KR20190051274A - Gas separation membrane comprising thin layer containing metal-organic polyhedra and preparation method thereof - Google Patents

Abstract

The present invention relates to a gas separation membrane comprising a thin film layer containing a metal-organic polyhedron and a method for manufacturing the same. The gas separation membrane comprises: a first gas separation layer formed on the upper surface of a porous substrate; a second gas separation layer formed on the upper surface of the formed first gas separation layer; and a gas selection layer formed on the upper surface of the second gas separation layer. The gas permeability is significantly enhanced as compared to a conventional gas separation membrane while maintaining the gas selectivity to the extent similar to that of the conventional gas separation membrane.

Description

[0001] The present invention relates to a gas separation membrane including a metal-organic polyhedra containing thin film layer and a manufacturing method thereof,

The present invention relates to a gas separation membrane comprising three layers including a thin film layer containing a metal-organic polyhedra, wherein the gas selectivity and the gas permeability are simultaneously enhanced, and a method for producing the same.

Background Art [0002] Gas separation membranes processes have recently been attracting attention as energy-saving processes for separating carbon dioxide from syngas, natural gas, and exhaust gas synthesized from large-scale plants such as hydrogen production or urea production.

As the gas separation membrane used in the gas separation membrane process, various separation membranes have heretofore been proposed.

For example, in JP-A-07-112122 (Patent Document 1), a carbon dioxide separation gel film formed of a hydrogel film formed by absorbing an aqueous solution containing a carbon dioxide carrier into a vinyl alcohol-acrylate copolymer having a crosslinking structure . The invention described in Patent Document 1 is a polymeric material which absorbs an aqueous solution containing a carbon dioxide carrier to hydrogel the polymeric material, and the absorption capacity of an electrolyte polymer such as polyacrylic acid conventionally known by using a vinyl alcohol-acrylate copolymer is high Provided is a carbon dioxide promoting transport membrane which can solve the problem that it is difficult to form into a film because of its weak strength and can be put to practical use.

As a gas separation membrane using polyacrylic acid as a polymer material for hydro gelling, JP-A-08-193156 (Patent Document 2) discloses a carbon dioxide separation film formed of a resin composition composed of a reaction mixture of polyacrylic acid and a predetermined equivalent amount of an aliphatic amine Has been proposed. Japanese Patent Application Laid-Open No. 2013-049048 (Patent Document 3) proposes a carbon dioxide-promoted transport film in which a gel layer comprising glycine and a deprotonating agent in a hydrogel film is carried on a heat-resistant porous film.

As a conventional method for separating carbon dioxide, there is a technique using a polymer membrane or a zeolite inorganic film. However, the polymer membrane is difficult to obtain high carbon dioxide selectivity, and the zeolite inorganic membrane is difficult to make large area.

In recent years, mixed membrane separators capable of producing a large area while exhibiting high selectivity to carbon dioxide by adding zeolite to a polymer have been extensively studied. Especially, a gas separator having high selectivity to carbon dioxide and permeability is required.

Japanese Patent Laid-open No. Hei 07-112122 Japanese Patent Publication No. Hei 08-193156 Japanese Patent Application Laid-Open No. 2013-049048

It is an object of the present invention to provide a gas separation membrane including a thin film layer containing a metal-organic polyhedrone having significantly improved gas selectivity and gas permeability at the same time.

It is another object of the present invention to provide a method of manufacturing the gas separation membrane.

It is still another object of the present invention to provide a gas separation membrane module having the gas separation membrane.

It is still another object of the present invention to provide a gas separation apparatus to which the gas separation membrane module is applied.

According to an aspect of the present invention, there is provided a gas separation membrane including a first gas separation layer formed on an upper surface of a porous substrate, a second gas separation layer formed on an upper surface of the first gas separation layer, A gas-selective layer, and the like.

The first gas separation layer may be coated with a first gas separation layer material prepared by stirring the compound of Formula 1 and the compound of Formula 2 in an organic solvent according to the following Reaction Scheme 1:

[Reaction Scheme 1]

[Chemical Formula 1] < EMI ID =

The second gas separation layer may be coated with a second gas separation layer material prepared by stirring the compound of Formula 3 and the compound of Formula 4 in an organic solvent according to the following Reaction Formula 2;

[Reaction Scheme 2]

[Chemical Formula 3]

The gas-selective layer is formed by immersing a substrate coated to the second gas-separation layer in a solution containing a polyethylene glycol-based material, a halogen-substituted metal, a metal-organic polyhedron (EG-MOP), an ATRP ligand and a reducing agent May be deposited by radical polymerization (ATRP).

