Asymmetric hollow fiber mixed matrix membrane as well as preparation method and application thereof

Abstract

The invention relates to the technical field of membrane separation, in particular to an asymmetric hollow fiber mixed matrix membrane as well as a preparation method and application thereof. The asymmetric hollow fiber mixed matrix membrane comprises a supporting layer and a separation layer arranged on the outer side of the supporting layer in a contact mode. The raw material of the separation layer is a membrane casting solution X, and the membrane casting solution X is composed of an organic polymer A, multiple layers of MXene and a solvent B; the raw material of the supporting layer is a membrane casting solution Y and is composed of an organic polymer C, a pore forming agent and a solvent D; in the membrane casting solution X, the content of the multi-layer MXene is 5 to 15 weight percent. According to the asymmetric hollow fiber mixed matrix membrane and the preparation method thereof, the multiple layers of MXene and the organic polymer are compounded according to a specific proportion, the multiple layers of MXene are added into the separation layer of the asymmetric hollow fiber mixed matrix membrane, the asymmetric composite hollow fiber membrane is prepared from the multiple layers of MXene and the organic polymer, and the obtained asymmetric hollow fiber mixed matrix membrane has good gas permeability, mechanical strength and pressure resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of membrane separation, and particularly relates to an asymmetric hollow fiber mixed matrix membrane, a preparation method thereof, and an application thereof. Background Art

[0002] Helium (He) is a colorless inert gas and belongs to strategic rare gas resources. Because of its rarity and preciousness, it is said to be the "gold gas". Helium mainly comes from the radioactive decay of uranium and thorium and mantle degassing. The helium resources on the earth are extremely limited and unevenly distributed. Because of its chemical inertness and extremely low boiling point (4.3 K), helium is widely used in fields such as cryogenic superconductivity, rockets, missiles, laser technology, nuclear technology, and medical technology.

[0003] Purifying helium from natural gas is the main way to capture helium resources. Membrane separation technology is a "green technology". Its typical characteristics are room temperature operation, no phase change, low energy consumption, high safety, and low device investment. It is the most likely separation technology to achieve efficient and low-cost helium purification. Hollow fiber membrane is an efficient gas separation technology. It can achieve selective separation of different gas molecules by using special membrane materials and structural designs. The characteristic of this kind of membrane is that it has a hollow fiber structure and can separate different gases according to the size and properties of gas molecules under a certain pressure difference. However, the existing hollow fiber membranes have problems such as the inability to have both high permeability and high selectivity, and poor uniformity, making it difficult to achieve efficient helium separation and purification, and large-scale commercialization is restricted.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

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

[0006] Based on this, the present invention has the following technical solutions: In the first aspect, the present invention provides an asymmetric hollow fiber mixed matrix membrane, including a support layer and a separation layer 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, multilayer 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; in the casting solution X, the content of the multilayer MXene is 5wt% - 15wt%.

[0007] MXene is a new type of two-dimensional material, which is a transition metal carbide (nitride), and its chemical formula is M n+1 X n T X, where M is an early transition metal such as titanium, vanadium, chromium, manganese, etc., X is carbon or (and) nitrogen, n is an integer such as 1, 2, 3, etc., and T X represents its surface functional groups. For example, common MXenes include 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.

[0008] The multi-layer MXene is obtained by partial etching of the MAX phase. It has the characteristics of high porosity and uniform controllability of the interlayer spacing at the sub-nanometer scale. As a filler for mixed matrix membranes, it can not only change the packing of polymer chains and improve permeability, but also precisely screen gas molecules, thereby increasing selectivity.

[0009] In the prior research of the present invention, multi-layer MXene was used to prepare an organic-inorganic composite hollow fiber membrane. This composite hollow fiber membrane has good gas permeability, mechanical strength and pressure resistance. However, subsequent research found that there is still room for further improvement. The present invention further studies and finds that by adding multi-layer MXene to the separation layer of the asymmetric hollow fiber mixed matrix membrane and jointly making an asymmetric composite hollow fiber membrane with an organic polymer, the gas permeability, mechanical strength and pressure resistance of this asymmetric hollow fiber mixed matrix membrane can be further improved.

[0010] Preferably, the maximum lateral dimension L (μm), thickness d (nm) of the multi-layer MXene and M also satisfy: M = Z×(d / L) 1 / 2 , where Z is a correction coefficient, and the range is: 1.12~2.12.

