JP2015188867A - gas separation membrane - Google Patents
gas separation membrane Download PDFInfo
- Publication number
- JP2015188867A JP2015188867A JP2014069838A JP2014069838A JP2015188867A JP 2015188867 A JP2015188867 A JP 2015188867A JP 2014069838 A JP2014069838 A JP 2014069838A JP 2014069838 A JP2014069838 A JP 2014069838A JP 2015188867 A JP2015188867 A JP 2015188867A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- separation membrane
- gas separation
- polymer
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000012528 membrane Substances 0.000 title claims abstract description 145
- 238000000926 separation method Methods 0.000 title claims abstract description 77
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 64
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 64
- -1 hydrophilicity Chemical compound 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 47
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 37
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 37
- 150000001450 anions Chemical class 0.000 claims abstract description 21
- 239000011342 resin composition Substances 0.000 claims abstract description 18
- 150000001768 cations Chemical class 0.000 claims abstract description 13
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 35
- 239000000412 dendrimer Substances 0.000 claims description 25
- 229920000736 dendritic polymer Polymers 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 18
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 6
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910001423 beryllium ion Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 71
- 238000006116 polymerization reaction Methods 0.000 description 22
- 239000002131 composite material Substances 0.000 description 17
- 238000007127 saponification reaction Methods 0.000 description 16
- 239000011550 stock solution Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 239000004695 Polyether sulfone Substances 0.000 description 13
- 229920006393 polyether sulfone Polymers 0.000 description 13
- 238000000108 ultra-filtration Methods 0.000 description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000004584 polyacrylic acid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 235000011181 potassium carbonates Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 229920000083 poly(allylamine) Polymers 0.000 description 5
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- LTMQZVLXCLQPCT-UHFFFAOYSA-N 1,1,6-trimethyltetralin Chemical compound C1CCC(C)(C)C=2C1=CC(C)=CC=2 LTMQZVLXCLQPCT-UHFFFAOYSA-N 0.000 description 2
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PECYZEOJVXMISF-UHFFFAOYSA-N 3-aminoalanine Chemical compound [NH3+]CC(N)C([O-])=O PECYZEOJVXMISF-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical group NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002550 PolyAPTAC Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- DSFHXKRFDFROER-UHFFFAOYSA-N 2,5,8,11,14,17-hexaoxabicyclo[16.4.0]docosa-1(22),18,20-triene Chemical compound O1CCOCCOCCOCCOCCOC2=CC=CC=C21 DSFHXKRFDFROER-UHFFFAOYSA-N 0.000 description 1
- OAJNZFCPJVBYHB-UHFFFAOYSA-N 2,5,8,11-tetraoxabicyclo[10.4.0]hexadeca-1(16),12,14-triene Chemical compound O1CCOCCOCCOC2=CC=CC=C21 OAJNZFCPJVBYHB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- UPSXAPQYNGXVBF-UHFFFAOYSA-N 2-bromobutane Chemical compound CCC(C)Br UPSXAPQYNGXVBF-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- ONUXAGYOFJLIQM-UHFFFAOYSA-N 2-ethenylnaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=C(C=C)C=CC2=C1 ONUXAGYOFJLIQM-UHFFFAOYSA-N 0.000 description 1
- TUBVZEPYQZWWNG-UHFFFAOYSA-N 2-ethenylpiperidine Chemical group C=CC1CCCCN1 TUBVZEPYQZWWNG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LVNQVIZBPSRXAN-UHFFFAOYSA-N 4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]icosane Chemical compound C1COCCOCCN2CCOCCN1CCOCC2 LVNQVIZBPSRXAN-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- IDPBFZZIXIICIH-UHFFFAOYSA-N 4-ethenylpiperidine Chemical group C=CC1CCNCC1 IDPBFZZIXIICIH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 102000003846 Carbonic anhydrases Human genes 0.000 description 1
- 108090000209 Carbonic anhydrases Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
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- PMMYEEVYMWASQN-DMTCNVIQSA-N Hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 description 1
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- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
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- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 108010020346 Polyglutamic Acid Proteins 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229960002591 hydroxyproline Drugs 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical group CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 102000040430 polynucleotide Human genes 0.000 description 1
- 108091033319 polynucleotide Proteins 0.000 description 1
- 239000002157 polynucleotide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- QYUMESOEHIJKHV-UHFFFAOYSA-M prop-2-enamide;trimethyl(propyl)azanium;chloride Chemical compound [Cl-].NC(=O)C=C.CCC[N+](C)(C)C QYUMESOEHIJKHV-UHFFFAOYSA-M 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000010936 titanium Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
本発明は、混合ガスから特定のガス種を選択的に分離することのできるガス分離膜に関する。 The present invention relates to a gas separation membrane capable of selectively separating a specific gas species from a mixed gas.
