Asymmetric hollow fiber mixed matrix membranes, methods of making and applications thereof

Abstract

The application relates to the field of membrane separation technology, in particular to an asymmetric hollow fiber mixed matrix membrane and a preparation method and application thereof. The asymmetric hollow fiber mixed matrix membrane comprises a support layer and a separation layer which is in contact with the outside of the support layer; the raw material of the separation layer is casting solution X which is composed of an organic polymer A, multilayer MXene and a solvent B; the raw material of the support layer is casting solution Y which is composed of an organic polymer C, a pore-forming agent and a solvent D; the content of the multilayer MXene in the casting solution X is 5wt%-15wt%. The multilayer MXene and the organic polymer are compounded according to a specific proportion, the multilayer MXene is added into the separation layer of the asymmetric hollow fiber mixed matrix membrane, and the multilayer MXene and the organic polymer are jointly used to prepare an asymmetric composite hollow fiber membrane, and the obtained asymmetric hollow fiber mixed matrix membrane has good gas permeability, mechanical strength and pressure resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of membrane separation technology, in particular to an asymmetric hollow fiber mixed matrix membrane and a preparation method and application thereof. BACKGROUND

[0002] Helium (He) is a colorless noble gas, which is a strategic rare gas resource. It is rare and precious, and is called "golden gas". Helium is mainly derived from uranium, thorium radioactive decay and mantle degassing. The helium resource on earth is extremely limited and extremely unevenly distributed. Due to its chemical inertness and extremely low boiling point (4.3 K), helium is widely used in low-temperature superconducting, rocket, missile, laser technology, nuclear technology and medical technology fields.

[0003] Purification of helium from natural gas is the main way to capture helium resources. Membrane separation technology is a "green technology". Its typical characteristics are normal temperature operation, no phase change, low energy consumption, high safety, and low investment. It is the most likely separation technology to realize efficient and low-cost helium purification. Hollow fiber membrane is a kind of high-efficiency gas separation technology, which can realize selective separation of different gas molecules by using special membrane material and structure design. The characteristics of this kind of membrane are hollow fiber structure, which can realize the separation of different gases under certain pressure difference according to the size and properties of gas molecules. However, the existing hollow fiber membrane has problems such as high permeability and high selectivity, poor uniformity, and it is difficult to realize efficient helium separation and purification, and large-scale commercialization is limited.

[0004] In view of this, the present application is proposed. SUMMARY

[0005] In order to solve the above-mentioned problems in the prior art, the present application provides an asymmetric hollow fiber mixed matrix membrane and a preparation method and application thereof.

[0006] Based on this, the present application has the following technical solutions:

[0007] In a first aspect, the present application provides an asymmetric hollow fiber mixed matrix membrane, comprising a support layer and a separation layer arranged in contact with the outside of the support layer; the raw material of the separation layer is casting solution X, which is composed of organic polymer A, multi-layer MXene and solvent B; the raw material of the support layer is casting solution Y, which is composed of organic polymer C, pore former and solvent D; the content of the multi-layer MXene in the casting solution X is 5wt%-15wt%.

[0008] MXene is a new type of two-dimensional material, which is a transition metal carbon (nitrogen) compound, and its chemical formula is M n+1 X n T Xwherein M is an early transition metal, such as titanium, vanadium, chromium, manganese, etc., X is carbon or (and) nitrogen, n is an integer 1, 2, 3, etc., T X represents its surface functional groups, such as common MXenes are titanium carbide, niobium carbide, vanadium carbide, chromium carbide, titanium nitride, vanadium nitride, niobium nitride, chromium nitride, titanium carbonitride, niobium carbonitride, vanadium carbonitride, chromium carbonitride, titanium niobium carbide, vanadium chromium carbide, etc.

[0009] The multi-layer MXene is obtained by partial etching of the MAX phase, which has the characteristics of high porosity and uniform and controllable interlayer spacing in sub-nanometer scale, and as a filler of the mixed matrix membrane, it can not only change the packing of polymer chains and improve permeability, but also accurately screen gas molecules, thereby increasing selectivity.

