Mesoporous silica and Pebax mixed matrix membrane and preparation method thereof
By using a hybrid matrix membrane of mesoporous silica and Pebax, the contradiction between permeability and selectivity in gas separation membrane materials was resolved, achieving a highly efficient CO2 gas separation effect and improving the permeability and selectivity of CO2 gas.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-02-09
- Publication Date
- 2026-03-31
AI Technical Summary
Existing gas separation membrane materials cannot simultaneously and significantly improve gas permeability and selectivity, and traditional modification methods suffer from high energy consumption and cumbersome operation.
A mixed matrix membrane of mesoporous silica and Pebax was used. By mixing nano-sized SiO2 filler with Pebax-1657 solution to form a uniform casting solution, the mixed matrix membrane was prepared by solvent evaporation, which enhanced the CO2 gas adsorption and permeability of the membrane material.
It significantly improved the CO2 gas permeation performance (PCO2) to 71.84~92.14 Barrer and the CO2/N2 selectivity to 58.69~69.4, achieving efficient separation and capture of gas by the gas separation membrane.
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Figure CN121755075A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of gas membrane separation technology and discloses a mixed matrix membrane of mesoporous silica and Pebax and its preparation method. Background Technology
[0002] In recent years, with rapid social development, industrial demand for energy has exploded. This has intensified the extraction and use of fossil fuels such as coal and oil, thereby exacerbating the problem of excessive CO2 emissions from fossil fuel combustion. Ultimately, this exacerbates the greenhouse effect, causing irreversible damage to ecosystems and seriously threatening human survival and development. To effectively control carbon emissions and achieve carbon neutrality, the issue of CO2 separation, capture, and reuse has received widespread attention in recent years. Traditional CO2 separation and capture technologies mainly include pressure swing adsorption, cryogenic separation, and liquid phase absorption. These methods are not only energy-intensive but also require huge upfront investments and are cumbersome to operate. However, membrane separation technology, which has developed rapidly in recent years, can effectively overcome the shortcomings of traditional separation technologies, achieving simple, efficient, and low-cost separation and capture of CO2.
[0003] After decades of exploration and research, although organic polymers have found some applications in industrial production, their application in many industrial fields is limited due to their low gas permeability, the constraints between permeability and selectivity, poor chemical stability, and susceptibility to plasticization during use. Therefore, appropriate modification treatments are needed for organic polymer membranes. Currently, the simplest method for modifying gas separation membrane materials is doping modification.In his research paper "Solid-solvent processing of ultrathin, highly loaded mixed-matrix membrane for gas separation" published in *Science*, Professor Jin Wanqin of Nanjing University of Technology points out that "MMMs are commonly fabricated through a solution-mixing strategy. Achieving interfacial compatibility between the polymer matrix and the MOF filler is challenging, particularly when the filler loading is high (>30 to 40 vol%). Issues such as filler agglomeration, sedimentation, and filler-polymer interfacial defects may arise during the solvent evaporation process." Similarly, in a review article titled "MOF membranes for gas separations" published in *Progress in Materials Science*, Professor Jürgen Caro, a member of the German Academy of Sciences, and Professor Wang Haihui of Tsinghua University, point out that "In practice, problems related to the dispersibility of MOF fillers, interfacial voids between the polymer and MOF fillers, polymer chain rigidification around MOF fillers, and pore blockage of the..." MOFs are made of polymer chains. MOF loading and particle size can also lead to suboptimal performance. Currently, common dopants used in doping modification processes include organic porous metal frameworks and porous zeolites, which are inorganic dopants. These fillers themselves have well-developed pore structures, thus effectively improving the permeability of gas separation membranes. However, the introduction of porous inorganic fillers, while improving the gas permeability of the membrane material, also reduces the gas selectivity.Therefore, the correct selection of dopants or the effective modification of dopants has become the key to improving the performance of gas separation membranes and ensuring their large-area, high-efficiency industrial application.
