Azos polymer mixed matrix membranes, methods of making and using the same

Abstract

The application discloses an Azos polymer mixed matrix membrane and a preparation method and application thereof, the method is as follows: one or more aniline compounds are dissolved in an organic solvent, and a coupling reaction is carried out under the action of a catalyst and a catalyst auxiliary agent thereof; after the reaction is completed, filtering, washing and drying are sequentially carried out, and Azos particles with an azo functional group are obtained; the Azos particles are ultrasonically dispersed in an organic solvent, and are added into a dissolved polymer matrix solution to blend, and a casting solution is obtained after uniform stirring; the obtained casting solution is treated by ultrasonic defoaming, and then a vacuum assisted film forming method or a high pressure and vacuum coupled film forming method or a solution casting method is adopted to form a film, finally, the film is placed into an oven for drying at 70-90 DEG C for 10-15 h, and an Azos / polymer mixed matrix membrane is obtained. The application has the advantages of simple operation, environmental friendliness, low cost and the like, and provides a new selection for the fields of bio-ethanol preparation, gas adsorption / separation and the like.

Description

Technical Field

[0001] This invention relates to the preparation method and application of Azos / polymer hybrid matrix membranes, belonging to the fields of hybrid matrix membrane preparation technology, membrane application, and environmental protection technology, and particularly to the field of CO2 gas separation. Background Technology

[0002] Since the Industrial Revolution, the global economy has been rapidly developing, leading to increased global demand for energy, particularly traditional fossil fuels (natural gas, oil, and coal). The resulting massive CO2 emissions not only cause environmental problems such as global warming and ocean acidification but also result in a significant waste of carbon resources. Therefore, the development of CO2 separation technologies is urgently needed. Compared to traditional separation technologies, membrane separation offers advantages such as simple operation, low energy consumption and cost, small footprint, and no secondary pollution, balancing high efficiency and economy, and thus possesses enormous potential.

[0003] The trade-off between permeability and selectivity remains a major constraint on membrane development. To overcome this constraint, numerous methods have been proposed to improve performance. Mixed matrix membranes (MMMs) prepared by dispersing highly selective adsorption fillers in a continuous phase are one of the most effective methods to overcome the Robeson 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 traditional mixed matrix membranes currently use inorganic fillers, which present compatibility and dispersibility issues with organic polymer matrices. Therefore, developing mixed matrix membranes with organic fillers holds great potential for CO2 separation. Summary of the Invention

[0004] The present invention aims to provide a method for preparing a mixed matrix membrane using Azos particles. Starting with the filler material, this invention increases the specific surface area of ​​the polymer particles by introducing three-dimensional and network-structured monomers, providing sufficient adsorption sites for CO2. Simultaneously, it increases the affinity for CO2 through azo bonds, tertiary amine groups, and other functional groups. Furthermore, the membrane fabrication method is improved to make the membrane layer more dense, reducing the permeation performance of the mixed matrix membrane to N2 and thus enhancing the CO2 / N2 separation performance.

[0005] The objective of this invention can be achieved through the following measures:

[0006] A method for preparing a hybrid 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 auxiliaries; after the reaction is completed, filter, wash and dry in sequence to obtain Azos particles with azo functional groups;

[0008] (2) Disperse Azos particles in an organic solvent by ultrasonication, add them to a well-dissolved polymer matrix solution for mixing, and stir until uniform to obtain a casting solution; after ultrasonic degassing treatment of the obtained casting solution, then use vacuum-assisted film formation method, high pressure and vacuum coupling film formation method or solution casting method to form a film, and finally put it into an oven at 70-90℃ for 10-15h to obtain an Azos / polymer mixed matrix film.