[0010] The previous research of the application uses multi-layer MXene to prepare an organic-inorganic composite hollow fiber membrane, which has good gas permeability, mechanical strength and pressure resistance, but subsequent research finds that there is still room for further improvement. The further research of the application finds that the multi-layer MXene is added to the separation layer of the asymmetric hollow fiber mixed matrix membrane to make an asymmetric composite hollow fiber membrane together with the organic polymer, and the gas permeability, mechanical strength and pressure resistance of the asymmetric hollow fiber mixed matrix membrane can be further improved.

[0011] As a preference, the maximum transverse size L (μm) and the thickness d (nm) of the multi-layer MXene and M further satisfy: M=Z×(d / L) 1 / 2 wherein Z is a correction coefficient, ranging from 1.12 to 2.12.

[0012] In the application, the MXene is not particularly limited and can be selected from one or more of the above common MXenes. The maximum transverse size refers to the maximum size in the horizontal direction perpendicular to the thickness direction.

[0013] As a preference, the outer diameter of the asymmetric hollow fiber mixed matrix membrane is 0.3-0.6 mm, and the wall thickness is 0.06-0.09 mm; wherein the thickness of the separation layer is 0.01-0.02 mm.

[0014] As a preference, the organic polymer A is selected from one or more of polydimethylsiloxane, poly(dimethylsiloxane-co-diphenylsiloxane) and polyimide; preferably, the content of the organic polymer A in the casting solution X is 20wt%-40wt%.

[0015] As a preference, the solvent B is selected from one or more of n-heptane, n-hexane and petroleum ether.

[0016] As preferred, the organic polymer C is selected from one or more of polysulfone, polyimide, polyetherimide, polyethersulfone, sulfonated polysulfone, polyether ether ketone, polyaryletherketone; preferably, the mass percentage content C% of the organic polymer C in the casting solution Y is 30% to 50%.

[0017] As preferred, the pore-forming agent is selected from one or more of polyvinyl alcohol, polyethylene glycol; preferably, the mass percentage content S% of the pore-forming agent in the casting solution Y is 1% to 5%.

[0018] As preferred, the solvent D is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide.

[0019] In a second aspect, the present application provides a preparation method of the asymmetric hollow fiber mixed matrix membrane, comprising:

[0020] S1: uniformly mixing an organic polymer A, a multi-layer MXene and a solvent B to obtain a casting solution X; uniformly mixing an organic polymer C, a pore-forming agent and a solvent D, and vacuum degassing to obtain a casting solution Y; preferably, the solid content of the casting solution X is 25% to 55%; and / or, the solid content of the casting solution Y is 30% to 55%;

[0021] S2: using dry-wet combined spinning technology to spin the casting solution Y to obtain a hollow fiber support layer;

[0022] S3: drying the hollow fiber support layer at room temperature, and then immersing in the casting solution X; wherein the drying temperature is 60 to 80℃.

[0023] As preferred, in S3, the immersion time t1 is 30 to 60 min, the drying temperature T3 is 60 to 80℃, and the drying time t2 is 10 to 24 h.

[0024] As preferred, in S2, the spinning pressure P1 is 0.2 to 0.6 MPa, the core liquid is water, the core liquid pressure P2 is 0.05 to 0.1 MPa, the core liquid temperature T1 is 50 to 80℃, the coagulation bath temperature T2 is 30 to 50℃, and the air gap L0 is 1 to 10 cm.

[0025] In a third aspect, the present application provides an application of the asymmetric hollow fiber mixed matrix membrane in gas separation.

[0026] The asymmetric hollow fiber mixed matrix membrane of the present application can be used for separation of helium and methane, separation of hydrogen and methane, etc. Specifically, the asymmetric hollow fiber mixed matrix membrane of the present application has high helium / methane separation selectivity, and has good application prospect in the fields of natural gas helium extraction and helium recovery.

