A method for preparing a mixed matrix membrane using a multi-component hybrid system

Abstract

The application discloses a method for preparing a mixed matrix membrane by using a multi-element hybrid system, and comprises the following steps: a multi-element hybrid system solution preparation step, selecting an organic macromolecule, and simultaneously selecting an inorganic filler, mixing the organic macromolecule and the inorganic filler uniformly in a solvent to form a multi-element hybrid system solution; a matrix solution configuration step, dissolving a polyether block amide into a solvent to form a matrix solution; a membrane preparation liquid configuration step, mixing the multi-element hybrid system solution and the matrix solution, stirring and dispersing to obtain a membrane preparation liquid; and a solidification treatment step, compounding the membrane preparation liquid to a surface of a membrane forming support to obtain a pretreated membrane, drying the pretreated membrane to solidify the pretreated membrane and obtain the mixed matrix membrane. The matrix solution is a polyether block amide solution, the organic macromolecule and the inorganic filler are simultaneously introduced, a multi-element hybrid system is formed in the mixed matrix membrane, and the gas separation performance of the mixed matrix membrane is enhanced by virtue of the adsorption group of the organic macromolecule and the rich pores of the inorganic filler.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of separation technology in the discipline of chemical engineering and technology, and particularly relates to a method for preparing a mixed matrix membrane by using a multi-element hybrid system. BACKGROUND

[0002] In recent years, membrane separation technology has been developed, which can well realize efficient and low-cost separation, capture and recovery of CO2 gas (Liu M, et al., Prog Polym Sci, 2022, 126: 101504; Kunalan S, et al., Environ Sci Pollut Res, 2022, 29(26): 38735-38767). Therefore, research and development of high-performance CO2 separation membrane materials have great commercial prospects and social value. When summarizing all gas separation membrane materials in the world, American scholar Robeson found that there is a constraint relationship between the permeability and selectivity of the membrane material, that is, when the two are plotted on a graph, the data points are below a straight line, which is called the Robeson upper limit. Therefore, current researchers and engineers are committed to breaking through the Robeson upper limit, hoping to prepare membrane materials with good permeability and selectivity for CO2 / N2 system gas separation performance (Robeson LM, J Membr Sci, 2008, 320(1-2): 390-400).

[0003] In the prior art, organic macromolecules are often introduced into the membrane material in order to expect that the membrane material has good permeability and selectivity for CO2 / N2 system gas separation performance, but the result is only that the permeability of the membrane material is good, and the selectivity is low. In the patent CN10809707013, a mixed matrix membrane is prepared by using Zn / Ni doped modification block polyether amide, which has high permeability to CO2 gas, up to 321 Barrer, but the selectivity to CO2 is only 43. Moreover, single doping of inorganic fillers is easy to cause defect pores at the phase interface and brittle fracture of the membrane body due to the hard effect caused by the phase difference between the membrane matrix, resulting in loss of gas separation (Liu G, et al., Chem. Asian J. 2020, 15, 2364.).

[0004] Therefore, in order to solve the above problems, it is necessary to study a method for preparing a mixed matrix membrane by using a multi-element hybrid system. SUMMARY

[0005] The application aims to provide a method for preparing a mixed matrix membrane by using a multi-hybrid system, and the mixed matrix membrane prepared by the multi-hybrid system has the following advantages: on the one hand, the mixed matrix membrane has a high solubility of CO2 gas due to a large number of hydroxyl active groups carried by the organic macromolecule, and a large number of channels for the transmission of CO2 gas are formed in the mixed matrix membrane due to the rich pores of the inorganic filler, so that the permeability of CO2 gas is improved, and the selectivity of the mixed matrix membrane to CO2 gas is significantly improved, and the mixed matrix membrane has good permeability and selectivity for the gas separation performance of the CO2 / N2 system; on the other hand, the mixed matrix membrane prepared by the multi-hybrid system forms a buffer area at the interface between the inorganic filler and the matrix, so that the hard action is converted into the soft action, the problem of defective pores and the brittleness of the membrane body of the mixed matrix membrane is avoided, and the gas separation performance of the mixed matrix membrane is ensured.