石炭ガス化火力発電用途の分離膜の検討が進んでいる。かかる用途においては、水蒸気が含まれる混合ガスから二酸化炭素を選択的に分離することが求められる。 Studies on separation membranes for coal gasification thermal power generation are in progress. In such applications, it is required to selectively separate carbon dioxide from a mixed gas containing water vapor.
二酸化炭素を含む混合ガスから二酸化炭素を選択的に分離する上では、その選択性(二酸化炭素選択性)を高め、高濃度の二酸化炭素を回収することが課題となる。二酸化炭素選択性に優れた分離膜を得るため、二酸化炭素に対する親和性が高い素材を用いることが提案されており、例えば、架橋剤で架橋された親水性高分子材料をマトリックスとしてその中に特定のアミン化合物を包含させた層を多孔質性支持膜の表面に形成させたガス分離膜が提案されている(特許文献1)。 In selectively separating carbon dioxide from a mixed gas containing carbon dioxide, it becomes a problem to improve its selectivity (carbon dioxide selectivity) and recover high-concentration carbon dioxide. In order to obtain a separation membrane with excellent carbon dioxide selectivity, it has been proposed to use a material with high affinity for carbon dioxide. For example, a hydrophilic polymer material cross-linked with a cross-linking agent is used as a matrix. A gas separation membrane has been proposed in which a layer containing an amine compound is formed on the surface of a porous support membrane (Patent Document 1).
また、以前に本発明者らはカルボキシル基で特定量変性されたビニルアルコール系重合体とアゼチジニウム基を有する架橋剤の組み合わせにポリアミドアミンデンドリマーを包含させるガス分離膜を提案した(特許文献2)。このガス分離膜は、水蒸気が含まれた環境下でも安定にポリアミドアミンデンドリマーを担持することができ、優れた二酸化炭素の選択性を発現する。 In addition, the present inventors previously proposed a gas separation membrane in which a polyamidoamine dendrimer is included in a combination of a vinyl alcohol polymer modified with a specific amount with a carboxyl group and a crosslinking agent having an azetidinium group (Patent Document 2). This gas separation membrane can stably support a polyamidoamine dendrimer even in an environment containing water vapor, and exhibits excellent carbon dioxide selectivity.
さらに、本発明者らはカルボキシル基で特定量変性されたビニルアルコール系重合体に、ポリアミドアミンデンドリマーと1級アミノ基重合体を併用したガス分離膜を提案した(特許文献3)。このガス分離膜は、特許文献2記載のガス分離膜よりもさらに多くのアミノ基を安定的に包含することができる点から、優れた二酸化炭素の選択性を発現する。 Furthermore, the present inventors have proposed a gas separation membrane in which a polyamidoamine dendrimer and a primary amino group polymer are used in combination with a vinyl alcohol polymer modified by a specific amount with a carboxyl group (Patent Document 3). This gas separation membrane expresses excellent carbon dioxide selectivity because it can stably contain more amino groups than the gas separation membrane described in Patent Document 2.
特許文献1に開示の分離膜は、高い二酸化炭素選択性を持つだけでなく、一定の圧力差にも耐えることが可能な分離膜と言える。しかしながら、分離対象となる混合ガスに水蒸気が含まれている場合、混合ガスと膜表面との間に親和性が発現するための適度な親水性と、水蒸気雰囲気下において分離膜の構造変化が起こることのない耐水性という相反した性質が要求される。前記の複合膜では、水蒸気雰囲気下において混合ガスが供給されると、包含されていたアミン化合物が経時的に複合膜より流出して、二酸化炭素選択性を維持することが出来ないため、実用に供することが困難である。 The separation membrane disclosed in Patent Document 1 can be said to be a separation membrane that not only has high carbon dioxide selectivity but can withstand a certain pressure difference. However, when water vapor is contained in the mixed gas to be separated, moderate hydrophilicity for developing affinity between the mixed gas and the membrane surface and structural change of the separation membrane occur in a water vapor atmosphere. The contradictory nature of water resistance is required. In the composite membrane, when a mixed gas is supplied in a water vapor atmosphere, the contained amine compound flows out from the composite membrane over time, and carbon dioxide selectivity cannot be maintained. It is difficult to provide.