[0027] Based on this, the technical scheme of the present application has the following beneficial effects:

[0028] The asymmetric hollow fiber mixed matrix membrane provided by the present application, the preparation method and application thereof, by compounding the multilayer MXene and the organic polymer according to a specific ratio, adding the multilayer MXene into the separation layer of the asymmetric hollow fiber mixed matrix membrane, and jointly making the asymmetric composite hollow fiber membrane with the organic polymer, the obtained asymmetric hollow fiber mixed matrix membrane has good gas permeability, mechanical strength and pressure resistance. Especially, it has high helium / methane separation selectivity, and has good application prospect in the fields of natural gas helium extraction and helium recovery. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the present application or prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0030] Figure 1 The scanning electron microscope graph of the multilayer MXene used in example 1 provided by the present application.

[0031] Figure 2 The cross-section scanning electron microscope graph of the asymmetric hollow fiber mixed matrix membrane based on multilayer MXene prepared in example 1 provided by the present application, the left side is a low magnification graph, and the right side is a high magnification graph. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical scheme and advantages of the present application more clear, the following will combine the drawings in the present application to clearly and completely describe the technical scheme in the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0033] The specific technology or condition not mentioned in the embodiments is carried out according to the technology or condition described in the literature in the art, or according to the product instruction. The reagent or instrument not mentioned by the manufacturer is a conventional product that can be purchased through a regular channel.

[0034] Example 1

[0035] The present embodiment provides an asymmetric hollow fiber mixed matrix membrane based on multilayer MXene, and the casting solution X of the separation layer thereof is composed of the following components:

[0036] Organic polymer A: polydimethylsiloxane, mass percentage of 20%;

[0037] Multi-layer MXene: titanium carbide, L = 5 μm, d = 100 nm, mass percentage of 5%; the scanning electron microscope image of the multi-layer MXene is shown in Figure 1 ;

[0038] Solvent B: n-heptane, mass percentage of 75%;

[0039] The casting solution Y of the support layer has the following composition:

[0040] Organic polymer C: polysulfone, mass percentage of 30%;

[0041] Pore-forming agent: polyethylene glycol, mass percentage of 1%;

[0042] Solvent D: N,N-dimethylformamide, mass percentage of 69%;

[0043] The embodiment also provides a preparation method of the asymmetric hollow fiber mixed matrix membrane described above, comprising the following steps:

[0044] (1) Mix the formula amount of organic polymer A, multi-layer MXene, and solvent B, and heat and stir to obtain a casting solution X;

[0045] (2) After heating and stirring and vacuum degassing, the formula amount of organic polymer C, pore-forming agent, and solvent D are obtained to obtain a casting solution Y;

[0046] (3) The casting solution Y is added to a pressure tank, a spinning head is connected, steel cylinder gas is used as a pressure source, dry-wet combined spinning technology is used for spinning, and a hollow fiber support layer is obtained; in the dry-wet spinning process, the spinning pressure is 0.2 MPa, the core liquid is tap water, the core liquid pressure is 0.05 MPa, the core liquid temperature is 50°C, the coagulation bath is tap water, the coagulation bath temperature is 30°C, and the air gap is 1 cm;

[0047] (4) The obtained hollow fiber support layer is collected and dried at room temperature for 24 hours.

[0048] (5) The obtained hollow fiber support layer is immersed in the formula amount of the casting solution X for 30 min, and then taken out and dried at 60°C for 24 hours;

[0049] The outer diameter of the asymmetric hollow fiber mixed matrix membrane obtained in the embodiment is 0.3 mm, the wall thickness is 0.06 mm, and the separation layer thickness is 0.01 mm. The cross-sectional scanning electron microscope image is shown in Figure 2 .

[0050] Example 2

[0051] The embodiment provides a multi-layer MXene-based asymmetric hollow fiber mixed matrix membrane, and a casting solution X of a separation layer of the asymmetric hollow fiber mixed matrix membrane is composed as follows:

[0052] An organic polymer A: poly (dimethylsiloxane-co-diphenylsiloxane) with a mass percentage of 40%;

[0053] A multi-layer MXene: vanadium carbide, L=1 μm, d=50 nm, and a mass percentage of 15%;

[0054] A solvent B: n-hexane with a mass percentage of 45%;

[0055] A casting solution Y of a support layer of the asymmetric hollow fiber mixed matrix membrane is composed as follows:

[0056] An organic polymer C: polyether sulfone with a mass percentage of 50%;

[0057] A pore-forming agent: polyethylene glycol with a mass percentage of 5%;

[0058] A solvent D: N,N-dimethylacetamide with a mass percentage of 45%.