[0006] The application provides a method for preparing a mixed matrix membrane by using a multi-hybrid system, comprising the following steps: a multi-hybrid system solution configuration step, selecting an organic macromolecule, and simultaneously selecting an inorganic filler, mixing the organic macromolecule and the inorganic filler uniformly in a solvent to form a multi-hybrid system solution;

[0007] A matrix solution configuration step is performed, in which the polyether block amide is dissolved in the solvent to form a matrix solution.

[0008] A membrane preparation solution configuration step is performed, in which the multi-hybrid system solution and the matrix solution are mixed, stirred, dispersed and configured to obtain a membrane preparation solution.

[0009] A solidification treatment step is performed, in which the membrane preparation solution is compounded on the surface of a film-forming support to obtain a pretreated membrane, and the pretreated membrane is dried and solidified to obtain the mixed matrix membrane.

[0010] Preferably, in the multi-hybrid system solution configuration step, the organic macromolecule is any one or any two of ethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) or polydimethylsiloxane (PDMS).

[0011] Preferably, in the multi-hybrid system solution configuration step, the inorganic filler is any one or any two of NaY zeolite, NaX zeolite, ZSM zeolite, mordenite, SAPO zeolite or silicon zeolite.

[0012] Preferably, in the multi-hybrid system solution configuration step, the particle size of the inorganic filler is 0.01-100 μm, and the mass ratio of the organic macromolecule to the inorganic filler is 0.1-1.2:1.

[0013] Preferably, the solvent is any one of n-butanol, ethanol, acetic acid or dichloroethane.

[0014] Preferably, in the base solution preparation step: the polyether block amide is any one of Pebax 1074, Pebax 1657, Pebax 5533, Pebax 4033, Pebax 3533, Pebax 63R53 or Pebax 6333.

[0015] Preferably, in the membrane forming solution configuration step: the mass concentration of the multi-hybrid system solution is 2-12%, the mass concentration of the base solution is 2-12%, and the mass ratio between the multi-hybrid system solution and the base solution is 0.1-1.2:1.

[0016] Preferably, in the solidification treatment step: the drying temperature is 30-150°C, and the drying time is 2-24 hours.

[0017] Preferably, in the solidification treatment step: the membrane forming support is any one of non-woven fabric, iron mesh, polysulfone filter membrane, glass plate or plastic plate.

[0018] Preferably, in the CO2 / N2 system gas separation performance test, the selectivity of the mixed matrix membrane to CO2 gas is 29-196.

[0019] Compared with the prior art, the present application provides a method for preparing a mixed matrix membrane using a multi-hybrid system. By simultaneously introducing organic macromolecules and inorganic fillers, a multi-hybrid system is formed in the mixed matrix membrane. The solubility of CO2 gas in the mixed matrix membrane is greatly improved by the adsorptive groups of the organic macromolecules. A large number of channels conducive to the transmission of CO2 gas are generated in the mixed matrix membrane by the abundant pores of the inorganic fillers, thereby improving the permeability to CO2 gas. The mixed matrix membrane has good permeability and selectivity for the gas separation performance of the CO2 / N2 system. At the same time, the mixed matrix membrane prepared by using the multi-hybrid system forms a buffer region at the interface between the inorganic filler and the base, which converts the hard action into soft action, avoiding the problems of defective pores and membrane body brittleness in the mixed matrix membrane, effectively ensuring that the mixed matrix membrane has high gas separation performance. BRIEF DESCRIPTION OF DRAWINGS

[0020] The above and other objects, features and advantages of the exemplary embodiments of the present application will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which several embodiments of the present application are shown by way of example, and wherein like reference numerals refer to like elements throughout. In the drawings:

[0021] Figure 1 A scanning electron microscope photograph of the mixed matrix membrane prepared in Example 1 in the present application;

[0022] Figure 2 A scanning electron microscope photograph of the mixed matrix membrane prepared in Example 2 in the present application;

[0023] Figure 3 This is a scanning electron microscope image of the hybrid matrix membrane prepared in Example 3 of this invention;

[0024] Figure 4 This is a scanning electron microscope image of the hybrid matrix membrane prepared in Example 4 of this invention;

[0025] Figure 5 The X-ray diffraction patterns are those of the mixed matrix films prepared in Examples 1 to 4 of this invention.