[0011] In the present invention, the MXene has no special limitation and can be selected from one or more of the above common MXenes. The maximum lateral dimension refers to the maximum dimension in the horizontal direction perpendicular to the thickness direction.

[0012] Preferably, 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; the thickness of the separation layer is 0.01~0.02 mm.

[0013] Preferably, 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 20 wt%~40 wt%.

[0014] Preferably, the solvent B is selected from one or more of n-heptane, n-hexane, and petroleum ether.

[0015] Preferably, the organic polymer C is selected from one or more of polysulfone, polyimide, polyetherimide, polyethersulfone, sulfonated polysulfone, polyetheretherketone, and polyaryletherketone; preferably, the mass percentage content C% of the organic polymer C in the casting solution Y is 30% - 50%.

[0016] Preferably, the pore former is selected from one or more of polyvinyl alcohol and polyethylene glycol; preferably, the mass percentage content S% of the pore former in the casting solution Y is 1% - 5%.

[0017] Preferably, the solvent D is selected from one or more of dimethyl sulfoxide, N,N - dimethylformamide, and N,N - dimethylacetamide.

[0018] In a second aspect, the present invention provides a method for preparing the asymmetric hollow fiber mixed matrix membrane, comprising: S1: Mix the organic polymer A, the multilayer MXene, and the solvent B uniformly to obtain a casting solution X; mix the organic polymer C, the pore former, and the solvent D uniformly, and then perform vacuum degassing to obtain a casting solution Y; preferably, the solid content of the casting solution X is 25 - 55%; and / or, the solid content of the casting solution Y is 30 - 55%; S2: Spin the casting solution Y using the dry - wet spinning technique to obtain a hollow fiber support layer; S3: Dry the hollow fiber support layer at room temperature, and then immerse it in the casting solution X; wherein, the drying temperature is 60 - 80 °C.

[0019] Preferably, in S3, the impregnation time t1 is 30 - 60 min, the drying temperature T3 is 60 - 80 °C, and the drying time t2 is 10 - 24 h.

[0020] Preferably, in S2, the spinning pressure P1 is 0.2 - 0.6 MPa, the core liquid is water, the core liquid pressure P2 is 0.05 - 0.1 MPa, the core liquid temperature T1 is 50 - 80 °C, the coagulation bath temperature T2 is 30 - 50 °C, and the air gap L0 is 1 - 10 cm.

[0021] In a third aspect, the present invention provides the application of the asymmetric hollow fiber mixed matrix membrane in gas separation.

[0022] The asymmetric hollow fiber mixed matrix membrane of the invention can be used for the separation of helium and methane, the separation of hydrogen and methane, etc. Specifically, the asymmetric hollow fiber mixed matrix membrane of the present invention has a high helium / methane separation selectivity and has good application prospects in the fields of helium extraction from natural gas and helium recovery, etc.

[0023] Based on this, the technical solution of the present invention has the following beneficial effects: The asymmetric hollow fiber mixed matrix membrane provided by the present invention, its preparation method and application, by compounding multiple layers of MXene and an organic polymer in a specific ratio, adding the multiple layers of MXene into the separation layer of the asymmetric hollow fiber mixed matrix membrane, and jointly making an asymmetric composite hollow fiber membrane with the organic polymer. The obtained asymmetric hollow fiber mixed matrix membrane has both good gas permeability, mechanical strength and pressure resistance. In particular, it has a high helium / methane separation selectivity and has good application prospects in the fields of helium extraction from natural gas, helium recovery, etc. Description of the Drawings

[0024] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0025] Figure 1 It is the scanning electron microscope image of the multiple layers of MXene used in Example 1 provided by the present invention.

[0026] Figure 2 It is the cross-sectional scanning electron microscope image of the asymmetric hollow fiber mixed matrix membrane based on multiple layers of MXene prepared in Example 1 provided by the present invention. The left side is the low-magnification image and the right side is the high-magnification image. Detailed Embodiments

[0027] To make the objectives, technical solutions and advantages of the present invention clearer, the following will clearly and completely describe the technical solutions in the present invention in conjunction with the drawings in the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art without creative efforts based on the embodiments in the present invention belong to the scope of protection of the present invention.