[0059] The embodiment further provides a preparation method of the asymmetric hollow fiber mixed matrix membrane, and the preparation method comprises the following steps:

[0060] (1) mixing the formula amount of the organic polymer A, the multi-layer MXene and the solvent B, and uniformly stirring after heating to obtain a casting solution X;

[0061] (2) mixing the formula amount of the organic polymer C, the pore-forming agent and the solvent D, and obtaining a casting solution Y after heating, stirring and vacuum degassing;

[0062] (3) adding the casting solution Y into a pressure tank, connecting a spinning head, using steel cylinder gas as a pressure source, and using dry-wet combination spinning technology to perform spinning to obtain a hollow fiber support layer; in the dry-wet spinning process, the spinning pressure is 0.6 MPa, the core liquid is tap water, the core liquid pressure is 0.1 MPa, the core liquid temperature is 80 DEG C, the coagulation bath is tap water, the coagulation bath temperature is 50 DEG C, and the air gap is 10 cm;

[0063] (4) collecting the obtained hollow fiber support layer and drying at room temperature for 24 hours;

[0064] (5) immersing the obtained hollow fiber support layer into the formula amount of the casting solution X, immersing for 60 min, and then taking out and drying at 80 DEG C for 10 hours;

[0065] The asymmetric hollow fiber mixed matrix membrane obtained in this embodiment has an outer diameter of 0.6 mm and a wall thickness of 0.09 mm, wherein the separation layer has a thickness of 0.02 mm.

[0066] Example 3

[0067] This embodiment provides an asymmetric hollow fiber mixed matrix membrane based on multi-layer MXene, and the composition of the casting solution X of the separation layer is as follows:

[0068] Organic polymer A: polyimide, mass percentage of 30%;

[0069] Multi-layer MXene: titanium carbide, L = 2 pm, d = 40 nm, mass percentage of 8%;

[0070] Solvent B: petroleum ether, mass percentage of 62%;

[0071] The composition of the casting solution Y of the support layer is as follows:

[0072] Organic polymer C: polysulfone, mass percentage of 40%;

[0073] Pore-forming agent: polyvinyl alcohol, mass percentage of 3%;

[0074] Solvent D: dimethyl sulfoxide, mass percentage of 57%.

[0075] This embodiment also provides a preparation method of the asymmetric hollow fiber mixed matrix membrane described above, comprising the following steps:

[0076] (1) Mix the formula amount of organic polymer A, multi-layer MXene, and solvent B, and heat and stir until uniform to obtain a casting solution X;

[0077] (2) Mix the formula amount of organic polymer C, pore-forming agent, and solvent D, and heat and stir, and then vacuum degas to obtain a casting solution Y;

[0078] (3) Add the casting solution Y into a pressure tank, connect a spinning head, use steel cylinder gas as the pressure source, and use dry-wet combined spinning technology to spin to obtain a hollow fiber support layer; in the dry-wet spinning process, the spinning pressure is 0.4 MPa, the core liquid is tap water, the core liquid pressure is 0.07 MPa, the core liquid temperature is 70°C, the coagulation bath is tap water, the coagulation bath temperature is 40°C, and the air gap is 5 cm;

[0079] (4) Collect the obtained hollow fiber support layer and dry at room temperature for 24 hours;

[0080] (5) Dip the obtained hollow fiber support layer into the formula amount of casting solution X for 50 minutes, and then take it out and dry at 70°C for 18 hours;

[0081] The asymmetric hollow fiber mixed matrix membrane obtained in this embodiment has an outer diameter of 0.5 mm and a wall thickness of 0.07 mm, wherein the separation layer has a thickness of 0.015 mm.