[0026] Figure 6 Thermogravimetric spectra of the mixed matrix membranes prepared in Examples 1 to 4 of this invention;

[0027] Figure 7 This is a graph showing the relationship between permeability and selectivity of the gas separation performance of the mixed matrix membranes prepared in Examples 1 to 4 of this invention. Detailed Implementation

[0028] Exemplary embodiments of the present disclosure will now be described in more detail with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. Unless otherwise specified, the techniques used in the embodiments are conventional means well known to those skilled in the art.

[0029] It should be noted that, unless otherwise stated, the technical or scientific terms used in this invention should be understood in their ordinary sense by those skilled in the art. The terms "comprising," "including," or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0030] This embodiment presents a method for preparing a hybrid matrix membrane using a multi-component hybrid system, comprising four steps: preparation of the multi-component hybrid system solution, preparation of the matrix solution, preparation of the film-forming solution, and curing treatment.

[0031] The steps for preparing the multi-component hybrid system solution are as follows: Select any one or any two of polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), or polydimethylsiloxane (PDMS) as the organic macromolecule; select any one or any two of NaY zeolite, NaX zeolite, ZSM zeolite, mordenite, SAPO zeolite, or silica zeolite as the inorganic filler; mix the organic macromolecule and inorganic filler uniformly in a solvent, wherein the solvent is any one of n-butanol, ethanol, acetic acid, or dichloroethane; the particle size of the inorganic filler is 0.01–100 μm; the mass ratio of organic macromolecule to inorganic filler is 0.1–1.2:1; and a multi-component hybrid system solution with a mass concentration of 2–12% is formed.

[0032] The matrix solution preparation step involves selecting any one of Pebax1074, Pebax1657, Pebax5533, Pebax4033, Pebax3533, Pebax 63R53, or Pebax6333 and dissolving it in a solvent to form a matrix solution with a mass concentration of 2-12%. The solvent is any one of n-butanol, ethanol, acetic acid, or dichloroethane.

[0033] The preparation steps for the film-forming solution are as follows: the multi-component hybrid system solution and the matrix solution are mixed at a mass ratio of 0.1 to 1.2:1, and after thorough stirring and dispersion, a uniform film-forming solution is obtained.

[0034] The curing process involves applying the film-forming liquid to the surface of any film-forming support, such as nonwoven fabric, wire mesh, polysulfone filter membrane, glass plate, or plastic plate, using any one of the following methods: brushing, spraying, casting, or spin coating, to obtain a pretreated membrane. The pretreated membrane is then cured at a drying temperature of 30–150°C for 2–24 hours to obtain a mixed matrix membrane.

[0035] The pre-treatment membrane formed on the glass or plastic plate needs to be softened with a small amount of warm water, and then peeled off to finally obtain a mixed matrix membrane with a certain degree of non-support.

[0036] The gas separation performance of the mixed matrix membrane for the CO2 / N2 system, namely permeability and selectivity, was tested using a single-component gas constant-volume pressure swing permeation method. The test conditions were room temperature and a transmembrane pressure difference of 0.1 MPa.

[0037] The gas separation performance test process is as follows: First, the mixed matrix membrane is sealed in a stainless steel membrane tank with sealant or sealing gasket. High-purity gas from the gas cylinder is fixed by a pressure regulating valve to permeate through the mixed matrix membrane. After stabilization, the effective gas flux is measured, and the permeability of the mixed matrix membrane is calculated according to formula (1). The selectivity of the mixed matrix membrane is calculated according to formula (2) (see reference: Yao Yanhu, et al. Journal of Chemical Industry and Engineering, 2021, 72(8): 4418-4424).