[0009] In the technical solution of this invention: In step (1), the aniline compound is selected from 2,6,14-triaminotriphenylene, N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine, tris(4-aminophenyl)amine, 1,4-phenylenediamine, 4,4'-(4,4'-isopropylidene diphenyl-1,1'-dioxane)diphenylamine, 4-aminophenyl sulfone, o-phenylenediamine, m-phenylenediamine, 1,4-phenylenediamine, benzidine, 4-propoxy-1,2-diaminebenzene, 3-(2,4-diaminophenoxy)propane-1,2-diol, 4-(2-methoxyethoxy)-5-methylbenzene-1,3-diphenylene Amines, 2,7-diaminobenzo-9,10-diones, 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”-di Amino-4-terphenyl, 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'-diaminobenzoyl aniline, 2,4-diaminoanisole, 2,7-diaminodiphenyl sulfone, 3,6-thioanthraquinone diamine, o-toluidine sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, 3,3'-diaminodiphenyl sulfone, diaminodiphenylmethane, 3,3'-bis(2,4-diaminophenyl)sulfone (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, 2,4,5,6-tetrafluoro-1,3-phenylenediamine;

[0010] Preferably, the aniline compound monomer is one or more of 2,6,14-triaminotriptene, N,N,N',N'-tetratetra(p-aminophenyl)p-phenylenediamine, 4-propoxy-1,2-diaminebenzene, 1,4-phenylenediamine, and benzidine;

[0011] Further preferred: the aniline compound monomers are 2,6,14-triaminotriptene and N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine in a molar ratio of 1-3:1-3.

[0012] In the technical solution of this 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, diethyl ether, ethyl cyanide, xylene, benzene, brominated benzene, chloroform, 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 auxiliary is one of pyridine, furan, or thiophene;

[0015] 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.

[0016] The molar ratio between aniline compounds, catalysts, and catalyst auxiliaries is 0.1–2:0.1–2:0.1–10;

[0017] Preferred molar ratio of aniline compound, catalyst and catalyst auxiliary agent: 1-2:1-2:3-8.

[0018] In the technical solution of this invention: 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;

[0019] Preferably, the reaction is initiated at an initial temperature (10°C) and heated at a rate of 5–8°C / min until reaching 25–30°C, at which point the reaction lasts for 45–50 hours. Subsequently, the temperature is increased at a rate of 5–8°C / min until reaching 55–65°C, at which point the reaction lasts for 20–25 hours. Finally, the temperature is increased at a rate of 5–8°C / min until reaching 75–85°C, at which point the reaction lasts for 20–25 hours.

[0020] In the technical solution of the present invention: in step (1), the filter uses a polyamide support with a pore size distribution of 0.1 to 1000 nm; the drying conditions are drying in an oven at 60 to 100°C for 3 to 48 hours.

[0021] Preferably, the pore size distribution of the support is 1-500 nm, and the drying conditions are drying in an oven at 70-90℃ for 10-30 h.

[0022] In the technical solution of this invention: 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, dichloroethane, diethyl ether, ethyl cyanide, xylene, benzene, brominated benzene, chloroform, acetone, isopropanol, tert-butanol, and 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), self-porous polymers (PIMs), and cellulose acetate (AT).

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

[0026] In the technical solution of this invention, in step (2), the solvent for dissolving the polymer matrix is ​​one or more of the following solvents in different proportions: distilled water, ethanol, methanol, n-hexane, n-heptane, toluene, tetrahydrofuran, chloroform, methanol, acetone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, carbon tetrachloride, and n-butanol; the conditions for dissolving the polymer matrix are reflux at 60–95°C for 1–3 hours.

[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 ​​selected from a mixture of distilled water and ethanol with a mass ratio of 1 to 5:1 to 10; the concentration of the matrix polymer solution is 0.1 to 10 wt.%; and the mass ratio of Azos particles to polymer matrix is ​​1:20 to 200.

[0029] The blending conditions are stirring at 20–30°C for 1–20 hours; preferably, the blending time is 3–10 hours.

[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. The support material is one or more of polytetrafluoroethylene, polyamide, cellulose acetate, ceramic, silicon carbide, alumina, polyvinylidene fluoride and polyacrylonitrile, with a pore size of 50-200 nm.

[0031] In vacuum-assisted film formation, the pressure on the lower surface of the support is 100–10000 PaA, while the pressure on 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 to 10000 PaA; the upper surface is pressurized with a pressure of 20 to 1000 kPaG.