特許文献2および特許文献3に開示の分離膜は、水蒸気が含まれた環境下でも安定的にアミノ基の機能を発揮させることができ、優れた二酸化炭素の選択性を発現することに成功した。
しかしながら実用に供せられる分離膜を提供するという観点に立つと、水蒸気の含まれた混合ガスに対し、水蒸気と膜材料の間にさらに高い親和性が発現するための親水性を膜材料に担保させ、二酸化炭素の膜透過速度をより向上させることが望まれる。実用に供せられるだけの二酸化炭素の膜透過速度を得るという点では、前記分離膜よりもさらなる親水性の向上を図ることが望ましい。
例えば、親水性付与の観点から特許文献2のビニルアルコール系重合体のカルボキシル基変性量をさらに上げることが考えられるが、通常5mol%より多くラジカル共重合しようとすると、重合性が悪いため、重合速度が低下したり、重合度が低下するため、所望のビニルアルコール系重合体を得ることが困難であり、その結果分離膜を得ることができない。
以上より、従来よりも高い親水性を膜材料に担保させることで、水蒸気が含まれる混合ガスから二酸化炭素を効率よく分離できる分離膜の開発が切望されている。
The separation membranes disclosed in Patent Document 2 and Patent Document 3 were able to exhibit the function of an amino group stably even in an environment containing water vapor, and succeeded in expressing excellent carbon dioxide selectivity. .
However, from the standpoint of providing a separation membrane for practical use, the membrane material is guaranteed to have a hydrophilic property for developing a higher affinity between the water vapor and the membrane material for the mixed gas containing water vapor. It is desirable to further improve the membrane permeation rate of carbon dioxide. In terms of obtaining a membrane permeation rate of carbon dioxide sufficient for practical use, it is desirable to further improve hydrophilicity than the separation membrane.
For example, from the viewpoint of imparting hydrophilicity, it is conceivable to further increase the carboxyl group-modified amount of the vinyl alcohol polymer of Patent Document 2. However, if the radical copolymerization is usually more than 5 mol%, the polymerization property is poor, and thus the polymerization is poor. Since the speed is lowered or the degree of polymerization is lowered, it is difficult to obtain a desired vinyl alcohol polymer, and as a result, a separation membrane cannot be obtained.
In view of the above, development of a separation membrane that can efficiently separate carbon dioxide from a mixed gas containing water vapor has been eagerly desired by ensuring that the membrane material has higher hydrophilicity than before.
本発明は上記課題を解決するためになされたものであり、水蒸気が含まれる混合ガスから二酸化炭素を選択的に分離できるガス分離膜を提供することを課題とするものである。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a gas separation membrane capable of selectively separating carbon dioxide from a mixed gas containing water vapor.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、ビニルアルコール系重合体に対して、イオン性重合体を組み合わせ、さらにこれらに対してアルカリ金属化合物を併用する組み合わせにおいて、驚くべきことに、イオン性重合体の添加が膜の吸水性向上に寄与し、二酸化炭素親和材として添加したアルカリ金属化合物の機能をさらに発揮することが出来るため、これらを含む樹脂組成物から形成されたガス分離膜では、高温下(例えば、70℃以上)で水蒸気が含まれる混合ガスを分離する場合であっても、二酸化炭素の膜透過速度が向上するだけでなく、二酸化炭素選択性を高めることができ、上記課題が解決されることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have combined an ionic polymer with a vinyl alcohol-based polymer, and further combined an alkali metal compound with these in combination. Surprisingly, the addition of the ionic polymer contributes to the improvement of the water absorption of the film, and can further exert the function of the alkali metal compound added as a carbon dioxide affinity material, so it is formed from a resin composition containing these. In the gas separation membrane, even when a mixed gas containing water vapor is separated at a high temperature (for example, 70 ° C. or higher), not only the membrane permeation rate of carbon dioxide is improved, but also the carbon dioxide selectivity is improved. It has been found that the above problems can be solved and the present invention has been achieved.