[0038]

[0039] Among them, P i The permeability of a gas (general unit: Barrer, 1 Barrer = 0.33 × 10⁻⁶) -15 kmol·m·m -2 ·s -1 ·kPa -1 ), i is CO2 gas or N2 gas, F is the gas flux through the membrane, ΔP is the transmembrane pressure difference, A is the effective membrane area, and L is the effective membrane thickness.

[0040]

[0041] Among them, S A / B For the selectivity between CO2 and N2 gases, P A For the permeability of CO2 gas, P B The permeability of N2 gas.

[0042] from Figure 5 It can be seen that the mixed matrix membranes prepared in Examples 1 to 4, under the combined action of organic macromolecules and inorganic fillers, have organic macromolecules and inorganic fillers uniformly distributed inside the mixed matrix membrane substrate, indicating that a multi-component hybrid system is formed inside the mixed matrix membrane.

[0043] from Figure 6 The thermogravimetric data show that the multi-component hybrid system introduced into the interior of the mixed matrix membrane prepared in Examples 1 to 4 did not affect the main pyrolysis temperature range and pyrolysis mechanism of the mixed matrix membrane, indicating that the mixed matrix membrane has good thermal stability after modification in this example.

[0044] from Figure 7 It is evident that the gas separation performance of the hybrid matrix membrane prepared by the method of this invention exceeds the Robeson upper limit.

[0045] The method for preparing hybrid matrix membranes using a multi-component hybrid system in this embodiment has the following advantages compared with the prior art:

[0046] This embodiment uses Pebax as the matrix solution material. By mixing organic macromolecules with inorganic fillers in a solvent, porous zeolite with a porous structure and organic macromolecule fillers with numerous hydroxyl active groups are introduced. This creates a large number of microporous structures within the mixed matrix membrane, allowing for gas transport and permeation. The addition of organic macromolecule fillers also introduces numerous hydroxyl active groups capable of adsorbing CO2, further enhancing the specific adsorption of CO2 gas by the mixed matrix membrane at the microscopic level and increasing the solubility of CO2 gas within the membrane. This improves both the permeability and solubility selectivity of the mixed matrix membrane for CO2 gas. Furthermore, the synergistic blending of organic and inorganic materials improves the compatibility between the inorganic porous zeolite and the matrix, thus avoiding the defects, porosity, and membrane embrittlement problems that occur when using inorganic fillers alone, ensuring the permeability and selectivity of the mixed matrix membrane.

[0047] Example 1

[0048] Polyethylene glycol (PEG) or polydimethylsiloxane (PDMS) was selected as the organic macromolecule; NaY zeolite or SAPO zeolite was selected as the inorganic filler; the organic macromolecule and inorganic filler were mixed uniformly in n-butanol as the solvent, wherein the mass ratio of organic macromolecule to inorganic filler was 0.1:1, forming a multi-component hybrid system solution with a mass concentration of 2%.

[0049] Choose any one of Pebax1074, Pebax1657, Pebax5533, Pebax4033, Pebax3533, Pebax63R53, or Pebax6333, and dissolve it in n-butanol to form a matrix solution with a mass concentration of 2-12%.

[0050] The multi-component hybrid system solution and the matrix solution were mixed at a mass ratio of 1.2:1, and after thorough stirring and dispersion, a uniform film-forming solution was obtained.

[0051] The film-forming solution is applied to the surface of the nonwoven fabric by casting. The pre-prepared film is then cured at a drying temperature of 30–150°C for 2–24 hours to obtain a mixed matrix film.

[0052] The gas separation performance of the mixed matrix membrane for the CO2 / N2 system was determined by measuring its gas separation performance, as shown in Table 1. For ease of comparison, Table 1 also lists the preparation conditions and gas separation performance of the mixed matrix membrane without added organic macromolecular fillers, i.e., number 0.

[0053] Table 1. Experimental data of hybrid matrix membranes with wide-range tunable permeability and selectivity prepared by multi-component hybrid systems.