[0033] The solution casting method involves directly pouring the casting solution of the mixed matrix membrane into a petri dish and drying it in a drying oven at 60–100℃ for 12–24 hours.

[0034] Preferably, the pressure on the lower surface of the support in the vacuum-assisted film formation method is 100–5000 PaA; more preferably, the pressure on the lower surface of the support in the vacuum-assisted film formation method is 500–3000 PaA.

[0035] Preferably, in the high-pressure and vacuum coupled film formation method, the pressure on the lower surface of the support is 100–5000 PaA, and the upper surface is pressurized with a pressure of 50–800 kPaG. More preferably, in the high-pressure and vacuum coupled film formation method, the pressure on the lower surface of the support is 500–3000 PaA, and the upper surface is pressurized with a pressure of 50–600 kPaG.

[0036] In the technical solution of the present invention, the mixed matrix membrane prepared by the method is used in CO2 gas separation; preferably, it is used in CO2 / N2, H2 / CO2, and CO2 / CH4 gas separation.

[0037] Preferred settings: The pressure on the raw material side is 10–1000 kPaG, and the test temperature is 0–100℃;

[0038] Further optimization: the pressure on the raw material side is 30-500 kPaG, and the test temperature is 10-50℃.

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

[0040] The beneficial effects of this invention are as follows: This invention prepares a hybrid matrix membrane by synthesizing a novel Azos-filled membrane. The core of this invention lies in the preparation of a hybrid matrix membrane for separating CO2 / N2 systems using a vacuum-assisted membrane formation method and a high-pressure and vacuum coupling membrane formation method. Compared with solution casting, this method improves separation selectivity without changing the permeation rate. Matrix polymer membrane materials possess good ductility, thermal stability, and chemical stability. However, matrix polymer membrane materials inherently involve a trade-off between permeability and selectivity. Therefore, the microporous organic polymer particles introduced in this invention can improve the separation selectivity of the homogeneous membrane prepared. Furthermore, the membrane material is prepared by vacuum filtration, and the membrane thickness is precisely controlled by adjusting the casting solution quality, reducing accidental errors caused by human intervention. Studies have shown that the denser the hybrid matrix membrane structure, the higher the separation selectivity of the membrane layer, which is beneficial for efficient CO2 / N2 separation [CN118356812A]. Attached Figure Description

[0041] Figure 1 This is an electron microscope image of the Azo-3 particles in Example 3.

[0042] Figure 2 The infrared spectra of the Azos particles in Examples 1-5 are shown.

[0043] Figure 3 The images shown are electron microscope images of the surface and cross-section of the mixed matrix membrane in Example 3.

[0044] Figure 4 This is a CO2 / N2 adsorption selectivity diagram of the polymer particles in Example 3. Detailed Implementation

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

[0046] This invention uses the constant-volume pressure-switching method to measure the permeability coefficient P (Barrer) of the prepared hybrid matrix membrane, where 1 Barrer = 10⁻⁶. -10 cm 3 (STP)cm / (cm 2 The calculation formula for (·s·cmHg) is as follows:

[0047]

[0048] Where l is the film thickness (cm) and A is the film area (cm²). 2 T is the test temperature (K), p is the atmospheric pressure (cmHg), and V is the volume of soap bubble flowing through (cm³). 3 ), t is time (s), ΔP i x is the transmembrane pressure (cmHg). i and y iP0 and P1 represent the volume fractions of component i on the feed side and permeate side, respectively, and the pressures on the feed side and permeate side, respectively.

[0049] The formula for calculating the selectivity of Azos / polymer hybrid matrix membranes is as follows:

[0050]

[0051] Among them, P CO2 and P N2 These correspond to the permeability coefficients of CO2 and N2, respectively.

