Structured metal-organic framework fiber adsorbent for capturing carbon dioxide and manufacturing method therefor
View Patent ↗Provided is a method for manufacturing a polymer fiber adsorbent having an MOF uniformly distributed in the matrix thereof, the method comprising the steps of: spinning a spinning dope comprising a polymer matrix and a metal precursor of an MOF to prepare a polymer fiber adsorbent precursor comprising the metal precursor; and contacting the polymer fiber adsorbent precursor with an organic ligand of the MOF to form an MOF in the polymer fiber adsorbent precursor. A polymer fiber adsorbent manufacturing method provided by an aspect of the present invention offers a method capable of easy synthesis of an MOF which is sensitive to water, thereby obtaining a polymer fiber adsorbent excellent in terms of adsorption performance and long-term stability.
1. A method of preparing a polymer fiber adsorbent comprising MOFs (Metal-Organic Frameworks) uniformly distributed in a polymer matrix, the method comprising:
(a) spinning a spinning dope comprising the polymer matrix and a metal precursor of the MOFs to form a polymer fiber adsorbent precursor containing the metal precursor;
(b) immersing the polymer fiber adsorbent precursor formed in step (a) in a solution containing an amine group to crosslink the polymer fiber adsorbent precursor with the amine group; and
(c) contacting the polymer fiber adsorbent precursor with the organic ligand of the MOFs to form MOFs inside the polymer matrix of the polymer fiber adsorbent precursor.
2. The method of preparing a polymer fiber adsorbent of claim 1 , wherein the metal precursor of the MOFs comprises one or more selected from the group consisting of metal oxide, metal nitrate, metal acetate, metal bromide and metal chloride.
3. The method of preparing a polymer fiber adsorbent of claim 1 , wherein the metal of the metal precursor of the MOFs comprises one or more selected from the group consisting of Mg, Al, Y, Sc, Mo, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Cd, Ca, Pd, Pt, Au, Ag, Ru, Gd, Eu, Tb and Zn.
4. The method of preparing a polymer fiber adsorbent of claim 1 , wherein the organic ligand of the MOFs comprises one or more selected from the group consisting of 4,4′-dioxido-3,3′-biphenyl dicarboxylate, 2,5-dioxido-1,4-benzene dicarboxylate, 1,5-dioxide-2,6-naphthalenedicarboxylate, 4,4′-dioxido-3,3′-triphenyldicarboxylate, 2,5-dihydroxyterephthalic acid, 4-(4-carboxy-3-hydroxy-phenyl)-2-hydroxy-benzoic acid, 4,4′-ethynylenedibenzoic acid, 1,3,5-benzenetricarboxylate, 2-bromo-1,4-benzenedicarboxylic acid, pyridine-3-carboxylic acid, 2-methyl-1H-imidazole, 4-methyl-5-imidazolecarboxaldehyde, and biphenyl-4,4′-dicarboxylic acid.
5. The method of preparing a polymer fiber adsorbent of claim 1 , wherein step (b) is performed at a temperature of 25 to 150° C.
6. The method of preparing a polymer fiber adsorbent of claim 1 , wherein step (a) is performed through phase transition.
7. The method of preparing a polymer fiber adsorbent of claim 1 , wherein the spinning dope further comprises a pore former.
8. The method of preparing a polymer fiber adsorbent of claim 1 , further comprising (d) immersing the polymer fiber adsorbent precursor in a solution containing an amine group to functionalize the amine group in the MOFs, after step (c).
9. The method of preparing a polymer fiber adsorbent of claim 1 , wherein in step (a), a content of the metal precursor of the MOFs is 30 wt % to 95 wt %.
10. The method of preparing a polymer fiber adsorbent of claim 1 , wherein the MOF comprises:
one or more metal elements selected from the group consisting of Mg, Al, Y, Sc, Mo, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Cd, Ca, Pd, Pt, Au, Ag, Ru, Gd, Eu, Tb and Zn; and
one or more organic molecules selected from the group consisting of 4,4′-dioxido-3,3′-biphenyl dicarboxylate, 2,5-dioxido-1,4-benzene dicarboxylate, 1,5-dioxide-2,6-naphthalenedicarboxylate, 4,4′-dioxido-3,3′-triphenyldicarboxylate, 2,5-dihydroxyterephthalic acid, 4-(4-carboxy-3-hydroxy-phenyl)-2-hydroxy-benzoic acid, 4,4′-ethynylenedibenzoic acid, 1,3,5-benzenetricarboxylate, 2-bromo-1,4-benzenedicarboxylic acid, pyridine-3-carboxylic acid, 2-methyl-1H-imidazole, 4-methyl-5-imidazolecarboxaldehyde, and biphenyl-4,4′-dicarboxylic acid.
11. The method of preparing a polymer fiber adsorbent of claim 1 , wherein step (c) further comprises supplying a metal ion.
12. The method of preparing a polymer fiber adsorbent of claim 1 , wherein the polymer fiber adsorbent is a monolithic fiber or a hollow fiber.
13. A method of manufacturing a polymer fiber adsorbent module, the method comprising:
spinning a spinning dope comprising a polymer matrix and a metal precursor of MOFs to form a polymer fiber adsorbent precursor containing the metal precursor;
loading a plurality of polymer fiber adsorbent precursors including the polymer fiber adsorbent precursor in a module to form a polymer fiber adsorbent precursor module;
immersing the polymer fiber adsorbent precursor module in a solution containing an amine group to crosslink the polymer fiber adsorbent precursor module with the amine group; and
contacting the polymer fiber adsorbent precursor module with an organic ligand of the MOFs to form the MOFs inside the polymer matrix of the polymer fiber adsorbent precursor.
14. A polymer fiber adsorbent module manufactured by the method of claim 13 , and comprising a monolithic fiber or a hollow fiber in which MOFs are uniformly distributed throughout a polymer matrix.
15. The polymer fiber adsorbent module of claim 14 , wherein the polymer fiber adsorbent module comprises a hollow fiber, and has an outer surface thickness of 100 μm to 1,000 μm, a bore thickness of 50 μm to 1,000 μm, and a porosity of 30 vol % to 80 vol %.
16. The polymer fiber adsorbent module of claim 14 , comprising functionalized amine groups inside the MOFs.