[0054]

[0055]

[0056] Note: In Table 1, when two organic macromolecules or two inorganic fillers are used at the same time, the ratio of the amount of organic macromolecules or inorganic fillers is 1:1 (mass ratio), and the particle size of the inorganic filler is the average particle size value.

[0057] Combined with Table 1, Figure 1 , Figure 5 and Figure 6 It is evident that the mixed matrix membrane prepared by adding only inorganic fillers exhibits extremely low selectivity, indicating the presence of defective pores within the membrane. In contrast, simultaneously introducing organic macromolecules and inorganic fillers into the mixed matrix membrane, constructing a multi-component hybrid system, significantly improves the selectivity of the mixed matrix membrane for CO2 gas. Simultaneously, the permeability of some mixed matrix membranes is also enhanced. Furthermore, from... Figure 7 It is evident that by adjusting the Pebax type, matrix solution concentration, drying temperature, drying time, and inorganic filler particle size as the main preparation process conditions, the solubility and diffusivity of CO2 gas within the mixed matrix membrane were simultaneously improved. Under the action of the dissolution-diffusion separation mechanism, effective control of the permeability of the mixed matrix membrane material was achieved over a wide range, and the permeability and selectivity of the mixed matrix membrane for CO2 gas were both higher than the Robeson upper limit. These experimental data fully demonstrate that the mixed matrix membrane prepared by this embodiment effectively avoids the problems of defective pores and membrane embrittlement, ensuring the gas separation performance of the mixed matrix membrane while taking into account both the permeability and selectivity of the mixed matrix membrane for CO2 gas.

[0058] Example 2

[0059] Choose one or both of polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) as the organic macromolecule; choose one or both of NaX zeolite, ZSM zeolite, mordenite or silica zeolite as the inorganic filler; mix the organic macromolecule and the inorganic filler uniformly in ethanol as the solvent, wherein the mass ratio of organic macromolecule to inorganic filler is 0.1 to 1.2:1, to form a multi-component hybrid system solution with a mass concentration of 2 to 12%.

[0060] Pebax1657 was selected and diluted with a mixture of ethanol and water (volume ratio of 70:30) as a solvent. Pebax1657 was dissolved in the diluted ethanol solvent to form a matrix solution with a mass concentration of 2-12%.

[0061] The multi-component hybrid system solution and the matrix solution are mixed at a mass ratio of 1:1, and after thorough stirring and dispersion, a uniform film-forming solution is obtained.

[0062] A membrane-forming solution was coated onto the surface of a polysulfone filter membrane using a brush coating method. The pre-formed membrane was then cured at a drying temperature of 30–150℃ for 2–24 hours to obtain a mixed matrix membrane. The gas separation performance of the mixed matrix membrane for the CO2 / N2 system was measured, as shown in Table 2. For ease of comparison, Table 2 also lists the preparation conditions and gas separation performance of the mixed matrix without added organic macromolecular fillers (number 0).

[0063] Table 2 Experimental data of hybrid matrix membranes with high permeability and selectivity prepared by multi-component hybrid systems.

[0064]

[0065] Note: In Table 2, when two organic macromolecules or two inorganic fillers are used at the same time, the ratio of the amount of organic macromolecules or inorganic fillers is 1:1 (mass ratio), and the particle size of the inorganic filler is the average particle size value.

[0066] Combined with Table 1, Figure 2 , Figure 5 and Figure 6 It can be seen that the extremely low selectivity of the mixed matrix membrane prepared by adding only inorganic filler indicates the presence of defective pores within the membrane, i.e., number 0. In contrast, mixed matrix membranes that simultaneously introduce organic macromolecules and inorganic fillers to construct a multi-component hybrid system significantly improve gas separation selectivity. Furthermore, from... Figure 7 It is evident that by adjusting the mass ratio of organic macromolecules to inorganic fillers, the concentration of the multi-component hybrid system solution, and the particle size of the inorganic fillers as the main preparation process conditions, the solubility and diffusivity of CO2 gas within the mixed matrix membrane were altered. Under the action of the dissolution-diffusion separation mechanism, the permeability and selectivity of the mixed matrix membrane material could be effectively controlled simultaneously, and the permeability and selectivity of the mixed matrix membrane for CO2 gas both exceeded the Robeson upper limit. These experimental data fully demonstrate that the mixed matrix membrane prepared in this embodiment effectively avoids the problems of defective pores and membrane embrittlement, ensuring the gas separation performance of the mixed matrix membrane while balancing the permeability and selectivity of the mixed matrix membrane for CO2 gas.