[0052] Example 1

[0053] 0.38 g (1.26 mmol) of 2,6,14-triaminotriptene was added to a mixture of 50 mL THF and 50 mL toluene and stirred until dissolved. 0.234 g (1.63 mmol) of cuprous bromide was then added, followed by 0.5 mL (6.21 mmol) of pyridine. The initial temperature was 10 °C, and the temperature was increased to 25 °C at a rate of 5 °C / min. The mixture was stirred for 48 h, then increased to 60 °C at a rate of 5 °C / min for 24 h, and finally increased to 80 °C at a rate of 5 °C / min for 24 h. After the reaction, the reaction solution was washed three times with tetrahydrofuran, hydrochloric acid, and water, respectively, and then filtered through a polyamide support with a pore size of 100 nm. The resulting polymer was dried in an 80 °C oven for 12 h to obtain Azo-1 particles.

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

[0055] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, it was filtered for another 1 hour. After filtration, it was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-1 / Pebax mixed matrix membrane.

[0056] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 55.69 Barrer, and the N2 permeability coefficient was 0.81 Barrer. The ideal selectivity was 68.75.

[0057] Example 2

[0058] 0.25 g (0.84 mmol) of 2,6,14-triaminotriptene and 0.19 g (0.42 mmol) of N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine were weighed and added to a mixture of 50 mL THF and 50 mL toluene. The mixture was stirred, followed by the addition of 0.23 g (1.63 mmol) of cuprous bromide, and then 0.5 mL (6.21 mmol) of pyridine. The initial temperature was 10 °C, and the temperature was increased to 25 °C at a rate of 5 °C / min. The mixture was stirred for 48 h, then increased to 60 °C at a rate of 5 °C / min for 24 h, and finally increased to 80 °C at a rate of 5 °C / min for 24 h. After the reaction, the reaction solution was washed three times with tetrahydrofuran, hydrochloric acid, and water, and then filtered through a polyamide support with a pore size of 100 nm. The resulting polymer was dried in an 80 °C oven for 12 h to obtain Azo-2 particles.

[0059] 0.003 g of Azo-2 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-2 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0060] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, it was filtered for another 1 hour. After filtration, it was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-2 / Pebax mixed matrix membrane.

[0061] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 49.23 Barrer, and the N2 permeability coefficient was 0.66 Barrer. The ideal selectivity was 71.09.

[0062] Example 3

[0063] 0.19 g (0.63 mmol) of 2,6,14-triaminotriptene and 0.29 g (0.63 mmol) of N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine were weighed and added to a mixture of 50 mL THF and 50 mL toluene and stirred. Then, 0.23 g (1.63 mmol) of cuprous bromide was added, followed by 0.5 mL (6.21 mmol) of pyridine. The initial temperature was 10 °C, and the temperature was increased to 25 °C at a rate of 5 °C / min. The mixture was stirred for 48 h, then increased to 60 °C at a rate of 5 °C / min for 24 h, and finally increased to 80 °C at a rate of 5 °C / min for 24 h. After the reaction, the reaction solution was washed three times with tetrahydrofuran, hydrochloric acid, and water, respectively, and then filtered through a polyamide support with a pore size of 100 nm. The resulting polymer was dried in an 80 °C oven for 12 h to obtain Azo-3 particles.

[0064] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0065] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was filtered for another 1 hour. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80°C forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0066] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 47.33 Barrer, and the N2 permeability coefficient was 0.5 Barrer. The ideal selectivity was 94.66.

[0067] Example 4

[0068] 0.25 g (0.42 mmol) of 2,6,14-triaminotriptene and 0.39 g (0.84 mmol) of N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine were weighed and added to a mixture of 50 mL THF and 50 mL toluene and stirred. Then, 0.23 g (1.63 mmol) of cuprous bromide was added, followed by 0.5 mL (6.21 mmol) of pyridine. The initial temperature was 10 °C, and the temperature was increased to 25 °C at a rate of 5 °C / min. The mixture was stirred for 48 h, then increased to 60 °C at a rate of 5 °C / min for 24 h, and finally increased to 80 °C at a rate of 5 °C / min for 24 h. After the reaction, the reaction solution was washed three times with tetrahydrofuran, hydrochloric acid, and water, respectively, and then filtered through a polyamide support with a pore size of 100 nm. The resulting polymer was dried in an 80 °C oven for 12 h to obtain Azo-4 particles.

[0069] 0.003 g of Azo-4 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-4 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0070] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, it was filtered for another 1 hour. After filtration, it was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-4 / Pebax mixed matrix membrane.