The polyethylene glycol-based material may be at least one selected from the group consisting of polyethylene glycol diacrylate (PEGDA) and polyethylene glycol methyl ether acrylate (PEGMEA9).

The metal-organic polyhedra (EG-MOP) may be represented by the following formula (5);

[Chemical Formula 5]

The M ₁ and M ₂ may be Cu ²⁺ .

L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently an organic ligand represented by the following formula (6).

[Chemical Formula 6]

Preferably, L ₁ , L ₂ , L ₃ and L ₄ may be organic ligands represented by the following formula (7).

(7)

Preferably, L ₁ , L ₂ , L ₃ and L ₄ may be organic ligands represented by the following formula (8).

[Chemical Formula 8]

The metal-organic polyhedron may have a pore inlet of 5 to 8 angstroms and an inner pore of 10 to 15 angstroms.

The ATRP ligand may be a tris [2- (dimethylamino) ethyl] amine, tris [2- ) aminoethyl) amine and 2- (dimethylamino) ethyl methacrylate) (2- (dimethylamino) ethyl methacrylate).

The reducing agent may be at least one selected from the group consisting of sodium ascorbate and sodium azide.

The thickness of the gas separation membrane may be 10 to 400 탆.

The thickness of the gas-selective layer may be 50 to 300 nm.

According to another aspect of the present invention, there is provided a method of manufacturing a gas separation membrane, including: (A) forming a first gas separation layer on a surface of a porous substrate; (B) forming a second gas separation layer on the upper surface of the first gas separation layer; And (C) forming a gas selective layer on the upper surface of the second gas separation layer.

The first gas separation layer may be formed by coating a first gas separation layer material obtained by ultrasonic treatment by mixing the compound of Formula 1 and the compound of Formula 2 in an organic solvent according to the Reaction Scheme 1 described above.

The second gas separation layer may be formed by coating a second gas separation layer material obtained by ultrasonication by mixing the compound of the formula (3) and the compound of the formula (4) in an organic solvent according to the scheme 2.

The gas-selective layer is formed by immersing a substrate coated to the second gas-separation layer in a solution containing a polyethylene glycol-based material, a halogen-substituted metal, a metal-organic polyhedron (EG-MOP), an ATRP ligand and a reducing agent May be deposited by radical polymerization (ATRP).

The polyethylene glycol-based material and the metal-organic polyhedron (EG-MOP) may be mixed in a weight ratio of 90-99: 1-10.

The polyethylene glycol-based material may be at least one selected from the group consisting of polyethylene glycol diacrylate (PEGDA) and polyethylene glycol methyl ether acrylate (PEGMEA9).

The metal-organic polyhedra (EG-MOP) is represented by the following formula (5): (a) reacting a solution containing a metal precursor, a first solvent and an organic ligand represented by the following formula , ≪ / RTI >

L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently an organic ligand represented by the following formula (6).

[Chemical Formula 6]

The metal precursor may be Cu.

The organic ligand represented by the above formula (6)

(a-I) reacting a solution containing dimethyl-5-hydroxyisophthalate, a second solvent and a monomer represented by the following formula (9) in the presence of a catalyst to obtain a first reaction solution; (a-II) reacting a solution containing the first reaction solution, a third solvent and a hydroxide to obtain a second reaction solution; And (a-III) adding an acid to the second reaction solution to obtain a precipitate;

[Chemical Formula 9]

The first, second and third solvents may be the same or different from each other and each independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone (MEK), formaldehyde Dimethylformamide (DEF), dimethylacetamide (DMA), methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF) ), Water (H ₂ O), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), diethyl ether ), And mixtures thereof.

According to another aspect of the present invention, there is provided a gas separation membrane module including the gas separation membrane.

According to another aspect of the present invention, there is provided a gas separation apparatus comprising the gas separation membrane module and a gas supply unit for supplying a gas mixture containing at least gas and water vapor to the gas separation membrane module.

The gas separation membrane of the present invention can significantly improve the gas permeability compared to the conventional gas separation membrane while maintaining the gas selectivity similar to that of the conventional gas separation membrane having excellent gas selectivity. That is, the gas separation membrane of the present invention has excellent gas selectivity and gas permeability.

Furthermore, the gas separation membrane of the present invention exhibits superior gas selectivity and gas permeability by using a metal-organic polyhedron having a hydrophilic functional group.