[0028] For those not specifying specific technologies or conditions in the embodiments, they shall be carried out according to the technologies or conditions described in the literature in this field or according to the product specifications. For those reagents or instruments without specifying the manufacturer, they are all conventional products that can be obtained through regular channels.

[0029] Example 1 This example provides an asymmetric hollow fiber mixed matrix membrane based on multiple layers of MXene. The composition of the casting solution X of its separation layer is as follows: Organic polymer A: Polydimethylsiloxane, with a mass percentage content of 20%; Multiple layers of MXene: Titanium carbide, L = 5 μm, d = 100 nm, with a mass percentage content of 5%; The scanning electron microscope image of the multiple layers of MXene can be seen inFigure 1 ; Solvent B: n - heptane, mass percentage content is 75%; The casting solution Y of its support layer is composed as follows: Organic polymer C: polysulfone, mass percentage content is 30%; Pore - forming agent: polyethylene glycol, mass percentage content is 1%; Solvent D: N,N - dimethylformamide, mass percentage content is 69%; This embodiment also provides a preparation method of the above - mentioned asymmetric hollow - fiber mixed - matrix membrane, including the following steps: (1) Mix the formulated amounts of organic polymer A, multi - layer MXene, and solvent B, and heat and stir evenly to obtain casting solution X; (2) Mix the formulated amounts of organic polymer C, pore - forming agent, and solvent D, heat and stir, and then perform vacuum degassing to obtain casting solution Y; (3) Add casting solution Y to a pressure tank, connect a spinneret, use the gas in a steel cylinder as the pressure source, and perform spinning using the dry - wet spinning technique to obtain a hollow - fiber support layer; 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; (4) After collecting the obtained hollow - fiber support layer, dry it at room temperature for 24 hours.

[0030] (5) Immerse the above - obtained hollow - fiber support layer in the formulated amount of casting solution X for 30 min, then take it out and dry it at 60 °C for 24 hours; The outer diameter of the asymmetric hollow - fiber mixed - matrix membrane obtained in this embodiment is 0.3 mm, the wall thickness is 0.06 mm, and the thickness of the separation layer is 0.01 mm. Its cross - sectional scanning electron micrograph is as Figure 2 shown, the left is a low - magnification picture and the right is a high - magnification picture.

[0031] Example 2 This embodiment provides an asymmetric hollow - fiber mixed - matrix membrane based on multi - layer MXene. The casting solution X of its separation layer is composed as follows: Organic polymer A: poly(dimethylsiloxane - co - diphenylsiloxane), mass percentage content is 40%; Multi - layer MXene: vanadium carbide, L = 1 μm, d = 50 nm, mass percentage content is 15%; Solvent B: n - hexane, mass percentage content is 45%; The casting solution Y of its support layer is composed as follows: Organic polymer C: Polyethersulfone, mass percentage content is 50%; Pore former: Polyethylene glycol, mass percentage content is 5%; Solvent D: N,N-Dimethylacetamide, mass percentage content is 45%.

[0032] This embodiment also provides a preparation method of the above asymmetric hollow fiber mixed matrix membrane, including the following steps: (1) Mix the formulated amounts of organic polymer A, multi-layer MXene, and solvent B, and heat and stir evenly to obtain casting solution X; (2) Mix the formulated amounts of organic polymer C, pore-forming agent, and solvent D, heat and stir, and then perform vacuum degassing to obtain casting solution Y; (3) Add casting solution Y to a pressure tank, connect the spinning head, use the gas in the cylinder as the pressure source, and perform spinning using the dry-wet spinning technique 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 °C, the coagulation bath is tap water, the coagulation bath temperature is 50 °C, and the air gap is 10 cm; (4) After collecting the obtained hollow fiber support layer, dry it at room temperature for 24 hours; (5) Immerse the above-obtained hollow fiber support layer into the formulated amount of casting solution X for 60 min, then take it out and dry it at 80 °C for 10 hours; The outer diameter of the asymmetric hollow fiber mixed matrix membrane obtained in this embodiment is 0.6 mm, the wall thickness is 0.09 mm, and the thickness of the separation layer is 0.02 mm.

