional group; (2) Ultrasonic dispersion of Azos particles in an organic solvent, adding the dissolved polymer matrix solution to the organic solvent for blending, and stirring to obtain a casting solution; ultrasonic degassing the obtained casting solution, and then using a vacuum-assisted film-forming method, a high-pressure and vacuum-coupled film-forming method, or a solution casting method to prepare a film, and finally putting the film into an oven at 70 to 90° C. for 10 to 15 hours to obtain an Azos / polymer mixed matrix membrane.

2. The preparation method according to claim 1, characterized in that: In step (1), the aniline compound is selected from 2,6,14-triaminotriptycene, N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, tris(4-aminophenyl)amine, 1,4-phenylenediamine, 4,4'-(4,4'-isopropylidene diphenyl-1,1'-dioxy)diphenylamine, 4-aminophenyl sulfone, o-phenylenediamine, m-phenylenediamine, 1,4-phenylenediamine, benzidine, 4-propoxy-1,2-diaminobenzene, 3-(2,4-diaminophenoxy)propane-1,2-diol, 4-(2-methoxyethoxy)-5-methylbenzene-1,3-diamine, 2,7-diaminobenzene, Aminobenzo-9,10-dione, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 4-[2-(4-aminophenyl)ethynyl]aniline, 4-(4-amino-2-methyl-phenyl)-2,3,6-trimethylaniline, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 2,5-diamino-4-nitro-4'-dimethylaminostilbene, 2,4-diaminophenol, 2,5-diaminophenol, 2,3-diaminophenol, 4-fluoro-1,3-diaminobenzene, 4,4'-diaminobiphenyl-2,2-dicarboxylic acid, 4,4"-diaminotriphenylamine benzene, 3,5-diamino-1,2,4-triazole, 2-chloro-4,6-diamino-1,3,5-triazine, 1,4-diamino-2,3-dicyano-9,10-anthraquinone, 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,2'-diaminoethylene glycol diphenyl ether, 4,4'-diaminobenzanilide, 2,4-diaminoanisole, 2,7-diaminodiphenyl sulfone, 3,6-thioanthracene diamine, o-toluidine sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, 3,3'-diaminodiphenyl sulfone, diaminodiphenylmethane, 3,3'-bis(trifluoromethyl)ethane Any one or more of 2,4-diaminophenyl ether, 2,2'-bis(trifluoromethyl)-1,1'-biphenyl]-4,4'-diamine, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 3,3'-oxybis[5-(trifluoromethyl)aniline], 5,5'-(hexafluoroisomethylene)di-o-toluidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 3,4,4'-triaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 2-aminophenyl ether, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine; Preferably, the aniline compound monomer is one or more of 2,6,14-triaminotriptycene, N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, 4-propoxy-1,2-diaminobenzene, 1,4-phenylenediamine, and benzidine; More preferably, the aniline compound monomer is 2,6,14-triaminotriptycene and N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine in a molar ratio of 1-3:1-3.

3. The preparation method according to claim 1, characterized in that: In step (1), the organic solvent is one or two of tetrahydrofuran, toluene, ethanol, carbon tetrachloride, dimethyl sulfoxide, chloroform, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, ethylene dichloride, ether, acetonitrile, xylene, benzene, benzene bromide, chloroform, acetone, isopropanol, tert-butyl alcohol and carbon tetrachloride; The catalyst is any one of cuprous chloride, cuprous bromide, cuprous iodide, sodium nitrite, and potassium nitrite; The catalyst auxiliary agent is one of pyridine, furan and thiophene; Preferably: the organic solvent is one or two of tetrahydrofuran, toluene, carbon tetrachloride, and dimethyl sulfoxide; the catalyst is cuprous chloride or cuprous bromide, and the catalyst auxiliary is pyridine; The molar ratio of the aniline compound, the catalyst and the catalyst auxiliary is 0.1-2:0.1-2:0.1-10; Preferably, the molar ratio of the aniline compound, the catalyst and the catalyst auxiliary is 1-2:1-2:3-8.

4. The preparation method according to claim 1, characterized in that: In step (1), the coupling reaction temperature is in the range of 10 to 100° C., and the reaction time is 80 to 120 h; Preferably, the reaction is heated from the initial temperature (10°C) at a rate of 5-8°C / min to 25-30°C for 45-50h; then heated at a rate of 5-8°C / min to 55-65°C for 20-25h, and finally heated at a rate of 5-8°C / min to 75-85°C for 20-25h.