1 is a view illustrating a process of manufacturing a gas separation membrane according to an embodiment of the present invention.
2 is a schematic diagram showing a process for synthesizing EG ₃ -Tos according to Preparation Example 1 of the present invention.
3 is a ¹ H-NMR spectrum of EG ₃ -Tos according to Production Example 1 of the present invention.
4 is a schematic diagram showing a process of synthesizing EG ₃ -BDC according to Production Example 1 of the present invention.
5 shows the ¹ H-NMR spectrum of EG ₃ -BDC according to Production Example 1 of the present invention.
6 is a schematic view illustrating a process of synthesizing a first gas separation layer material according to an embodiment of the present invention.
7 is a schematic view illustrating a process of synthesizing a second gas separation layer material according to an embodiment of the present invention.

The present invention relates to a gas separation membrane including a metal-organic polyhedron-containing thin film layer having enhanced gas selectivity and gas permeability at the same time, and a method for producing the same.

The present invention relates to a gas-selective layer comprising a metal-organic polyhedron, which simultaneously enhances selectivity and permeability for a hydrophilic gas such as carbon dioxide in a mixed gas, and has high gas permeability and high gas permeability by the first gas- It shows separation.

The gas is separated in the present invention include H ₂ O, SF _4, H _2, CH _4,, propane, propene, ethylene, acetylene NO _2, H ₂ S, SO _2, O _2, CO, Ar, He, N ₂ , CO ₂ , Kr, Ne, CFCs, and O ₃ , but is not limited thereto. Particularly, the gas separation membrane of the present invention is excellent in separation characteristics against carbon dioxide (CO ₂ ).

Hereinafter, the present invention will be described in detail.

The gas separation membrane of the present invention includes a first gas separation layer formed on the upper surface of the porous substrate, a second gas separation layer formed on the upper surface of the first gas separation layer, and a gas selection layer formed on the upper surface of the second gas separation layer .

Porous substrate

The porous substrate is not particularly limited as long as it is a porous substrate on which a gas can pass, but preferably a polyacrylonitrile (PAN) substrate, a cellulose (Regenerated Cellulose) substrate, a polyimide- Polysulfone or polycarbonate substrates may be mentioned.

The first gas-

The first gas separation layer is formed on the upper surface of the porous substrate by stirring a compound of formula (1) and a compound of formula (2) in an organic solvent according to Reaction Scheme 1 below, Thereby preventing the material for the second gas-separation layer from permeating into the porous substrate and separating gas such as carbon dioxide, which is regarded as impurities in the gas mixture.

[Reaction Scheme 1]

[Chemical Formula 1] < EMI ID =

Wherein R ₁ represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1- A substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 alkylaryl group, An arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms Lt; / RTI >

N is an integer from 1 to 100;

In Formula 2, R ₂ to R ₇ are the same or different from each other and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted C2-C30 heteroaryl group, or a substituted or unsubstituted C2-C30 heteroaryloxy group.

The second gas-

The second gas-phase separation layer is formed on the upper surface of the first gas-phase separation layer in such a manner that the compound represented by the general formula (3) and the compound represented by the general formula (4) The gas is formed by coating the material, which is regarded as an impurity in the mixed gas. The second gas-phase separation layer has a halogen functional group on the surface thereof, and can polymerize with the last gas-selective layer. Further, in the gas separation membrane of the present invention, since the gas is separated twice through the first gas separation layer and the second gas separation layer, the degree of gas separation is high.

[Reaction Scheme 2]

[Chemical Formula 3]

In Formula 3, R ₈ represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1- A substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 alkylaryl group, An arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms Lt; / RTI >

M is an integer of 1 to 100;

이거나, R₉가 수소원자, 할로겐원자, 히드록시기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 1 내지 20의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬아민기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 알킬아릴기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴아민기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴옥시기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴기, 혹은 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴옥시기이고;The formula (4)

Or R ₉ represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylamine having 1 to 20 carbon atoms A substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 alkyl aryl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or a substituted or unsubstituted heteroaryloxy group having 2 to 30 carbon atoms ;

X is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) and is a necessary substituent for carrying out an atom transfer radical polymerization (ATRP) reaction.

Gas-selective layer

The gas-selective layer is formed by depositing a gas-selective layer material including a metal-organic polyhedron (EG-MOP) on the upper surface of the second gas-separation layer, thereby increasing the selectivity and permeability of the gas desired to be separated in the gas mixture.

The gas-selective layer is formed by immersing a substrate coated to the second gas-phase separation layer in a solution containing a polyethylene glycol-based material, a metal-organic polyhedron (EG-MOP), a halogen-substituted metal, an ATRP ligand and a reducing agent (ATRP) to produce a polymer with a uniform gas permeability without damage to the metal-organic polyhedron (EG-MOP) and having a uniform gas permeability.