[0033] Example 3 This embodiment provides an asymmetric hollow fiber mixed matrix membrane based on multi-layer MXene, and the composition of the casting solution X of its separation layer is as follows: Organic polymer A: Polyimide, mass percentage content is 30%; Multi-layer MXene: Titanium carbide, L = 2 μm, d = 40 nm, mass percentage content is 8%; Solvent B: Petroleum ether, mass percentage content is 62%; The composition of the casting solution Y of its support layer is as follows: Organic polymer C: Polysulfone, mass percentage content is 40%; Pore former: Polyvinyl alcohol, mass percentage content is 3%; Solvent D: Dimethyl sulfoxide, mass percentage content is 57%.

[0034] This embodiment also provides a preparation method of the above asymmetric hollow fiber mixed matrix membrane, including the following steps: (1) Mix the formulated amount of organic polymer A, multi-layer MXene, and solvent B, and heat and stir evenly to obtain casting solution X; (2) Mix the formulated amount of organic polymer C, pore-forming agent, and solvent D, heat and stir, and then perform vacuum degassing to obtain casting solution Y; (3) Add casting solution Y to a pressure tank, connect a spinneret, use cylinder gas as the pressure source, and perform spinning using the dry-wet spinning technique 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; (4) After collecting the obtained hollow fiber support layer, dry it at room temperature for 24 hours; (5) Immerse the obtained hollow fiber support layer in the formulated amount of casting solution X for 50 min, then take it out and dry it at 70 °C for 18 hours; The outer diameter of the asymmetric hollow fiber mixed matrix membrane obtained in this example is 0.5 mm, the wall thickness is 0.07 mm, and the thickness of the separation layer is 0.015 mm.

[0035] Example 4 This example provides an asymmetric hollow fiber mixed matrix membrane based on multi-layer MXene, and the composition of casting solution X for its separation layer is as follows: Organic polymer A: Polydimethylsiloxane, mass percentage content is 30%; Multi-layer MXene: Titanium carbide, L = 2 μm, d = 5 nm, mass percentage content is 8%; Solvent B: n-Hexane, mass percentage content is 62%; The composition of casting solution Y for its support layer is as follows: Organic polymer C: Polysulfone, mass percentage content is 40%; Pore-forming agent: Polyethylene glycol, mass percentage content is 3%; Solvent D: N,N-Dimethylformamide, mass percentage content is 57%.

[0036] This example also provides a preparation method for the above asymmetric hollow fiber mixed matrix membrane, including the following steps: (1) Mix the formulated amount of organic polymer A, multi-layer MXene, and solvent B, and heat and stir evenly to obtain casting solution X; (2) Mix the formulated amount of organic polymer C, pore-forming agent, and solvent D, heat and stir, and then perform vacuum degassing to obtain casting solution Y; (3) Add the casting solution Y into a pressure tank, connect the spinning head, use the gas in the cylinder as the pressure source, and carry out spinning by using the dry-wet spinning technique 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. (4) After collecting the obtained hollow fiber support layer, dry it at room temperature for 24 hours.

[0037] (5) Immerse the obtained hollow fiber support layer into the casting solution X with the formulated amount for 50 min, then take it out and dry it at 70 °C for 18 hours. The outer diameter of the asymmetric hollow fiber mixed matrix membrane obtained in this example is 0.55 mm, the wall thickness is 0.075 mm, and the separation layer thickness is 0.018 mm.

[0038] Example 5 This example provides an asymmetric hollow fiber mixed matrix membrane based on multi-layer MXene. The difference from Example 1 is only that the organic polymer A, polydimethylsiloxane, is replaced with an equal amount of polyvinyl butyral.

[0039] Example 6 This example provides an asymmetric hollow fiber mixed matrix membrane based on multi-layer MXene. The difference from Example 1 is only that the solvent n-heptane is replaced with an equal amount of dimethyl sulfoxide.

[0040] Comparative Example 1 This comparative example provides an asymmetric hollow fiber mixed matrix membrane. The difference from Example 1 is that the casting solution X does not contain multi-layer MXene, and the amounts of the organic polymer and the solvent are scaled up proportionally so that the sum is 100%.

[0041] Comparative Example 2 This comparative example provides an asymmetric hollow fiber mixed matrix membrane. The difference from Example 1 is that the multi-layer MXene is replaced with ceramic particles with an average particle size of 50 nm.

[0042] Test Example - Performance Test Test the gas permeability, mechanical strength, and pressure resistance of the hollow fiber membranes obtained in each example and comparative example respectively.