[0071] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 45.5 Barrer, and the N2 permeability coefficient was 0.58 Barrer. The ideal selectivity was 78.44.

[0072] Example 5

[0073] 0.59 g (1.26 mmol) of N,N,N',N'-tetra(p-aminophenyl)-p-phenylenediamine was added to a mixture of 50 mL THF and 50 mL toluene and stirred. Then, 0.23 g (1.63 mmol) of cuprous bromide was added, followed by 0.5 mL (6.21 mmol) of pyridine. The initial temperature was 10 °C, and the temperature was increased to 25 °C at a rate of 5 °C / min. The mixture was stirred for 48 h, then increased to 60 °C at a rate of 5 °C / min for 24 h, and finally increased to 80 °C at a rate of 5 °C / min for 24 h. After the reaction, the reaction solution was washed three times with tetrahydrofuran, hydrochloric acid, and water, respectively, and then filtered through a polyamide support with a pore size of 100 nm. The resulting polymer was dried in an 80 °C oven for 12 h to obtain Azo-5 particles.

[0074] 0.003 g of Azo-5 particles were weighed and added to 0.597 g of DMF solution, and then ultrasonically dispersed to prepare a polymer particle dispersion. Subsequently, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-5 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0075] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, it was filtered for another 1 hour. After filtration, it was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-5 / Pebax mixed matrix membrane.

[0076] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 41.97 Barrer, and the N2 permeability coefficient was 0.57 Barrer. The ideal selectivity was 73.63.

[0077] Example 6

[0078] 0.0008 g of Azo-3 particles were weighed and added to 0.1492 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.146 g of Pebax polymer was weighed and dissolved in 4.704 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0079] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was filtered for another 1 hour. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80°C forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0080] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 27.78 Barrer, and the N2 permeability coefficient was 0.46 Barrer. The ideal selectivity was 60.

[0081] Example 7

[0082] 0.0015 g of Azo-3 particles were weighed and added to 0.2985 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.141 g of Pebax polymer was weighed and dissolved in 4.559 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0083] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was filtered for another 1 hour. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80°C forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0084] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 30.31 Barrer, and the N2 permeability coefficient was 0.41 Barrer. The ideal selectivity was 74.68.

[0085] Example 8

[0086] 0.0023 g of Azo-3 particles were weighed and added to 0.4477 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.1365 g of Pebax polymer was weighed and dissolved in 4.4135 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0087] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was filtered for another 1 hour. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80°C forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0088] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 34.72 Barrer, and the N2 permeability coefficient was 0.39 Barrer. The ideal selectivity was 89.72.

[0089] Example 9

[0090] 0.0038 g of Azo-3 particles were weighed and added to 0.7462 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.1275 g of Pebax polymer was weighed and dissolved in 4.1225 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0091] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was filtered for another 1 hour. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80°C forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0092] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 59.57 Barrer, and the N2 permeability coefficient 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. Then, 0.123 g of Pebax polymer was weighed and dissolved in 3.977 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0095] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was filtered for another 1 hour. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80°C forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0096] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 86.45 Barrer, and the N2 permeability coefficient was 1.72 Barrer. The ideal selectivity was 50.34.

[0097] Example 11

[0098] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0099] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). Filtration was completed once no liquid remained on the surface. The membrane was then allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax hybrid matrix membrane.

[0100] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 72 Barrer, and the N2 permeability coefficient was 1.1 Barrer. The ideal selectivity was 65.47.

[0101] Example 12

[0102] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0103] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was vacuum filtered for another 10 minutes. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0104] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 64.48 Barrer, and the N2 permeability coefficient was 0.93 Barrer. The ideal selectivity was 68.97.

[0105] Example 13

[0106] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0107] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was vacuum filtered for another 30 minutes. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0108] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 58.73 Barrer, and the N2 permeability coefficient was 0.75 Barrer. The ideal selectivity was 78.72.