[0004] The present invention aims to provide a mixed matrix membrane of mesoporous silica and Pebax and its preparation method. This method involves mixing SiO2 nanoparticle filler with a Pebax-1657 solution to form a uniform casting solution, and then preparing the mixed matrix membrane using a solvent evaporation method. By introducing abundant porous nano-SiO2 filler with selective CO2 gas molecule transport channels into the Pebax organic membrane material, the adsorption and permeability of the membrane material for CO2 gas are effectively enhanced. Simultaneously, the introduced nano-SiO2 filler can effectively regulate the arrangement of the Pebax polymer chains, selectively adjusting the phase separation state of the Pebax membrane material to a certain extent. The nano-SiO2 filler is effectively dispersed between the Pebax molecular chains, inhibiting the crystallization of hard segments, increasing the free volume of the membrane material, and further improving the gas permeability of the membrane material. The increased free volume of Pebax provides more gas storage cavities for CO2 gas molecules to be transported within the membrane, while the nano-porous SiO2 selectively transports and permeates CO2 gas molecules stored in the free cavities of the body. The two complement each other, improving both the permeability and selectivity of CO2 gas molecules.
[0005] Its CO2 permeability (PCO2) can reach 71.84~92.14 Barrer, while the CO2 / N2 selectivity reaches 58.69~69.4.
[0006] To address the problem that membrane materials typically cannot simultaneously and significantly improve gas permeability and selectivity, this invention provides a mixed matrix membrane of mesoporous silica and Pebax, and a method for preparing the same. The method is as follows:
[0007] A mixed matrix film of mesoporous silica and Pebax and its preparation method, comprising the following steps:
[0008] Step 1: Dissolve Pebax-1657 in a mixed solvent of ethanol and water, heat and stir to obtain a homogeneous Pebax-1657 solution;
[0009] Step 2: Dissolve tetraethyl orthosilicate in anhydrous ethanol at a stirring rate of 50-60 rpm, add ammonia dropwise, and let stand for 2-5 hours. After separation and drying, obtain mesoporous silica powder, disperse it in ethanol, and obtain mesoporous silica filler dispersion by ultrasonic dispersion and mechanical stirring.
[0010] Step 3: Mix the Pebax-1657 solution obtained in Step 1 with the mesoporous silica filler dispersion obtained in Step 2, and then treat it with vibration and ultrasound to make the filler uniformly dispersed. After that, let it stand to remove bubbles to obtain a mixed casting solution.
[0011] Step 4: The mixed casting solution is poured into a mold, the solvent is evaporated under heating conditions, and then dried in a vacuum environment to obtain the mesoporous silica / Pebax mixed matrix membrane.
[0012] Further, in step 1, the mass ratio of Pebax-1657 to the mixed solvent is 1:7~32; the heating temperature is 60~80℃.
[0013] Further, in step 1, the mass ratio of ethanol to water in the mixed solvent is 6-9:1-4.
[0014] Further, in step 2, the mass ratio of the mesoporous silica powder to ethanol is 1:10~50; the ultrasonic dispersion time is 2~4 hours; the mechanical stirring rate is 400~600 rpm; and the stirring time is 24~36 hours.
[0015] Furthermore, in step 3, the oscillation treatment lasts for 2 to 4 hours, and the ultrasonic treatment lasts for 10 to 20 minutes.
[0016] Further, in step 3, the mass ratio of the Pebax-1657 solution to the mesoporous silica filler dispersion is 4~20:1.
[0017] Furthermore, in step 4, the conditions for solvent evaporation are: standing at 60~80℃ for 18~24 hours; and the conditions for vacuum drying are: drying at 50~80℃ for 10~12 hours.
[0018] Furthermore, a method for preparing a mesoporous silica / Pebax mixed matrix membrane yields a mesoporous silica / Pebax mixed matrix membrane.
[0019] Furthermore, the mesoporous silica / Pebax hybrid matrix membrane is used for the separation of CO2 / N2 mixed gases.
[0020] This invention provides a mixed matrix membrane of mesoporous silica and Pebax and its preparation method. The mixed matrix membrane is prepared by blending Pebax-1657 as matrix material and porous nano-SiO2 particles as filler, thereby effectively improving the permeability and selectivity of the membrane material to CO2 gas.