[0043] The test method is as follows: Gas separation performance: Seal the prepared hollow fiber membrane filaments with epoxy resin and test the gas separation performance by using gas chromatography.

[0044] Hydrostatic pressure test: One end of the prepared hollow fiber membrane filament was sealed, and high-pressure gas was introduced into the other end to test the hydrostatic pressure resistance. When the membrane filament could maintain integrity for 30 minutes under a certain pressure, the pressure at this time was determined as the hydrostatic pressure resistance.

[0045] Mechanical strength test: The prepared hollow fiber membrane filaments were cut into a certain length, and a universal testing machine was used to test the mechanical tensile properties.

[0046] The test results are shown in Table 1: Table 1

[0047] From the above results, it can be seen 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 among Embodiments 1 to 3 are superior to Embodiment 4.

[0048] It should be noted that the endpoints and any values in the ranges disclosed in this article are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this article.

[0049] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "specific implementation manners", or "some specific implementation manners" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the embodiments of the present invention. In this specification, the schematic descriptions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0050] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements 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 mixed matrix membrane, characterized in that, It includes a support layer and a separation layer in contact with the outer side 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-forming agent, and solvent D; in the casting solution X, the content of the multi-layer MXene is 5wt% - 15wt%.

2. The asymmetric hollow fiber mixed matrix membrane according to claim 1, wherein The maximum lateral dimension L (μm), thickness d (nm) of the multi-layer MXene and M also satisfy: M = Z×(d / L) 1 / 2 , where Z is a correction factor, and the range is: 1.12~2.

12.

3. The asymmetric hollow fiber mixed matrix membrane according to claim 1 or 2, characterized in that, The outer diameter of the asymmetric hollow fiber mixed matrix membrane is 0.3 - 0.6mm, and the wall thickness is 0.06 - 0.09mm; Among them, the thickness of the separation layer is 0.01 - 0.02mm.

4. The asymmetric hollow fiber mixed matrix membrane according to any one of claims 1 to 3, characterized in that, 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%.

5. The asymmetric hollow fiber mixed matrix membrane according to any one of claims 1 to 4, characterized in that, The solvent B is selected from one or more of n - heptane, n - hexane, and petroleum ether.

6. The asymmetric hollow fiber mixed matrix membrane according to any one of claims 1 to 5, characterized in that, The organic polymer C is selected from one or more of polysulfone, polyimide, polyetherimide, polyethersulfone, sulfonated polysulfone, polyetheretherketone, and polyaryletherketone; preferably, the mass percentage content C% of the organic polymer C in the casting solution Y is 30% - 50%; And / or, the pore - forming agent is selected from one or more of polyvinyl alcohol and polyethylene glycol; preferably, the mass percentage content S% of the pore - forming agent in the casting solution Y is 1% - 5%; And / or, the solvent D is selected from one or more of dimethyl sulfoxide, N,N - dimethylformamide, and N,N - dimethylacetamide.

7. The preparation method of the asymmetric hollow fiber mixed matrix membrane according to any one of claims 1 - 6, characterized in that, S1: Mix organic polymer A, multi - layer MXene, and solvent B evenly to obtain casting solution X; mix organic polymer C, pore - forming agent, and solvent D evenly, and then perform vacuum degassing to obtain casting solution Y; preferably, the solid content of the casting solution X is 25 - 55%; and / or, the solid content of the casting solution Y is 30 - 55%; S2: Spin the casting solution Y using the dry - wet spinning technique to obtain a hollow fiber support layer; S3: Dry the hollow fiber support layer at room temperature, and then immerse it in the casting solution X; among them, the drying temperature is 60 - 80°C.

8. The method for preparing the asymmetric hollow fiber mixed matrix membrane according to claim 7, wherein In S3, the impregnation time t1 is 30 - 60min, the drying temperature T3 is 60 - 80°C, and the drying time t2 is 10 - 24h.

9. The preparation method of the asymmetric hollow fiber mixed matrix membrane according to claim 7 or 8, 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°C, the coagulation bath temperature T2 is 30 - 50°C, and the air gap L0 is 1 - 10cm.

10. The application of the asymmetric hollow fiber mixed matrix membrane according to any one of claims 1 - 6 or the asymmetric hollow fiber mixed matrix membrane prepared by the preparation method according to any one of claims 7 - 9 in gas separation.

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