[0067] Example 3

[0068] One or two of polyethylene glycol (PEG) and polydimethylsiloxane (PDMS) are selected as organic macromolecules; one or two of NaY zeolite and NaX zeolite are selected as inorganic fillers; the organic macromolecules and inorganic fillers are mixed uniformly in acetic acid as solvent, wherein the mass ratio of organic macromolecules to inorganic fillers is 0.6:1, forming a multi-component hybrid system solution with a mass concentration of 4%.

[0069] Choose any one of Pebax 5533, Pebax 4033, Pebax 3533, Pebax 63R53 or Pebax 6333, and dissolve it in acetic acid to form a matrix solution with a mass concentration of 2-12%.

[0070] The multi-component hybrid system solution and the matrix solution were mixed at a mass ratio of 0.1:1, and after thorough stirring and dispersion, a uniform film-forming solution was obtained.

[0071] The film-forming liquid is coated onto the surface of a 2000-mesh steel wire mesh using a spraying method. The pre-prepared membrane is then cured at a drying temperature of 30–150°C for 2–24 hours to obtain a mixed matrix membrane.

[0072] The gas separation performance of the mixed matrix membrane for the CO2 / N2 system was determined by measuring its gas separation performance, as shown in Table 3.

[0073] Table 3. Experimental data of highly permeable hybrid matrix membranes prepared from multi-component hybrid systems.

[0074]

[0075] Note: In Table 3, when two organic macromolecules or two inorganic fillers are used at the same time, the ratio of the amount of organic macromolecules or inorganic fillers is 1:1 (mass ratio), and the particle size of the inorganic filler is the average particle size value.

[0076] Combined with Table 1, Figure 3 , Figure 5 and Figure 6 It can be seen that the prepared hybrid matrix membranes all exhibit excellent gas separation performance in terms of permeability and selectivity on a macroscopic scale. Furthermore, from... Figure 7 It is evident that by adjusting the main preparation process conditions—organic macromolecules, inorganic filler types, matrix solution concentration, drying temperature, drying time, and inorganic filler particle size—the solubility and diffusivity of CO2 gas within the mixed matrix membrane were altered. Under the dissolution-diffusion separation mechanism, effective control of the high permeability of the mixed matrix membrane material was achieved, and the permeability and selectivity of the mixed matrix membrane for CO2 gas both exceeded the Robeson upper limit. These experimental data fully demonstrate that the mixed matrix membrane prepared in this embodiment effectively avoids the problems of defective pores and membrane embrittlement, ensuring the gas separation performance of the mixed matrix membrane while balancing its permeability and selectivity for CO2 gas.

[0077] Example 4

[0078] Choose one or both of polyethylene glycol (PEG) and polyvinyl alcohol (PVA) as organic macromolecules; choose any one or any two of ZSM zeolite, mordenite, and SAPO zeolite as inorganic fillers; mix the organic macromolecules and inorganic fillers uniformly in dichloroethane as solvent, wherein the mass ratio of organic macromolecules to inorganic fillers is 1:1, to form a multi-component hybrid system solution with a mass concentration of 10%.

[0079] Pebax 3533 was selected and dissolved in dichloroethane to form a matrix solution with a mass concentration of 8%.

[0080] The solution of the multi-component hybrid system and the matrix solution are mixed at a mass ratio of 0.8:1, and after thorough stirring and dispersion, a uniform film-forming solution is obtained.

[0081] A pre-prepared membrane is obtained by spin coating a membrane-forming solution onto the surface of a non-woven fabric, wire mesh, polysulfone filter membrane, glass plate, or plastic plate. The pre-prepared membrane is then cured at a drying temperature of 60°C for 20 hours to obtain a mixed matrix membrane.