The polyethylene glycol-based material is used for enhancing gas selectivity by being bonded to a metal-organic polyhedron (EG-MOP), and specifically includes polyethylene glycol diacrylate (PEGDA) and polyethylene glycol methyl ether acrylate (PEGMEA9) . ≪ / RTI >

The halogen-substituted metal is a substance necessary for performing an atom transfer radical polymerization (ATRP) reaction. Examples of the metal include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ^{2 +} , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ^{2+, Ir +, Ni 2+,} Ni +, Pd 2+, Pd +, Pt 2+, Pt +, Cu 2+, Cu +, Ag +, Au +, Zn 2+, Cd 2+, Hg 2 ⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ ; The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), and is preferably the same as the halogen of the second gas separation layer.

In addition, the ATRP ligand is a substance necessary for carrying out the ATRP reaction, and specifically includes tris [2- (dimethylamino) ethyl] amine, tris [ (2-di (butylacrylate) aminoethyl) amine and 2- (dimethylamino) ethyl methacrylate) (2- (dimethylamino) ethyl methacrylate) And at least one selected.

In addition, the reducing agent may be at least one selected from the group consisting of sodium ascorbate and sodium azide, which are required to perform ATRP (atom transfer radical polymerization) .

In addition, the metal-organic polyhedra (EG-MOP) can be represented by the following formula (5).

[Chemical Formula 5]

In Formula 5, M ₁ and M ₂ are the same or different from each other and each independently represents Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ^{+ , Ni 2+, Ni +, Pd} 2+, Pd +, Pt 2+, Pt +, Cu 2+, Cu +, Ag +, Au +, Zn 2+, Cd 2+, Hg 2+, Al 3+ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ ;

X is an integer from 3 to 100;

Wherein L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently represents an organic ligand represented by the following formula (6);

[Chemical Formula 6]

R ₁₀ , R ₁₁ and R ₁₂ are the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms A substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6- A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, Or an unsubstituted heteroaryloxy group having 2 to 30 carbon atoms;

Y is an integer of 1 to 20;

The M ₁ and M ₂ may be Cu ²⁺ .

L ₁ , L ₂ , L ₃ and L ₄ may be the same or different from each other among the organic ligands represented by the following formulas (7) and (8).

(7)

[Chemical Formula 8]

The metal-organic polyhedra has a pore inlet of 5 to 8 A, preferably 6 to 7 A; And an inner pore of 10 to 15 angstroms, preferably 13 to 14 angstroms.

In preparing the gas-selective layer, the polyethylene glycol-based material and the metal-organic polyhedron (EG-MOP) are mixed at a weight ratio of 90-99: 1-10, preferably 95-99: 1-5. When the content of the polyethylene glycol-based material and the metal-organic polyhedra (EG-MOP) is out of the preferable range, both the gas selectivity and the gas permeability can be remarkably reduced.

The gas-selective layer thus formed has a thickness of 50 to 300 nm, preferably 100 to 200 nm, and is formed into a thin film to improve gas permeability. When the thickness of the gas-selective layer is less than the lower limit of the above-mentioned preferable range, the gas permeability may be improved but the gas selectivity may be lowered, and in the case of exceeding the upper limit, the gas permeability may be reduced.

The thickness of the gas separation membrane of the present invention is 10 to 400 占 퐉, preferably 100 to 300 占 퐉, and when the thickness of the gas separation membrane is out of the preferable range, gas selectivity and gas permeability can be remarkably reduced.

The present invention also provides a method for producing a gas separation membrane (Fig. 1).

The method for producing a gas separation membrane of the present invention comprises the steps of: (A) forming a first gas separation layer on an upper surface of a porous substrate; (B) forming a second gas separation layer on the upper surface of the first gas separation layer; And (C) forming a gas selective layer on the upper surface of the second gas separation layer.

In step (A), the compound of formula (1) and the compound of formula (2) are mixed in an organic solvent on the upper surface of the porous substrate for 10 to 60 seconds, The material for the first gas separation layer produced by ultrasonic treatment for 30 seconds is coated by various coating methods such as spin coating to form a first gas separation layer.

When the ultrasonic treatment time is less than the lower limit of the preferable range, the yield of the synthesized material is low and the gas separation can not be improved. If the ultrasonic treatment time exceeds the upper limit, a side reaction may occur and the yield may be significantly lowered.

Next, in the step (B), the compound of the formula (3) and the compound of the formula (4) are mixed in an organic solvent according to the reaction scheme 2 for 10 to 60 seconds on the upper surface of the first gas separation layer , The material for the second gas separation layer produced by ultrasonic treatment for 20 to 30 seconds is coated by various coating methods such as spin coating to form a second gas separation layer.

When the ultrasonic treatment time is less than the lower limit of the preferable range, the yield of the synthesized material is low and the gas separation can not be improved. If the ultrasonic treatment time exceeds the upper limit, a side reaction may occur and the yield may be significantly lowered.