[0109] Example 14

[0110] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0111] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was vacuum filtered for another 2 hours. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0112] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 44.99 Barrer, and the N2 permeability 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 ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0115] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, filtration was continued and the solution was placed under a pressure of 100 kPaG (upper surface) for 1 hour to assist in preparation. The solution was then allowed to stand at room temperature for 2 hours, and finally dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0116] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 42.57 Barrer, and the N2 permeability coefficient was 0.45 Barrer. The ideal selectivity was 95.03.

[0117] Example 16

[0118] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0119] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, filtration was continued and the solution was placed under a pressure of 200 kPaG (upper surface) for 1 hour to assist in preparation. The solution was then allowed to stand at room temperature for 2 hours, and finally dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0120] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 40.34 Barrer, and the N2 permeability coefficient was 0.42 Barrer. The ideal selectivity was 95.47.

[0121] Example 17

[0122] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0123] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, filtration was continued and the solution was placed under a pressure of 400 kPaG (upper surface) for 1 hour to assist in preparation. The solution was then allowed to stand at room temperature for 2 hours, and finally dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0124] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 37.48 Barrer, and the N2 permeability coefficient was 0.39 Barrer. The ideal selectivity was 95.73.

[0125] Example 18

[0126] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0127] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, filtration was continued and the solution was placed under a pressure of 600 kPaG (upper surface) for 1 hour to assist in preparation. The solution was then allowed to stand at room temperature for 2 hours, and finally dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0128] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 35.48 Barrer, and the N2 permeability coefficient was 0.36 Barrer. The ideal selectivity was 97.53.

[0129] Example 19

[0130] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0131] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, filtration was continued and the solution was placed under a pressure of 400 kPaG (upper surface) for 30 minutes to assist in preparation. The solution was then allowed to stand at room temperature for 2 hours and finally dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0132] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 40.21 Barrer, and the N2 permeability coefficient was 0.42 Barrer. The ideal selectivity was 95.52.

[0133] Example 20

[0134] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0135] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 1000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, filtration was continued and the solution was placed under a pressure of 400 kPaG (upper surface) for 2 hours to assist in preparation. The solution was then allowed to stand at room temperature for 2 hours, and finally dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0136] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 36.45 Barrer, and the N2 permeability coefficient was 0.38 Barrer. The ideal selectivity was 96.65.

[0137] Example 21

[0138] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0139] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polytetrafluoroethylene support (pore size: 150 nm). After the surface was free of liquid, it was filtered for another 1 hour. After filtration, it was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0140] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 50.64 Barrer, and the N2 permeability coefficient was 0.61 Barrer. The ideal selectivity was 82.65.

[0141] Example 22

[0142] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0143] First, the casting solution was ultrasonically degassed for 5 minutes, and then vacuum filtered (lower surface pressure was 1000 PaA) to make the casting solution uniformly cover the polyacrylonitrile support (pore size: 50 nm). After the surface was free of liquid, it was filtered for another 1 hour. After filtration, it was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0144] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 45.64 Barrer, and the N2 permeability coefficient was 0.49 Barrer. The ideal selectivity was 92.65.

[0145] Example 23

[0146] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0147] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure was 1000 PaA) to ensure that the casting solution was evenly covered on the polyvinylidene fluoride support (pore size: 200 nm). After the surface was free of liquid, the solution was filtered for another 1 hour. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80°C forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0148] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 60.64 Barrer, and the N2 permeability coefficient was 0.77 Barrer. The ideal selectivity was 78.85.

[0149] Example 24

[0150] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0151] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 500 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was vacuum filtered for another 1 hour. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0152] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 45.32 Barrer, and the N2 permeability coefficient was 0.47 Barrer. The ideal selectivity was 97.32.

[0153] Example 25

[0154] 0.003 g of Azo-3 particles were weighed and added to 0.597 g of DMF solution, and ultrasonically dispersed to prepare a polymer particle dispersion. Then, 0.132 g of Pebax polymer was weighed and dissolved in 4.268 g of an ethanol / water mixture (ethanol / water mass ratio = 70 / 30), refluxed at 80 °C and continuously stirred for 2 h to obtain a matrix polymer solution. The Azo-3 particle dispersion was then added to the Pebax matrix polymer solution, and the mixture was stirred uniformly at 25 °C for 8 h to obtain a casting solution.