[0082] Example 4

[0083] This embodiment provides an asymmetric hollow fiber mixed matrix membrane based on multilayer MXene, the casting solution X of the separation layer thereof has the following composition:

[0084] Organic polymer A: polydimethylsiloxane, mass percentage of 30%;

[0085] Multilayer MXene: titanium carbide, L = 2 pm, d = 5 nm, mass percentage of 8%;

[0086] Solvent B: n-hexane, mass percentage of 62%;

[0087] The casting solution Y of the support layer thereof has the following composition:

[0088] Organic polymer C: polysulfone, mass percentage of 40%;

[0089] Pore-forming agent: polyethylene glycol, mass percentage of 3%;

[0090] Solvent D: N,N-dimethylformamide, mass percentage of 57%.

[0091] This embodiment also provides a preparation method of the asymmetric hollow fiber mixed matrix membrane described above, comprising the following steps:

[0092] (1) Mix the formula amount of organic polymer A, multilayer MXene, and solvent B, and heat and stir to obtain a casting solution X;

[0093] (2) Mix the formula amount of organic polymer C, pore-forming agent, and solvent D, and heat and stir to obtain a casting solution Y after vacuum degassing;

[0094] (3) Add the casting solution Y into a pressure tank, connect a spinning head, use steel cylinder gas as the pressure source, and use dry-wet combined spinning technology to spin to obtain a hollow fiber support layer; in the dry-wet spinning process, the spinning pressure is 0.4 MPa, the core liquid is tap water, the core liquid pressure is 0.07 MPa, the core liquid temperature is 70°C, the coagulation bath is tap water, the coagulation bath temperature is 40°C, and the air gap is 5 cm;

[0095] (4) Collect the obtained hollow fiber support layer and dry at room temperature for 24 hours.

[0096] (5) The hollow fiber support layer obtained above is immersed in a casting solution X of a formulation amount for 50 min, and then taken out and dried at a temperature of 70°C for 18 hours;

[0097] The asymmetric hollow fiber mixed matrix membrane obtained in this example has an outer diameter of 0.55 mm and a wall thickness of 0.075 mm, wherein the separation layer has a thickness of 0.018 mm.

[0098] Example 5

[0099] This example provides an asymmetric hollow fiber mixed matrix membrane based on multi-layer MXene, which is different from Example 1 only in that the organic polymer A polydimethylsiloxane is replaced with an equal amount of polyvinyl butyral ester.

[0100] Example 6

[0101] This example provides an asymmetric hollow fiber mixed matrix membrane based on multi-layer MXene, which is different from Example 1 only in that the solvent n-heptane is replaced with an equal amount of dimethyl sulfoxide.

[0102] Comparative Example 1

[0103] This comparative example provides an asymmetric hollow fiber mixed matrix membrane, which is different from Example 1 in that the casting solution X does not contain multi-layer MXene, and the amounts of the organic polymer and the solvent are proportionally increased so that the total is 100%.

[0104] Comparative Example 2

[0105] This comparative example provides an asymmetric hollow fiber mixed matrix membrane, which is different from Example 1 in that the multi-layer MXene is replaced with ceramic particles with an average particle size of 50 nm.

[0106] Test Example Performance Test

[0107] The hollow fiber membranes obtained in each example and comparative example are respectively tested in terms of gas permeability, mechanical strength, and pressure resistance.

[0108] The test methods are as follows:

[0109] Gas separation performance: The prepared hollow fiber membrane filament is sealed with epoxy resin, and gas separation performance test is performed using gas chromatography.

[0110] Pressure resistance test: One end of the prepared hollow fiber membrane filament is sealed, and the other end is connected to a high-pressure gas, and the pressure resistance performance is tested. When the membrane filament can maintain 30 min without damage under a certain pressure, the pressure at this time is determined as the pressure resistance.

[0111] Mechanical strength test: The prepared hollow fiber membrane filaments are cut into certain lengths and tested for mechanical tensile properties using a universal testing machine.