[0021] Porous nano-SiO2 possesses an abundant pore structure capable of transporting gas molecules. Its dispersion within the membrane effectively provides ample channels for gas molecule transport. Simultaneously, the uniform distribution of nano-SiO2 particles between Pebax molecular chains increases the distance between chain segments, which to some extent inhibits the crystallization behavior of the PA segment and significantly increases the free volume fraction of the membrane matrix. The larger free volume cavities within the membrane provide more storage sites for CO2 during transport. These CO2 molecules stored in the cavities can permeate and be transported through the selective nanopores in the porous nano-SiO2 that connect the cavities, ultimately resulting in a significant improvement in the transport efficiency of CO2 gas molecules within the membrane. Macroscopically, this manifests as a substantial increase in both the permeability and selectivity of the membrane material for CO2 gas.
[0022] A hybrid matrix membrane of mesoporous silica and Pebax exhibits a CO2 permeability (PCO2) of 71.84 to 92.14 Barrer, while achieving a CO2 / N2 selectivity of 58.69 to 69.4. Attached Figure Description
[0023] Figure 1 The FT-IR spectra of the mixed matrix membranes obtained in Examples 1-4 and the comparative examples are shown below.
[0024] Figure 2 The XRD test curves of the mixed matrix membranes obtained in Examples 1-4 and the comparative examples are shown.
[0025] Figure 3 The TGA test curves are for the mixed matrix membranes obtained in Examples 1-4 and the comparative examples. Detailed Implementation
[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only a part of the embodiments of this invention, not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.
[0027] The following examples illustrate a mesoporous silica and Pebax hybrid matrix membrane and its preparation method provided by the present invention.
[0028] All materials used in the following examples were commercially available. Pebax-1657 was purchased from Arkema, France; ammonia and tetraethyl orthosilicate (TEOS) were purchased from Aladdin Chemical Reagents, Inc., USA.
[0029] Example 1:
[0030] Step 1: Place the Pebax-1657 and the ethanol-water mixture in a mass ratio of 7:3 in a flask, heat in an oil bath at 60°C and stir for 4 hours to obtain a homogeneous Pebax solution, wherein the mass ratio of Pebax-1657 to the mixed solvent is 1:7.
[0031] Step 2: Dissolve tetraethyl orthosilicate in anhydrous ethanol, stir at 50 rpm, then slowly add ammonia, let stand for 5 hours, then centrifuge and dry at 60°C to obtain mesoporous silica powder; add the dried mesoporous silica powder to an ethanol-water mixture with a mass ratio of 7:3, control the mass ratio of mesoporous silica to Pebax1657 to be 0.4:10, wherein the mass ratio of the ethanol-water solution used to disperse SiO2 to the ethanol-water solution used to dissolve Pebax1657 is 2:7. After ultrasonic dispersion for 4 hours, stir at a mechanical stirring rate of 500 rpm for 24 hours to obtain a mesoporous silica filler dispersion.
[0032] Step 3: Add the Pebax-1657 solution obtained in Step 1 to a reagent bottle, add the mesoporous silica filler dispersion obtained in Step 2 (corresponding to a filler content of approximately 4 wt% in the solid membrane), shake with a shaker for 4 hours and sonicate for 20 minutes to ensure uniform dispersion of the filler, and then allow the casting solution to stand to remove bubbles.
[0033] Step 4: Pour the prepared mixed casting solution into a polytetrafluoroethylene mold, adjust the mold to be level using a level, and place it in a 65℃ oven for 24 hours to allow the solvent to evaporate, forming a precursor film. Remove the precursor film, press it between glass plates, and dry it in an 80℃ vacuum oven for 12 hours to obtain a mesoporous silica / Pebax mixed matrix film, which should be sealed and stored.
[0034] The thickness of the prepared hybrid matrix membrane is approximately 55 μm. The separation performance of the hybrid matrix membrane was tested to be PCO2 = 71.84 Barrer and CO2 / N2 selectivity 58.69.
[0035] Example 2:
[0036] Step 1: Place the Pebax-1657 and ethanol-water (7:3) solution in a flask and heat in an oil bath at 60°C for 4 hours to obtain a Pebax solution of uniform concentration, wherein the mass ratio of Pebax-1657 to ethanol-water solution is 1:7.
