Gas separation membrane and method for producing the same, and gas separating method, module and separation apparatus using the same

1. A gas separation membrane to separate at least one acid gas from a mix gas, comprising in this order:

a first layer that is porous;

a second layer that is a separation-active layer containing a compound having a molecular weight of 150,000 or less and capable of interacting with the acid gas; and

a third layer having high gas permeability,

wherein the second layer comprises at least one hydrophilic cross-linked polymer and the hydrophilic cross-linked polymer comprises at least one repeating unit selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyethyleneimine and polyallylamine,

the third layer comprises a cross-linked polymer and the cross-linked polymer comprises at least one repeating unit selected from polyethylene glycol, polypropylene glycol, polysiloxane, and polyolefin; and

wherein the compound having a molecular weight of 150,000 or less and being capable of interacting with an acid gas is at least one acid gas carrier selected from hydroxide of alkali metal, alkoxide of alkali metal, alkali metal carbonate, alkali metal bicarbonate, alkali metal phosphate, hydroxide of alkaline earth metal, alkoxide of alkaline earth metal, alkaline earth metal carbonate, alkaline earth metal bicarbonate, alkali metal phosphate, organic amine, ion liquids and metal complexes.

2. The gas separation membrane according to claim 1 ,

wherein the cross-linked polymer of the third layer comprises a repeating unit represented by the following Formula (II):

wherein in Formula (II), R 1 each independently represents a hydrogen atom or a substituent, L 2 represents an n-valent linking group, n represents a positive integer of 2 or more, J 1 represents —CO—, —COO—, —CONR 2 —, —OCO—, a methylene group, a phenylene group, or a —C 6 H 4 CO— group, wherein R 2 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W 1 represents a single bond or a bivalent linking group, Ra represents an alkylene glycol residue or a propylene glycol residue, and each of a plurality of R 1 , J 1 , W 1 , and Ra may be the same or different.

3. The gas separation membrane according to claim 2 ,

wherein the cross-linked polymer of the third layer is a polymer comprising at least one repeating unit represented by the following Formula (III) and at least one repeating unit represented by Formula (II) above:

wherein in Formula (III), R 3 represents a hydrogen atom or a substituent, J 2 represents —CO—, —COO—, —CONR 2 —, —OCO—, a methylene group, a phenylene group, or a —C 6 H 4 CO— group, R 2 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, W 2 represents a single bond or a bivalent linking group, R b represents an alkylene glycol residue or a propylene glycol residue, R 4 represents a hydrogen atom, an alkyl group, or an aryl group, and each of a plurality of J 2 , W 2 , R 2 , R 3 , R 4 , and R b may be the same or different.

4. The gas separation membrane according to claim 1 ,

wherein the cross-linked polymer of the third layer is a polymer comprising at least one repeating unit selected from the following Formula (IV), the following Formula (V), the following Formula (VI) and the following Formula (VII):

5. The gas separation membrane according to claim 1 ,

wherein the gas separation membrane has a tensile strength of 15 N/mm 2 or more and a fracture elongation of 10% or more.

6. The gas separation membrane according to claim 1 ,

wherein the gas separation membrane has a heat resistance of 100° C. or more.

7. A method for producing the gas separation membrane according to claim 1 , comprising:

forming the third layer by irradiating an active radiation to a composition comprising a monomer of the cross-linked polymer, or heat-curing the composition comprising a monomer of the cross-linked polymer.

8. The method for producing the gas separation membrane according to claim 7 ,

wherein the composition comprising a monomer of the cross-linked polymer is a carrier solution having a solid concentration of 10 to 99% by mass and a viscosity of 50 to 5000 mPa·s,

wherein the gas separation membrane is formed by casting the carrier solution on the second layer and curing the carrier solution using active radiation or heating.

9. A gas separation membrane module comprising:

the gas separation membrane according to claim 1 .

10. A gas separation apparatus comprising:

at least one of the gas separation membrane module according to claim 9 .

11. A gas separation membrane to separate at least one acid gas from a mix gas, comprising in this order:

a first layer that is porous;

a second layer that is a separation-active layer containing a compound having a molecular weight of 150,000 or less and capable of interacting with the acid gas; and

a third layer having high gas permeability,

wherein the second layer comprises at least one hydrophilic cross-linked polymer and the hydrophilic cross-linked polymer comprises at least one repeating unit selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyethyleneimine and polyallylamine,

the third layer comprises a cross-linked polymer and the cross-linked polymer comprises at least one repeating unit selected from polyethylene glycol, polypropylene glycol, polysiloxane, and polyolefin, and

wherein the hydrophilic cross-linked polymer of the second layer is a polymer comprising a repeating unit represented by the following Formula (I):

wherein in Formula (I), L 1 represents an x-valent linking group, and x is an integer of 2 or more.

12. A gas separation membrane to separate at least one acid gas from a mix gas, comprising in this order:

a first layer that is porous;

a second layer that is a separation-active layer containing a compound having a molecular weight of 150,000 or less and capable of interacting with the acid gas; and

a third layer having high gas permeability,

wherein the second layer comprises at least one hydrophilic cross-linked polymer and the hydrophilic cross-linked polymer comprises at least one repeating unit selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyethyleneimine and polyallylamine,

the third layer comprises a cross-linked polymer and the cross-linked polymer comprises at least one repeating unit selected from polyethylene glycol, polypropylene glycol, polysiloxane, and polyolefin, and

wherein the gas separation membrane has a tensile modulus of 500 MPa or more.

13. A method for separating a gas mixture,

wherein the method separates at least one acid gas from a gas mixture comprising the at least one acid gas and at least one non-acid gas using a gas separation membrane to separate at least one acid gas from a mix gas, wherein the gas separation membrane comprises in this order:

a first layer that is porous;

a second layer that is a separation-active layer containing a compound having a molecular weight of 150,000 or less and capable of interacting with the acid gas; and

a third layer having high gas permeability,

wherein the second layer comprises at least one hydrophilic cross-linked polymer and the hydrophilic cross-linked polymer comprises at least one repeating unit selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyethyleneimine and polyallylamine,

the third layer comprises a cross-linked polymer and the cross-linked polymer comprises at least one repeating unit selected from polyethylene glycol, polypropylene glycol, polysiloxane, and polyolefin,

wherein the acid gas is at least one selected from carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxide (SOx), and nitrogen oxide (NOx), and

the non-acid gas is at least one selected from hydrogen, methane, nitrogen, and carbon monoxide.

14. The method for separating a gas mixture according to claim 13 ,

wherein the acid gas is carbon dioxide or hydrogen sulfide.

15. The method for separating a gas mixture according to claim 13 ,

wherein the gas mixture comprises carbon dioxide and methane, or carbon dioxide and hydrogen.