[0112] The test results are shown in Table 1:

[0113] Table 1

[0114]

[0115] The results above show that the organic-inorganic composite hollow fiber membrane prepared in the embodiments of the present invention has good helium / methane selectivity, mechanical strength and pressure resistance, and the embodiments 1 to 3 are better than the embodiment 4.

[0116] It should be noted that the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0117] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "detailed implementation," or "some specific implementations," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0118] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An asymmetric hollow fiber hybrid matrix membrane, characterized in that, The film includes a support layer and a separation layer disposed on the outer side of the support layer; the separation layer is made of casting solution X, which is composed of organic polymer A, multilayer MXene, and solvent B, wherein M in the multilayer MXene is an early transition metal; the support layer is made of casting solution Y, which is composed of organic polymer C, pore-forming agent, and solvent D; the content of multilayer MXene in casting solution X is 5wt%~15wt%. The maximum lateral dimension L (μm) and thickness d (nm) of the multilayer MXene also satisfy the following condition with respect to M: M = Z × (d / L) 1 / 2 Where M represents the mass percentage of multilayer MXene in the casting solution X as M%, and Z is a correction coefficient ranging from 1.12 to 2.

12. The organic polymer A is selected from one or more of polydimethylsiloxane, poly(dimethylsiloxane-co-diphenylsiloxane), and polyimide; Solvent B is selected from one or more of n-heptane, n-hexane, and petroleum ether; The organic polymer C is selected from one or more of polysulfone, polyimide, polyetherimide, polyethersulfone, sulfonated polysulfone, polyetheretherketone, and polyaryletherketone; The content of the organic polymer A in the casting solution X is 20wt%~40wt%; The organic polymer C in the casting solution Y has a mass percentage content of 30% to 50%.

2. The asymmetric hollow fiber hybrid matrix membrane according to claim 1, characterized in that, The asymmetric hollow fiber hybrid matrix membrane has an outer diameter of 0.3~0.6 mm and a wall thickness of 0.06~0.09 mm. The thickness of the separation layer is 0.01~0.02mm.

3. The asymmetric hollow fiber hybrid matrix membrane according to claim 1, characterized in that, The pore-forming agent is selected from one or more of polyvinyl alcohol and polyethylene glycol; And / or, the solvent D is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide.

4. The asymmetric hollow fiber hybrid matrix membrane according to claim 3, characterized in that, The pore-forming agent has a mass percentage (S%) of 1% to 5% in the casting solution Y.

5. The method for preparing the asymmetric hollow fiber hybrid matrix membrane according to any one of claims 1 to 4, characterized in that, S1: Mix organic polymer A, multilayer MXene and solvent B evenly to obtain casting solution X; mix organic polymer C, pore-forming agent and solvent D evenly, and then degas under vacuum to obtain casting solution Y; S2: The casting solution Y is spun using a dry-wet combined spinning technique to obtain a hollow fiber support layer; S3: The hollow fiber support layer is dried at room temperature and then immersed in casting solution X; wherein the drying temperature is 60~80℃.

6. The method for preparing the asymmetric hollow fiber hybrid matrix membrane according to claim 5, characterized in that, The solid content of the casting solution X in S1 is 25-55%; and / or the solid content of the casting solution Y is 30-55%.

7. The method for preparing the asymmetric hollow fiber hybrid matrix membrane according to claim 5, characterized in that, In S3, the soaking time t1 is 30~60 min, the drying temperature T3 is 60~80℃, and the drying time t2 is 10~24 h.

8. The method for preparing an asymmetric hollow fiber hybrid matrix membrane according to claim 6 or 7, characterized in that, In S2, the spinning pressure P1 is 0.2~0.6MPa, the core liquid is water, the core liquid pressure P2 is 0.05~0.1MPa, the core liquid temperature T1 is 50~80℃, the coagulation bath temperature T2 is 30~50℃, and the air gap L0 is 1~10cm.

9. The application of the asymmetric hollow fiber hybrid matrix membrane according to any one of claims 1 to 4 or the asymmetric hollow fiber hybrid matrix membrane prepared by the preparation method according to any one of claims 5 to 8 in gas separation.

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