[0037] Step 2: Dissolve tetraethyl orthosilicate in anhydrous ethanol, stir at 50 rpm, then slowly add ammonia, let stand for 5 hours, then centrifuge and dry at 60°C to obtain mesoporous silica powder; add the dried mesoporous silica powder to an ethanol-water mixture with a mass ratio of 7:3, control the mass ratio of mesoporous silica to Pebax1657 to be 0.6:10, wherein the mass ratio of the ethanol-water solution used to disperse SiO2 to the ethanol-water solution used to dissolve Pebax1657 is 2:7. After ultrasonic dispersion for 4 hours, stir at a mechanical stirring rate of 500 rpm for 24 hours to obtain a mesoporous silica filler dispersion.
[0038] Step 3: Add the Pebax-1657 solution obtained in Step 1 to a reagent bottle, add the mesoporous silica filler dispersion obtained in Step 2 (corresponding to a filler content of approximately 6 wt% in the solid membrane), shake with a shaker for 4 hours and sonicate for 20 minutes to ensure uniform dispersion of the filler, and then allow the casting solution to stand to remove bubbles.
[0039] Step 4: Pour the prepared mixed casting solution into a polytetrafluoroethylene mold, adjust the mold to keep it level using a level, and place it in a 65℃ oven for 24 hours to allow the solvent to evaporate, forming a precursor film. Remove the precursor film, press it between glass plates, and dry it in a 60℃ vacuum oven for 12 hours to obtain a mesoporous silica / Pebax mixed matrix film, which should be sealed and stored.
[0040] The prepared hybrid matrix membrane has a thickness of 60 μm. The separation performance of the hybrid matrix membrane was tested and found to be PCO2 = 82 Barrer, with a CO2 / N2 selectivity of 68.
[0041] Example 3:
[0042] Step 1: Place the Pebax-1657 and ethanol-water (7:3) solution in a flask and heat in an oil bath at 60°C for 4 hours to obtain a Pebax solution of uniform concentration, wherein the mass ratio of Pebax-1657 to ethanol-water solution is 1:7.
[0043] Step 2: Dissolve tetraethyl orthosilicate in anhydrous ethanol, stir at 50 rpm, then slowly add ammonia, let stand for 5 hours, then centrifuge and dry at 60°C to obtain mesoporous silica powder; add the dried mesoporous silica powder to an ethanol-water mixture with a mass ratio of 7:3, control the mass ratio of mesoporous silica to Pebax1657 to be 0.8:10, wherein the mass ratio of the ethanol-water solution used to disperse SiO2 to the ethanol-water solution used to dissolve Pebax1657 is 2:7. After ultrasonic dispersion for 4 hours, stir at a mechanical stirring rate of 500 rpm for 24 hours to obtain a mesoporous silica filler dispersion.
[0044] Step 3: Add the Pebax-1657 solution obtained in Step 1 to a reagent bottle, add the mesoporous silica filler dispersion obtained in Step 2 (corresponding to a filler content of approximately 8 wt% in the solid membrane), shake with a shaker for 4 hours and sonicate for 20 minutes to ensure uniform dispersion of the filler, and then allow the casting solution to stand to remove bubbles.
[0045] Step 4: Pour the prepared mixed casting solution into a polytetrafluoroethylene mold, adjust the mold to keep it level using a level, and place it in a 65℃ oven for 24 hours to allow the solvent to evaporate, forming a precursor film. Remove the precursor film, press it between glass plates, and dry it in a vacuum oven at 80℃ for 12 hours to obtain a mesoporous silica / Pebax mixed matrix film, which should be sealed and stored.
[0046] The prepared hybrid matrix membrane has a thickness of 65 μm. The separation performance of the hybrid matrix membrane was tested and found to be PCO2 = 88 Barrer, with a CO2 / N2 selectivity of 69.84.
[0047] Example 4:
[0048] Step 1: Place the Pebax-1657 and ethanol-water (7:3) solution in a flask and heat in an oil bath at 60°C for 4 hours to obtain a Pebax solution of uniform concentration, wherein the mass ratio of Pebax-1657 to ethanol-water solution is 1:7.