すなわち、本発明は、ビニルアルコール系重合体(A)と、カチオンおよび/またはアニオンを含有するイオン性重合体(B)と、アルカリ金属化合物(C)とを含む樹脂組成物で構成されることを特徴とするガス分離膜である。 That is, the present invention comprises a resin composition comprising a vinyl alcohol polymer (A), an ionic polymer (B) containing a cation and / or an anion, and an alkali metal compound (C). Is a gas separation membrane characterized by
イオン性重合体(B)は、カチオンとして、第四級アンモニウムカチオンを含んでいてもよく;アニオンとして、カルボキシラートアニオンおよび/もしくはスルホネートアニオンを含んでいてもよく、任意で、前記カチオンは、ハロゲン化物イオン、水酸化物イオン、リン酸イオン、カルボン酸イオンからなる群から選択される少なくとも一種を対イオンとして有していてもよく、前記アニオンはアルカリ金属を対イオンとして有していてもよい。 The ionic polymer (B) may contain a quaternary ammonium cation as a cation; it may contain a carboxylate anion and / or a sulfonate anion as an anion. At least one selected from the group consisting of fluoride ion, hydroxide ion, phosphate ion and carboxylate ion may be included as a counter ion, and the anion may have an alkali metal as a counter ion. .
前記アルカリ金属化合物(C)として、アルカリ金属炭酸塩を含むことが好ましい。 The alkali metal compound (C) preferably contains an alkali metal carbonate.
ビニルアルコール系重合体(A)とイオン性重合体(B)との質量比は、例えば、(A)/(B)=90/10〜10/90であってもよい。また、イオン性重合体(B)とアルカリ金属化合物(C)との質量比は、(B)/(C)=1/99〜50/50であってもよい。 The mass ratio between the vinyl alcohol polymer (A) and the ionic polymer (B) may be, for example, (A) / (B) = 90/10 to 10/90. Moreover, (B) / (C) = 1 / 99-50 / 50 may be sufficient as mass ratio of an ionic polymer (B) and an alkali metal compound (C).
前記ガス分離膜において、前記ビニルアルコール系重合体(A)、前記イオン性重合体(B)、前記アルカリ金属化合物(C)に加え、さらに加えてアミン系化合物(D)を含むことが好ましい。 The gas separation membrane preferably contains an amine compound (D) in addition to the vinyl alcohol polymer (A), the ionic polymer (B), and the alkali metal compound (C).
前記アミン系化合物(D)は、式(1) The amine compound (D) has the formula (1)
[式中、A1は炭素数1〜3の二価有機残基を示し、nは0または1の整数を示す。]
で示される基および/または式(2)
[Wherein, A 1 represents a C 1-3 divalent organic residue, and n represents an integer of 0 or 1. ]
And / or formula (2)
[式中、A2は炭素数1〜3の二価有機残基を示し、nは0または1の整数を示す。]
で示される基を含有するポリアミドアミンデンドリマー(D1)を含むことが好ましい。
[Wherein, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and n represents an integer of 0 or 1. ]
It is preferable that the polyamidoamine dendrimer (D1) containing the group shown by these is included.
前記アミン系化合物として、前記ポリアミドアミンデンドリマー(D1)と1級アミノ基を含有するアミン系重合体(D2)を含むことが好ましい。 The amine compound preferably includes the polyamide amine dendrimer (D1) and an amine polymer (D2) containing a primary amino group.
ポリアミドアミンデンドリマー(D1)とアミン系重合体(D2)との質量比は、例えば、(D1)/(D2)=100/0〜60/40であってもよい。 The mass ratio between the polyamide amine dendrimer (D1) and the amine polymer (D2) may be, for example, (D1) / (D2) = 100/0 to 60/40.
ガス分離膜は、樹脂組成物から形成されている。ガス分離膜は、さらに支持膜を備えていてもよい。その場合、ガス分離膜は、樹脂組成物が、支持膜に担持されていている複合膜であってもよい。 The gas separation membrane is formed from a resin composition. The gas separation membrane may further include a support membrane. In that case, the gas separation membrane may be a composite membrane in which the resin composition is supported on a support membrane.