Next, in step (C), a solution containing a polyethylene glycol-based material, a metal substituted with a halogen, a metal-organic polyhedron (EG-MOP), an ATRP ligand and a reducing agent is applied to the upper surface of the second gas- 2 The substrate coated to the gas separation layer is dipped into a gas selective layer through deposition.

The immersing time is 2 to 6 hours, preferably 3 to 4 hours. If the immersion time is less than the lower limit of the above-mentioned preferable range, the gas-selective layer may not be uniformly deposited, and a portion may not be deposited. If the immersion time is above the upper limit of the preferable range, further deposition is not performed.

The metal-organic polyhedra (EG-MOP) is represented by the following formula (5): (a) reacting a solution containing a metal precursor, a first solvent and an organic ligand represented by the formula (6); .

The metal precursor may be Cu and the metal precursor may be selected from the group consisting of pure metal nano powder, chloride, bromide, iodide, nitrate, nitrite, sulfate, But is not limited to, one or more types selected from acetate, sulfite, acetylacetoate and hydroxide. Specifically, it may be an acetic acid salt.

The organic ligand represented by the formula (6) can be obtained by reacting a solution containing (a-I) dimethyl-5-hydroxyisophthalate, a second solvent and a monomer represented by the following formula 1 to obtain a reaction solution; (a-II) reacting a solution containing the first reaction solution, a third solvent and a hydroxide to obtain a second reaction solution; And (a-III) adding an acid to the second reaction solution to obtain a precipitate.

[Chemical Formula 9]

And z is an integer of 1 to 20.

As a specific example, the step (a-I) may be carried out by a reflux reaction at 80 to 200 ° C, preferably 100 to 120 ° C for 5 to 30 hours, preferably 22 to 26 hours (A-II) may be carried out by a reflux reaction at 50 to 150 ° C, preferably 70 to 90 ° C for 5 to 30 hours, preferably 22 to 26 hours; The catalyst may preferably be potassium carbonate; The hydroxide may preferably be sodium hydroxide; The acid is preferably hydrochloric acid.

Further, the precipitate obtained after the step (a-III) may be washed with water and filtered to vacuum-dry the resulting product.

The first, second and third solvents may be the same or different from each other and each independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone (MEK), formaldehyde Dimethylformamide (DEF), dimethylacetamide (DMA), methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF) ), Water (H ₂ O), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), diethyl ether ), And mixtures thereof, but is not limited thereto. Preferably, the first solvent is dimethylformamide, the second solvent is methylethylketone, and the third solvent is ethanol.

A first gas separation layer formed on the upper surface of the porous substrate such as the gas separation membrane of the present invention, a second gas separation layer formed on the upper surface of the first gas separation layer, and a second metal separation layer formed on the upper surface of the second gas separation layer, EG-MOP), a gas separation membrane (8-15 GPU) manufactured using only a metal-organic polyhedron (EG-MOP) without a first gas separation layer and a second gas separation layer The gas permeability is significantly lower than that of the gas separation membrane (260-310 GPU) of the present invention.

In addition, the present invention can provide a gas separation membrane module provided with the gas separation membrane; It is possible to provide a gas separation device having the above-described gas separation membrane module, and a gas supply part for supplying a gas mixture containing at least gas and water vapor to the gas separation membrane module.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Production Example 1. EG ₃ -MOP manufacture

EG ₃ Synthesis of -Tos

To a 200 mL beaker was added 15 mL (91.72 mmol) of triethylene glycol monomethylether, 20.2841 g (106.2 mmol) of p-toluenesulphonyl chloride and 70 mL of tetrahydrofuran (THF) 70 mL solution of sodium hydroxide (5.634 g) dissolved in 10 mL of distilled water was slowly poured into the solution and stirred for 6 hours. 35% hydrochloric acid (HCl) was diluted 10-fold and slowly added to the stirred solution for 6 hours. After confirming that the pH was 1 to 2 by using a pH paper, chloroform and distilled water were used. (yield: ~ 100%) of EG ₃ -Tos (2- (2-methoxyethoxy) ethoxy) ethyl 4-methylbenzenesulfonate was synthesized by extracting the oily product (FIG. 2).