[0049] Step 2: Dissolve tetraethyl orthosilicate in anhydrous ethanol, stir at 50 rpm, then slowly add ammonia, let stand for 5 hours, then centrifuge and dry at 60°C to obtain mesoporous silica powder; add the dried mesoporous silica powder to an ethanol-water mixture with a mass ratio of 7:3, control the mass ratio of mesoporous silica to Pebax1657 to be 1:10, wherein the mass ratio of the ethanol-water solution used to disperse SiO2 to the ethanol-water solution used to dissolve Pebax1657 is 2:7. After ultrasonic dispersion for 4 hours, stir at a mechanical stirring rate of 500 rpm for 24 hours to obtain a mesoporous silica filler dispersion.
[0050] Step 3: Add the Pebax-1657 solution obtained in Step 1 to a reagent bottle, add the mesoporous silica filler dispersion obtained in Step 2 (corresponding to a filler content of approximately 10 wt% in the solid membrane), shake with a shaker for 4 hours and sonicate for 20 minutes to ensure uniform dispersion of the filler, and then allow the casting solution to stand to remove bubbles.
[0051] Step 4: Pour the prepared mixed casting solution into a polytetrafluoroethylene mold, adjust the mold to be level using a level, and place it in a 65°C oven for 24 hours to allow the solvent to evaporate, forming a precursor film. Remove the precursor film, press it between glass plates, and dry it in a 65°C vacuum oven for 12 hours to obtain a mesoporous silica / Pebax mixed matrix film, which should be sealed and stored.
[0052] The thickness of the prepared hybrid matrix membrane was 70 μm. The separation performance of the above hybrid matrix membrane was tested to be PCO2=92.14 Barrer and CO2 / N2 selectivity 62.3.
[0053] Comparative example:
[0054] Preparation of pure Pebax-1657 mixed matrix membrane:
[0055] Pebax-1657 and ethanol were placed in a flask at a mass ratio of 1:7 and heated in an oil bath at 60°C for 4 hours to obtain a Pebax solution of uniform concentration. The solution was then degassed by sonication for 10 minutes, allowed to stand for 10 minutes, and then poured into a clean polytetrafluoroethylene mold. The membrane was then placed in a constant temperature oven and dried at 60°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 12 hours to obtain a mixed matrix membrane with a filler content of 0 wt% Pebax-1657.
[0056] The prepared hybrid matrix membrane has a thickness of 40 μm. The separation performance of the above hybrid matrix membrane was tested to be PCO2 = 65.98 Barrer and CO2 / N2 selectivity 57.24.
[0057] Characterization test instructions:
[0058] like Figure 1 As shown, infrared observations were conducted at 1000-1100 cm. -1 It is the Si-O-Si antisymmetric stretching peak in the mesoporous SiO2 lattice; 500 cm⁻¹ -1 The O-Si-O bending peak is a universal characteristic peak of SiO2; observations of Examples 1-4 clearly show that as the SiO2 doping content increases, the peak located at 1000-1100 cm⁻¹ becomes more prominent. -1 The infrared characteristic peaks gradually increase, and in all embodiments, the 500 cm⁻¹ infrared spectrum of the film material shows this enhancement. -1 Significant new peaks appeared in all ranges, which are O-Si-O bending peaks in mesoporous SiO2. These phenomena are sufficient to prove that SiO2 was successfully doped into Pebax.
[0059] like Figure 2As shown, comparing the XRD patterns of Examples 1-4 and the comparative examples, it can be observed that the characteristic peaks of the PE and PA segments in the crystalline regions of Pebax-1657 are at 2θ = 20.8° and 24.2°, respectively; these peaks gradually become broad peaks with increasing SiO2 filler content. This indicates that the addition of SiO2 significantly reduces the crystallinity of the Pebax film material. This is mainly because the uniform distribution of nano-SiO2 around the Pebax1657 molecular chains hinders the aggregation of molecular chains, thereby inhibiting crystallization behavior. Simultaneously, comparing the examples and the comparative examples, it can be found that with the addition of nano-SiO2, the characteristic diffraction peak of the PA segment at 24.2° shifts to a lower angle, i.e., the 2θ angle shifts to the left. This indicates that the interchain spacing of the Pebax1657 crystalline segments increases. This is also because the nano-SiO2 interspersed around the Pebax molecular chains hinders the aggregation of molecular chains, resulting in an increase in their free volume and a decrease in crystallinity.