5. The preparation method according to claim 1, characterized in that: In step (1), the support used for filtration is polyamide, and the pore size distribution of the support is 0.1 to 1000 nm; the drying condition is drying in an oven at 60 to 100° C. for 3 to 48 hours. Preferably, the pore size distribution of the support is 1 to 500 nm, and the drying condition is drying in an oven at 70 to 90° C. for 10 to 30 hours.

6. The preparation method according to claim 1, characterized in that: In step (2), Azos particles are dispersed in an organic solvent, wherein the organic solvent is one or two of toluene, ethanol, carbon tetrachloride, dimethyl sulfoxide, chloroform, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, ethylene dichloride, ether, acetonitrile, xylene, benzene, benzene bromide, chloroform, acetone, isopropanol, tert-butanol, and carbon tetrachloride; Preferably, the organic solvent is any one or two of dimethylformamide, ethanol, N-methylpyrrolidone and dimethyl sulfoxide.

7. The preparation method according to claim 1, characterized in that In step (2), the polymer matrix is ​​any one of polydimethylsiloxane (PDMS), polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyether copolyamide (Pebax), polyamide (PA), polyimide (PI), self-microporous polymer (PIMs), and cellulose acetate (AT); Preferably, the polymer matrix is ​​polyether copolyamide (Pebax); more preferably, it is any one of Pebax-1074, Pebax-1657, and Pebax-2533.

8. The preparation method according to claim 1 or 7, characterized in that In step (2), the solvent for dissolving the polymer matrix is ​​one or a mixed solvent of two or more of distilled water, ethanol, methanol, n-hexane, n-heptane, toluene, tetrahydrofuran, chloroform, methanol, acetone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, carbon tetrachloride, and n-butanol in different proportions; the condition for dissolving the polymer matrix is ​​reflux at 60-95° C. for 1-3 hours; The concentration of the polymer matrix solution is 0.1-80 wt.%; the mass ratio of the Azos particles to the polymer matrix is ​​1:10-300; Preferably, the solvent for dissolving the polymer matrix is ​​selected from a mixture of distilled water and ethanol in a mass ratio of 1-5:1-10; the concentration of the matrix polymer solution is 0.1-10 wt.%; and the mass ratio of Azos particles to polymer matrix is ​​1:20-200. The blending condition is stirring at 20-30° C. for 1-20 h; preferably, the blending stirring time is 3-10 h.

9. The preparation method according to claim 1, characterized in that In step (2), the vacuum-assisted film forming method or the high pressure and vacuum coupled film forming method uses a support body for filtration, and the support body material is one or more of polytetrafluoroethylene, polyamide, cellulose acetate, ceramic, silicon carbide, aluminum oxide, polyvinylidene fluoride and polyacrylonitrile, and the pore size is 50 to 200 nm; In the vacuum-assisted film forming method, the pressure on the lower surface of the support is 100 to 10,000 PaA; the upper surface is at normal pressure; In the high pressure and vacuum coupling film forming method, the pressure on the lower surface of the support body is 100 to 10000 PaA; the upper surface is pressurized, and the pressure is 20 to 1000 kPaG. The solution casting method is to pour the casting solution of the mixed matrix membrane directly into a culture dish and dry it in a drying oven at 60-100°C for 12-24 hours; Preferably, the pressure on the lower surface of the support in the vacuum assisted film forming method is 100 to 5000 PaA; more preferably, the pressure on the lower surface of the support in the vacuum assisted film forming method is 500 to 3000 PaA; Preferably: in the high-pressure and vacuum coupled film-forming method, the pressure on the lower surface of the support body is 100-5000PaA, and the upper surface is pressurized with a pressure of 50-800kPaG; further preferably: in the high-pressure and vacuum coupled film-forming method, the pressure on the lower surface of the support body is 500-3000PaA, and the upper surface is pressurized with a pressure of 50-600kPaG.

10. Application of the mixed matrix membrane prepared by the method according to claim 1 in CO2 gas separation; preferably: application in CO2 / N2, H2 / CO2, CO2 / CH4 gas separation; Preferably: the pressure on the raw material side is 10-1000 kPaG, and the test temperature is 0-100°C; Further preferably, the pressure on the raw material side is 30-500 kPaG, and the test temperature is 10-50°C.

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