EG ₃ Synthesis of BDC

10 g of the synthesized PEO ₃ -Tos, 5 g of dimethyl-5-hydroxy isophthalate (DHI, 23.79 mmol) and potassium carbonate (K ₂ CO ₃ , 16.43 g) were dissolved in methyl ethyl ketone (MEK, 300 mL), and then subjected to a reflux reaction at 110 ° C. for one day. After cooling the mixed solution, the solvent was removed using a rotary evaporator, and oily product in chloroform layer 3 was extracted with chloroform and distilled water. After 200 mL of ethanol was added to the product solution, the solution was slowly poured into 100 mL of distilled water and sodium hydroxide (NaOH, 23.324 g) was slowly poured into the solution. After cooling the mixed solution, 150 ~ 200 mL of solvent was removed with a rotary evaporator and the solvent was removed. Then, 35% hydrochloric acid was slowly added to the remaining solution to obtain a precipitate. The resulting precipitate was filtered while washing with a small amount of water to obtain a product in the form of a white powder and vacuum dried (EGO ₃ -BDC, yield = 82%) [Fig.

Hydrophilic metal-organic polyhedra (EG ₃ -MOP)

The prepared EG ₃ -BDC (1.5 g), dimethylformamide (DMF, 50 mL) and Cu (CH ₃ CO ₂ ) ₂ .H ₂ O (0.86 g, 4.73 mmol) were mixed and dissolved. The dissolved blue solution was reacted in a Teflon reactor at 80 ° C for one day to synthesize EG ₃ -MOP.

Examples 1 to 3. Preparation of Gas Separation Membrane

First gas separation layer formation (step 1)

In order to fill the pores of the substrate with water, the peroxyacetyl nitrate (PAN) substrate was first ultrasonicated in deionized water for 10 minutes and excess water on the surface was removed using a tissue.

In a separate vial, TMC (Trimesoyl chloride, 7 mg, 0.0267 mmol) and polydimethylsiloxane (PDMS, Polydimethylsiloxane) (2 g, 0.04 mmol) were dissolved in 10 ml of hexane (2.0% w / v) respectively. The two solutions were mixed and ultrasonicated for 30 seconds, and 1 ml of the stirred solution (FIG. 6) was spin-coated on the substrate (1000 rpm, 15 seconds) to form a first gas separation layer. The substrate coated with the first gas separation layer was vacuum-dried overnight in an oven at 25 ° C.

Second gas separation layer formation (step 2)

To the mixture was added 0.35 mL of BIBB (2-Bromo-2-methylpropionyl bromide, 1.0% w / v, in hexane) to 10 mL of a solution of DMS-co-BIBAPMS (2.0% And sonicated for 30 seconds. 1 ml of the mixed solution was spin-coated (1000 rpm, 10 sec) on the previously coated PAN substrate to obtain a second gas separation layer. The coated substrate was dried at 25 캜 and checked for leaks before the formation of a thin gas-selective layer on the gas permeability characteristics.

Gas selective layer formation (step 3)

The PAN substrate coated to the second gas-containing layer was immersed in a PEGDMA ₉ linker (20 mM), CuBr ₂ (1 mM), and EG ₃ prepared in Preparation Example 1 in Milli-Q water degassed through a nitrogen bubbling Was immersed in a CAP solution containing -MOP, Me ₆ TREN (Tris [2- (dimethylamino) ethyl] amine, 1 mM ATRP ligand) and NaAsc (sodium ascorbate, 3 mM; reducing agent) to form a gas-selective layer. In the CAP solution, the content of EG ₃ -MOP relative to the PEGDMA ₉ content was 1, 2.5 and 5 wt% (PEGDMA ₉ : EG ₃ -MOP = 99: 1 weight ratio, 97.5: 2.5 weight ratio, 95: 5 weight ratio).

After 3 hours, the PAN substrate deposited to the gas-selective layer was washed with deionized water, immersed in water for 20 minutes, and vacuum-dried at 25 DEG C for 24 hours to prepare a gas separation membrane.

Comparative Example 1 EG ₃ -MOP Omission

A gas separation membrane was prepared in the same manner as in Example 1 except that EG ₃ -MOP was not used in the production of a gas selective layer.

Comparative Example 2. EG ₃ Only the layer containing -MOP is omitted; the first and second gas separation layers are omitted;

PEGDMA ₉ A macrocross-linker (20 mM) and EG ₃ -MOP prepared in Preparation Example 1 were mixed at a weight ratio of 95: 5 and then spin-coated on the PAN substrate to prepare a gas separation membrane.

<Test Example>

Test Example 1. Visual inspection of the surface of the gas separation membrane

The surfaces of the gas separation membranes prepared in Examples and Comparative Examples of the present invention (i.e., the surface of the gas selective layer) were measured by SEM.