また、本発明は、前記ガス分離膜を用いて、水蒸気を含む40℃以上の混合ガスから炭酸ガスを分離することを特徴とするガス分離方法を包含してもよい。 The present invention may also include a gas separation method characterized in that carbon dioxide gas is separated from a mixed gas containing water vapor at 40 ° C. or higher using the gas separation membrane.
本発明によれば、膜中に溶解拡散する水蒸気との間に高い親和性を有し、より高い二酸化炭素の膜透過速度および二酸化炭素選択性を発現するガス分離膜を得ることができる。
また、本発明のガス分離膜は、水蒸気が含まれた環境下でも、安定的に、二酸化炭素を透過するための透過能を維持することが可能であることが可能である。
According to the present invention, it is possible to obtain a gas separation membrane having a high affinity with water vapor dissolved and diffused in the membrane and exhibiting a higher carbon dioxide membrane permeation rate and carbon dioxide selectivity.
In addition, the gas separation membrane of the present invention can stably maintain the permeability for permeating carbon dioxide even in an environment containing water vapor.
本発明のガス分離膜は、ビニルアルコール系重合体(A)と、カチオンおよび/またはアニオン性を含有するイオン性重合体(B)と、アルカリ金属化合物(C)とを含む樹脂組成物で構成されることを特徴としており、以上の構成によって、特定のガス種の分離性能、さらには膜透過速度を著しく向上させることができる。 The gas separation membrane of the present invention comprises a resin composition containing a vinyl alcohol polymer (A), an ionic polymer (B) containing a cation and / or an anion, and an alkali metal compound (C). With the above configuration, the separation performance of a specific gas species and further the membrane permeation rate can be remarkably improved.
(ビニルアルコール系重合体(A))
本発明で用いるビニルアルコール系重合体(A)は、ビニルアルコール単位を主成分とするポリマーであり、通常、酢酸ビニルを重合して得られるポリ酢酸ビニルをけん化して製造される。
ビニルアルコール系重合体(A)は、ガス分離膜に対して、水蒸気を含む混合ガスに対する親水性と、二酸化炭素の分離性能を維持できる耐水性とを付与することができる限り、特に限定されるものではないが、けん化度としては50.0〜99.9モル%であることが好ましい。けん化度が低すぎる場合、分離膜の耐水性が低下する恐れがあり、けん化度が高すぎる場合、製膜時の作業性が低下したり、ガス分離膜を作製する際の溶液の粘度安定性が低下する恐れがある。けん化度は、70.0〜99.5モル%がより好ましい。このように、本発明で用いられるビニルアルコール系重合体(A)は、ビニルアルコール単位の他にけん化されていないビニルエステル単位を含有できる。
(Vinyl alcohol polymer (A))
The vinyl alcohol polymer (A) used in the present invention is a polymer having a vinyl alcohol unit as a main component, and is usually produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate.
The vinyl alcohol polymer (A) is particularly limited as long as it can impart hydrophilicity to the mixed gas containing water vapor and water resistance capable of maintaining the separation performance of carbon dioxide to the gas separation membrane. Although it is not a thing, it is preferable that it is 50.0-99.9 mol% as a saponification degree. If the degree of saponification is too low, the water resistance of the separation membrane may decrease.If the degree of saponification is too high, the workability during film formation will decrease, or the viscosity stability of the solution when producing a gas separation membrane May decrease. The saponification degree is more preferably 70.0 to 99.5 mol%. Thus, the vinyl alcohol polymer (A) used in the present invention can contain unsaponified vinyl ester units in addition to vinyl alcohol units.
ビニルアルコール系重合体(A)の粘度平均重合度(以下、重合度と略記することがある)は200〜5000が好ましく、300〜4000がより好ましい。重合度(P)はJIS−K6726に準じて測定される。すなわち、ビニルアルコール系重合体(A)を再けん化し、精製した後、30℃の水中で測定した極限粘度[η]から次式により求められる。
P=([η]×103/8.29)(1/0.62)
重合度が小さすぎる場合には、ガス分離膜のマトリックスを構成する機能が低下してガス分離膜の耐水性が低下するおそれがある。重合度が大きすぎる場合には、ガス分離膜を作製する際の溶液の粘度が高くなりすぎる場合があり、作業性が低下するのみならず均質なガス分離膜が得られないおそれがある。
200-5000 are preferable and, as for the viscosity average polymerization degree (henceforth abbreviated polymerization degree) of a vinyl alcohol-type polymer (A), 300-4000 are more preferable. The degree of polymerization (P) is measured according to JIS-K6726. That is, after re-saponifying and purifying the vinyl alcohol polymer (A), it is obtained from the intrinsic viscosity [η] measured in water at 30 ° C. by the following equation.