[0060] like Figure 3 As shown, comparing the TG spectra of Examples 1-4 with those of the comparative example reveals that Pebax begins to thermally decompose at temperatures above 350 °C. With the increase of SiO2 addition, the decomposition temperature of SiO2 / Pebax MMM in the final stage increases, and the thermal stability gradually improves.
[0061] Performance test description:
[0062] The comparative examples, Examples 1-4, show the component ratios and CO2 permeability (Barrer) and CO2 / N2 selectivity test results of the prepared mixed matrix membranes as shown in Table 1.
[0063] Table 1
[0064] Filler content (wt%) <![CDATA[CO2 Permeability Coefficient (Barrer)]]> <![CDATA[CO2 / N2 selectivity]]> Comparative Example 0 65.98 57.24 Example 1 4 71.84 58.69 Example 2 6 82 68 Example 3 8 88 69.4 Example 4 10 92.14 62.3
[0065] Conclusion: As can be seen from Table 1, the CO2 permeability coefficient and CO2 / N2 selectivity of Examples 1 to 4 of the present invention are better than those of the pure Pebax-1657 mixed matrix membrane prepared in the comparative example. In Example 3, when the filler content is 8 wt.%, the CO2 permeability coefficient can reach 88 Barrer and the CO2 / N2 selectivity is 69.4, which shows good permeability and selectivity.
[0066] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments described herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A method for preparing a mixed matrix film of mesoporous silica and Pebax, characterized in that, Includes the following steps: Step 1: Dissolve Pebax-1657 in a mixed solvent of ethanol and water, heat and stir to obtain a homogeneous Pebax-1657 solution; Step 2: Dissolve tetraethyl orthosilicate in anhydrous ethanol at a stirring rate of 50-60 rpm, add ammonia dropwise, and let stand for 2-5 hours. After separation and drying, obtain mesoporous silica powder, disperse it in ethanol, and obtain mesoporous silica filler dispersion by ultrasonic dispersion and mechanical stirring. Step 3: Mix the Pebax-1657 solution obtained in Step 1 with the mesoporous silica filler dispersion obtained in Step 2, and then treat it with vibration and ultrasound to make the filler uniformly dispersed. After that, let it stand to remove bubbles to obtain a mixed casting solution. Step 4: The mixed casting solution is poured into a mold, the solvent is evaporated under heating conditions, and then dried in a vacuum environment to obtain the mesoporous silica / Pebax mixed matrix membrane.
2. The method for preparing a mixed matrix film of mesoporous silica and Pebax according to claim 1, characterized in that, In step 1, the mass ratio of Pebax-1657 to the mixed solvent is 1:7~32; the heating temperature is 60~80℃.
3. The preparation method according to claim 1 or 2, characterized in that, In step 1, the mass ratio of ethanol to water in the mixed solvent is 6-9:1-4.
4. The method for preparing a mixed matrix film of mesoporous silica and Pebax according to claim 1, characterized in that, In step 2, the mass ratio of the mesoporous silica powder to ethanol is 1:10~50; the ultrasonic dispersion time is 2~4 hours; the mechanical stirring rate is 400~600 rpm; and the stirring time is 24~36 hours.
5. The method for preparing a mixed matrix membrane of mesoporous silica and Pebax according to claim 1, characterized in that, In step 3, the oscillation treatment lasts for 2 to 4 hours, and the ultrasonic treatment lasts for 10 to 20 minutes.
6. The method for preparing a mixed matrix film of mesoporous silica and Pebax according to claim 1, characterized in that, In step 3, the mass ratio of the Pebax-1657 solution to the mesoporous silica filler dispersion is 4~20:
1.
7. The method for preparing a mixed matrix film of mesoporous silica and Pebax according to claim 1, characterized in that, In step 4, the conditions for solvent evaporation are: standing at 60~80℃ for 18~24 hours; the conditions for vacuum drying are: drying at 50~80℃ for 10~12 hours.
8. A mesoporous silica / Pebax hybrid matrix membrane prepared by any one of the preparation methods of claims 1 to 7.
9. The mesoporous silica / Pebax hybrid matrix membrane according to claim 8, characterized in that, The membrane is used for the separation of CO2 / N2 mixed gases.