Example 1 Example 2 Example 3 Comparative Example 1

As shown in Table 1, it was confirmed that the gas separation membranes prepared according to Examples 1 to 3 of the present invention had higher specific surface area and higher porosity than the gas separation membranes of Comparative Example 1,

Test Example 2. Measurement of Carbon Dioxide Gas Separation Characteristics _ Using pure gas

The gas separation characteristics were measured by passing a gas mixture of carbon dioxide and nitrogen through the gas separation membranes prepared in Examples and Comparative Examples of the present invention.

division CO ₂ Transmittance (GPU) N ₂ transmittance (GPU) CO ₂ / N ₂ Selectivity Example 1 315 19 27 Example 2 381 12 28 Example 3 408 14 30 Comparative Example 1 377 13 20 Comparative Example 2 8.1 0.2 20.7

As shown in Table 2, the gas separation membranes prepared according to Examples 1 to 3 of the present invention were found to have improved both the carbon dioxide permeability and the selectivity. These values were significantly higher than those of the gas separation membranes of Comparative Examples 1 and 2 Respectively.

Specifically, it was confirmed that the gas separation membrane of Comparative Example 1 had a high carbon dioxide permeability but a low selectivity, and that the gas separation membrane of Comparative Example 2 had a significantly low carbon dioxide permeability but an excellent selectivity.

Test Example 3. Measurement of carbon dioxide gas separation characteristics _ Using mixed gas

The gas separation characteristics of the gas separation membranes prepared in Examples and Comparative Examples of the present invention were measured by passing a mixed gas of carbon dioxide and nitrogen, as well as methane, propane, and oxygen.

division CO ₂ Transmittance (GPU) N ₂ transmittance (GPU) CO ₂ / N ₂ selectivity Example 1 217 17.5 12.4 Example 2 269 19.9 13.9 Example 3 303 19 15.7 Comparative Example 1 243 24 10 Comparative Example 2 3.2 0.1 11.8

As shown in Table 3 above, the gas separation membranes prepared according to Examples 1 to 3 of the present invention were found to have improved both the carbon dioxide permeability and the selectivity even when mixed gases were mixed with various gases, 1 and 2, respectively.

Such carbon dioxide separation properties are suitable for commercial use.

Claims (23)

A first gas separation layer formed on the upper surface of the porous substrate,
A second gas separation layer formed on the upper surface of the first gas separation layer,
And a gas-selective layer formed on the upper surface of the second gas-separation layer. The method of claim 1, wherein the first gas separation layer is formed by coating a first gas separation layer material prepared by stirring a compound of Formula (1) and a compound of Formula (2) in an organic solvent according to Reaction Scheme 1 below A gas separation membrane characterized by comprising;
[Reaction Scheme 1]

[Chemical Formula 1] &lt; EMI ID =
Wherein R ₁ represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1- A substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 alkylaryl group, An arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms Lt; / RTI &gt;
N is an integer from 1 to 100;
In Formula 2, R ₂ to R ₇ are the same or different from each other and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted C2-C30 heteroaryl group, or a substituted or unsubstituted C2-C30 heteroaryloxy group. The method of claim 1, wherein the second gas separation layer is formed by coating a compound of formula (3) and a compound of formula (4) in an organic solvent according to the following reaction formula A gas separation membrane characterized by comprising;
[Reaction Scheme 2]

[Chemical Formula 3]
In Formula 3, R ₈ represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1- A substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 alkylaryl group, An arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms Lt; / RTI &gt;
M is an integer of 1 to 100;
The formula (4)

Or R ₉ represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylamine having 1 to 20 carbon atoms A substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 alkyl aryl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted aryloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or a substituted or unsubstituted heteroaryloxy group having 2 to 30 carbon atoms ;
X is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I). 2. The method according to claim 1, wherein the gas-selective layer is formed by coating a solution containing a polyethylene glycol-based material, a halogen-substituted metal, a metal-organic polyhedron (EG-MOP), an ATRP ligand and a reducing agent Characterized in that the substrate is immersed and deposited by atom transfer radical polymerization (ATRP). The gas separation membrane according to claim 4, wherein the polyethylene glycol-based material and the metal-organic polyhedron (EG-MOP) are mixed at a weight ratio of 90-99: 1-10. The gas separation membrane according to claim 4, wherein the polyethylene glycol-based material is at least one selected from the group consisting of polyethylene glycol diacrylate (PEGDA) and polyethylene glycol methyl ether acrylate (PEGMEA9). 5. The gas separation membrane according to claim 4, wherein the metal-organic polyhedra (EG-MOP) is represented by the following Chemical Formula 5:
[Chemical Formula 5]

In Formula 5, M ₁ and M ₂ are the same or different from each other and each independently represents Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ^{+ , Ni 2+, Ni +, Pd} 2+, Pd +, Pt 2+, Pt +, Cu 2+, Cu +, Ag +, Au +, Zn 2+, Cd 2+, Hg 2+, Al 3+ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ ;
X is an integer from 3 to 100;
Wherein L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently represents an organic ligand represented by the following formula (6);
[Chemical Formula 6]