[0155] First, the casting solution was ultrasonically degassed for 5 minutes, then vacuum filtered (lower surface pressure 3000 PaA) to ensure the casting solution uniformly covered the polyamide support (pore size: 100 nm). After the surface was free of liquid, the solution was vacuum filtered for another 1 hour. After filtration, the solution was allowed to stand at room temperature for 2 hours, and then dried in an 80℃ forced-air drying oven for 12 hours to obtain the Azo-3 / Pebax mixed matrix membrane.

[0156] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 54.32 Barrer, and the N2 permeability coefficient was 0.6 Barrer. The ideal selectivity was 90.62.

[0157] Comparative Example 1

[0158] Weigh 0.15 g of Pebax polymer and dissolve it in 4.85 g of an ethanol-water mixture (ethanol / water mass ratio = 70 / 30). Reflux at 80 °C and stir continuously for 2 h to obtain a Pebax polymer solution. Then, vacuum filter (absolute pressure on the lower surface: 1000 Pa) to ensure the Pebax polymer solution uniformly covers the polyamide support (pore size: 100 nm). After the surface is free of liquid, continue vacuum filtration for another 1 h. After filtration, allow to stand at room temperature for 2 h, then dry in an 80 °C forced-air drying oven for 12 h to obtain the Pebax mixed matrix membrane.

[0159] The separation performance of the hybrid matrix membrane obtained in this example for the CO2 / N2 system was tested. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 22.26 Barrer, and the N2 permeability coefficient was 0.4 Barrer. The ideal selectivity was 55.65.

[0160] Comparative Example 2

[0161] Weigh 0.15g of Pebax polymer and dissolve it in 4.85g of an ethanol-water mixture (ethanol / water mass ratio = 70 / 30). Reflux the solution at 80℃ and stir continuously for 2 hours to obtain a Pebax polymer solution. First, degas the Pebax polymer solution using ultrasonication for 5 minutes, then pour it into a polytetrafluoroethylene (PTFE) petri dish and dry it in an 80℃ oven for 12 hours to obtain a homogeneous Pebax membrane.

[0162] The Pebax homogenized membrane obtained in this example was tested for separation performance of the CO2 / N2 system. The effective area of ​​the polymer membrane was 10 cm². 2 The membrane feedstock side pressure was 200 kPaG, and the test temperature was 25℃. Permeation results showed that the CO2 permeability coefficient was 90.36 Barrer, and the N2 permeability coefficient was 1.87 Barrer. The ideal selectivity was 48.43.

Claims

1. A method for preparing a hybrid matrix membrane, characterized in that: The method includes the following steps: (1) Aniline compounds are dissolved in an organic solvent and coupled under the action of a catalyst and its catalyst auxiliaries; after the reaction is completed, the mixture is filtered, washed and dried to obtain Azos particles with coupled functional groups. The aniline compounds are 2,6,14-triaminotriptene and N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine in a molar ratio of 1~3:1~3; The reaction begins at an initial temperature of 10 °C and is heated at a rate of 5–8 °C / min until it reaches 25–30 °C, at which point the reaction lasts for 45–50 h. The temperature is then increased at a rate of 5–8 °C / min until it reaches 55–65 °C, at which point the reaction lasts for 20–25 h. Finally, the temperature is increased at a rate of 5–8 °C / min until it reaches 75–85 °C, at which point the reaction lasts for 20–25 h. (2) Disperse Azos particles in an organic solvent by ultrasonication, add them to a well-dissolved polymer matrix solution for mixing, and stir until uniform to obtain a casting solution; after ultrasonic degassing treatment, the casting solution is then formed by vacuum-assisted film formation or high-pressure and vacuum coupling film formation, and finally placed in an oven at 70~90 ℃ for 10~15 h to obtain an Azos / polymer mixed matrix membrane; The polymer matrix is ​​a polyether copolyamide Pebax, and the polyether copolyamide Pebax is any one of Pebax-1074, Pebax-1657, and Pebax-2533.