[0082] The pre-prepared membrane formed on a glass or plastic plate needs to be softened with a small amount of warm water before being peeled off, ultimately yielding an unsupported mixed matrix membrane. The gas separation performance of the mixed matrix membrane for the CO2 / N2 system was measured, as shown in Table 4.

[0083] Table 4. Experimental data of highly selective hybrid matrix membranes prepared from multi-component hybrid systems.

[0084]

[0085] Note: In Table 4, when two organic macromolecules or two inorganic fillers are used at the same time, the ratio of the amount of organic macromolecules or inorganic fillers is 1:1 (mass ratio), and the particle size of the inorganic filler is the average particle size value.

[0086] Combined with Table 1, Figure 4 , Figure 5 and Figure 6 It can be seen that the prepared hybrid matrix membranes all exhibit excellent gas separation performance in terms of permeability and selectivity. Furthermore, from... Figure 7It is evident that by adjusting the main preparation process conditions—the type of film-forming support, organic macromolecules, inorganic fillers, and the particle size of the inorganic fillers—the solubility and diffusivity of CO2 gas within the mixed matrix membrane were altered. Under the dissolution-diffusion separation mechanism, effective control of the high selectivity of the mixed matrix membrane material was achieved, and the permeability and selectivity of the mixed matrix membrane for CO2 gas both exceeded the Robeson upper limit. These experimental data fully demonstrate that the mixed matrix membrane prepared in this embodiment effectively avoids the problems of defective pores and membrane embrittlement, ensuring the gas separation performance of the mixed matrix membrane while balancing its permeability and selectivity for CO2 gas.

[0087] The above are merely specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a hybrid matrix membrane using a multi-component hybrid system, characterized in that, include: The steps for preparing a multi-component hybrid system solution are as follows: Select an organic macromolecule and an inorganic filler, and mix the organic macromolecule and the inorganic filler evenly in a solvent to form a multi-component hybrid system solution; The matrix solution preparation step involves dissolving the polyether block amide in a solvent to form a matrix solution. The membrane-forming solution preparation step involves mixing the multi-component hybrid system solution with the matrix solution, followed by stirring, dispersion, and preparation to obtain the membrane-forming solution. The curing process involves bonding the film-forming liquid to the surface of the film-forming support to obtain a pretreated film, followed by drying to cure the pretreated film and thus obtaining a mixed matrix film. In the solution preparation steps of a multi-component hybrid system: The organic macromolecule is any one or any two of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone or polydimethylsiloxane. In the solution preparation steps of a multi-component hybrid system: The inorganic filler is any one or any two of NaY zeolite, NaX zeolite, ZSM zeolite, mordenite, SAPO zeolite, or silica zeolite. The solvent is any one of n-butanol, ethanol, acetic acid, or dichloroethane; In the matrix solution preparation step: The polyether block amide is any one of Pebax1074, Pebax1657, Pebax5533, Pebax4033, Pebax3533, Pebax63R53 or Pebax6333; In the curing process step: The film-forming support is any one of non-woven fabric, wire mesh, polysulfone filter membrane, glass plate or plastic plate; The mass ratio of the organic macromolecule to the inorganic filler is 0.1~1.2:

1.

2. The method for preparing a hybrid matrix membrane using a multi-component hybrid system according to claim 1, characterized in that, In the solution preparation steps of a multi-component hybrid system: The particle size of the inorganic filler is 0.01–100 μm.

3. The method for preparing a hybrid matrix membrane using a multi-component hybrid system according to claim 1, characterized in that, In the preparation step of the film-forming solution: The mass concentration of the multi-component hybrid system solution is 2-12%, the mass concentration of the matrix solution is 2-12%, and the mass ratio between the multi-component hybrid system solution and the matrix solution is 0.1-1.2:

1.

4. The method for preparing a hybrid matrix membrane using a multi-component hybrid system according to claim 1, characterized in that, In the curing process step: The drying temperature is 30-150℃, and the drying time is 2-24 hours.

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