R ₁₀ , R ₁₁ and R ₁₂ are the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms A substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6- A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, Or an unsubstituted heteroaryloxy group having 2 to 30 carbon atoms;
Y is an integer of 1 to 20; The gas separation membrane according to claim 7, wherein M ₁ and M ₂ are Cu ²⁺ . The gas separation membrane according to claim 7, wherein L ₁ , L ₂ , L ₃ and L ₄ are organic ligands represented by the following formula (7):
(7)

. The gas separation membrane according to claim 7, wherein L ₁ , L ₂ , L ₃ and L ₄ are organic ligands represented by the following formula (8):
[Chemical Formula 8]

.  5. The gas separation membrane according to claim 4, wherein the metal-organic polyhedron has a pore inlet of 5 to 8 angstroms and an inner pore of 10 to 15 angstroms. 5. The method of claim 4 wherein the ATRP ligand is selected from the group consisting of tris [2- (dimethylamino) ethyl] amine, tris [2- (diethyl (butyl acrylate) aminoethyl] amine Wherein the membrane is at least one selected from the group consisting of 2-di (butylacrylate) aminoethyl) amine and 2- (dimethylamino) ethyl methacrylate. The gas separation membrane according to claim 4, wherein the reducing agent is at least one selected from the group consisting of sodium ascorbate and sodium azide. The gas separation membrane according to claim 1, wherein the thickness of the gas separation membrane is 10 to 400 탆. The gas separation membrane according to claim 1, wherein the thickness of the gas selection layer is 50 to 300 nm. (A) forming a first gas separation layer on an upper surface of a porous substrate;
(B) forming a second gas separation layer on the upper surface of the first gas separation layer; And
(C) forming a gas selective layer on the upper surface of the second gas separation layer. 17. The method of claim 16, wherein the gas-selective layer comprises a solution comprising a polyethylene glycol-based material, a halogen-substituted metal, a metal-organic polyhedron (EG-MOP), an ATRP ligand and a reducing agent, Wherein the substrate is immersed and deposited by radical transfer radical polymerization (ATRP). 18. The method of claim 17, wherein the metal-organic polyhedron (EG-MOP) comprises: (a) reacting a solution comprising a metal precursor, a first solvent and an organic ligand represented by Formula 6: A process for producing a gas separation membrane characterized by:
[Chemical Formula 5]

In Formula 5, M ₁ and M ₂ are the same or different from each other and each independently represents Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁴⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ^{+ , Ni 2+, Ni +, Pd} 2+, Pd +, Pt 2+, Pt +, Cu 2+, Cu +, Ag +, Au +, Zn 2+, Cd 2+, Hg 2+, Al 3+ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ ;
X is an integer from 3 to 100;
Wherein L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently represents an organic ligand represented by the following formula (6);
[Chemical Formula 6]

R ₁₀ , R ₁₁ and R ₁₂ are the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms A substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6- A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, Or an unsubstituted heteroaryloxy group having 2 to 30 carbon atoms;
Y is an integer of 1 to 20; The method according to claim 18, wherein the metal precursor is Cu. 19. The method according to claim 18, wherein the organic ligand represented by the formula (6)
(a-I) reacting a solution containing dimethyl-5-hydroxyisophthalate, a second solvent and a monomer represented by the following formula (9) in the presence of a catalyst to obtain a first reaction solution;
(a-II) reacting a solution containing the first reaction solution, a third solvent and a hydroxide to obtain a second reaction solution; and
(a-III) adding an acid to the second reaction solution to obtain a precipitate;
[Chemical Formula 9]

And z is an integer of 1 to 20. 21. The method of claim 20, wherein the first solvent, the second solvent, and the third solvent are the same or different from each other and are each independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone, MEK), formaldehyde (FA), N, N-Diethyl Formamide (DEF), dimethylacetamide (DMA), methanol, MeOH, ethanol, tetrahydrofuran (tetrahydrofuran, THF), water _{(water, H 2 O),} 1- methyl-2-pyrrolidinone (1-methyl-2-pyrrolidinone , NMP), dimethyl sulfoxide (dimethyl sulfoxide, DMSO), diethyl (Diethyl Ether, Ether), and mixtures thereof. &Lt; / RTI &gt; A gas separation membrane module comprising the gas separation membrane according to any one of claims 1 to 15. A gas separation membrane module according to claim 22,
And a gas supply unit for supplying a gas mixture containing at least a gas and water vapor to the gas separation membrane module.

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