2. The preparation method according to claim 1, characterized in that: In step (1), the organic solvent is one or two of tetrahydrofuran, toluene, ethanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, dichloroethane, diethyl ether, ethyl cyanide, xylene, benzene, brominated benzene, chloroform, acetone, isopropanol, tert-butanol and carbon tetrachloride; The catalyst is any one of cuprous chloride, cuprous bromide, cuprous iodide, sodium nitrite, and potassium nitrite; The catalyst auxiliary is one of pyridine, furan, or thiophene.

3. The preparation method according to claim 2, characterized in that: In step (1), 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 between the aniline compound, the catalyst, and the catalyst auxiliaries is 0.1~2:0.1~2:0.1~10.

4. The preparation method according to claim 3, characterized in that: The molar ratio between the aniline compound, the catalyst, and the catalyst auxiliaries is 1~2:1~2:3~8.

5. The preparation method according to claim 1, characterized in that: In step (1), the filter uses a polyamide support with a pore size distribution of 0.1–1000 nm; the drying conditions are drying in an oven at 60–100 °C for 3–48 h.

6. The preparation method according to claim 5, characterized in that: The pore size distribution of the support is 1~500 nm, and the drying conditions are drying in an oven at 70~90 ℃ for 10~30 h.

7. The preparation method according to claim 1, characterized in that: In step (2), the Azos particles are dispersed in an organic solvent, which is one or two of toluene, ethanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, dichloroethane, diethyl ether, ethyl cyanide, xylene, benzene, brominated benzene, chloroform, acetone, isopropanol, tert-butanol, and carbon tetrachloride.

8. The preparation method according to claim 7, characterized in that: The organic solvent is any one or two of dimethylformamide, ethanol, N-methylpyrrolidone, and dimethyl sulfoxide.

9. The preparation method according to claim 1, characterized in that... 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).

10. The preparation method according to claim 1, characterized in that... In step (2), the solvent for dissolving the polymer matrix is ​​selected from a mixture of distilled water and ethanol with a mass ratio of 1~5:1~10; the concentration of the polymer matrix solution is 0.1~10 wt.%; and the mass ratio of Azos particles to polymer matrix is ​​1:(20~200). The blending conditions are stirring at 20–30 °C for 1–20 h.

11. The preparation method according to claim 1, characterized in that... In step (2), the vacuum-assisted film formation method or the high-pressure and vacuum coupled film formation method uses a support for filtration. The support material is one or more of polytetrafluoroethylene, polyamide, cellulose acetate, ceramic, silicon carbide, alumina, polyvinylidene fluoride and polyacrylonitrile, with a pore size of 50~200 nm. In vacuum-assisted film formation, the pressure on the lower surface of the support is 100–10000 PaA, while the pressure on the upper surface is at atmospheric pressure. In the high-pressure and vacuum coupling film formation method, the pressure on the lower surface of the support is 100 to 10000 PaA; the upper surface is pressurized with a pressure of 20 to 1000 kPaG.

12. The preparation method according to claim 11, characterized in that... In the vacuum-assisted film formation method, the pressure on the lower surface of the support is 100–5000 PaA; in the high-pressure and vacuum coupled film formation method, the pressure on the lower surface of the support is 100–5000 PaA, and the upper surface is pressurized with a pressure of 50–800 kPaG.

13. The preparation method according to claim 12, characterized in that... In the vacuum-assisted film formation method, the pressure on the lower surface of the support is 500–3000 PaA; in the high-pressure and vacuum coupled film formation method, the pressure on the lower surface of the support is 500–3000 PaA, and the upper surface is pressurized with a pressure of 50–600 kPaG.

14. The application of the mixed matrix membrane prepared by the method of claim 1 in CO2 gas separation, wherein the application is in the separation of CO2 / N2, H2 / CO2, and CO2 / CH4 gases.

15. The application according to claim 14, characterized in that, The pressure on the raw material side is 10–1000 kPaG, and the test temperature is 0–100 ℃.

16. The application according to claim 15, characterized in that, The pressure on the raw material side is 30–500 kPaG, and the test temperature is 10–50 ℃.

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