P = ([η] × 10 3 /8.29) (1 / 0.62)
When the degree of polymerization is too small, the function of constituting the matrix of the gas separation membrane is lowered, and the water resistance of the gas separation membrane may be lowered. When the degree of polymerization is too large, the viscosity of the solution in producing the gas separation membrane may become too high, and not only the workability is lowered but there is a possibility that a homogeneous gas separation membrane cannot be obtained.
ビニルアルコール系重合体(A)は、本発明の効果を損なわない範囲であれば、上記してきたビニルアルコール単位、ビニルエステル単位以外の単量体単位を含有していても良い。このような単量体単位となる単量体としては、エチレン、アクリル酸メチル、アクリル酸エチル、アクリル酸n−プロピル、アクリル酸i−プロピル等のアクリル酸エステル;メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n−プロピル、メタクリル酸i−プロピル等のメタクリル酸エステル;アクリルアミド;N−エチルアクリルアミド等のアクリルアミド誘導体;メタクリルアミド;N−メチルメタクリルアミド、N−エチルメタクリルアミド等のメタクリルアミド誘導体;メチルビニルエーテル、エチルビニルエーテル、n−プロピルビニルエーテル、i−プロピルビニルエーテル等のビニルエーテル;アクリロニトリル、メタクリロニトリル等のニトリル;塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン等のハロゲン化ビニル;酢酸アリル、塩化アリル等のアリル化合物;ビニルトリメトキシシラン等のビニルシリル化合物;酢酸イソプロペニル等の単量体由来の単位が挙げられる。これらの単量体単位の含有率としては10mol%以下が好ましく、5mol%以下がより好ましい。 The vinyl alcohol polymer (A) may contain monomer units other than the vinyl alcohol units and vinyl ester units described above as long as the effects of the present invention are not impaired. Examples of such a monomer unit include ethylene, methyl acrylate, ethyl acrylate, acrylic acid esters such as n-propyl acrylate and i-propyl acrylate; methyl methacrylate, ethyl methacrylate, Methacrylic acid esters such as n-propyl methacrylate and i-propyl methacrylate; acrylamide; acrylamide derivatives such as N-ethylacrylamide; methacrylamide; methacrylamide derivatives such as N-methylmethacrylamide and N-ethylmethacrylamide; methyl vinyl ether , Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride Halogenated vinyl; allyl acetate, allyl compounds allyl chloride; vinyl silyl compounds such as vinyltrimethoxysilane; a unit derived from monomers such as isopropenyl acetate and the like. The content of these monomer units is preferably 10 mol% or less, and more preferably 5 mol% or less.
また、ビニルアルコール系重合体(A)は、実質的に、ビニルアルコール単位およびビニルエステル単位のみで構成されていてもよく、その場合、ビニルアルコール単位、ビニルエステル単位以外の単量体単位の含有率としては、1mol%以下であってもよく、0.5mol%以下であってもよい。 In addition, the vinyl alcohol polymer (A) may be substantially composed only of vinyl alcohol units and vinyl ester units, in which case the inclusion of monomer units other than vinyl alcohol units and vinyl ester units. As a rate, 1 mol% or less may be sufficient and 0.5 mol% or less may be sufficient.
(カチオンおよび/またはアニオンを含有するイオン性重合体)
次に、本発明で用いるカチオンおよび/またはアニオンを含有するイオン性重合体(B)について説明する。
本発明で用いるイオン性重合体(B)は、イオン性基が含有されていることで吸水機能が発現するため、分離膜の親水性が向上し、結果として二酸化炭素の膜透過速度を向上させることができる。本発明の効果を損なわない限り、特に限定されることなく、あらゆるイオン性重合体を用いても良く、各種イオン性重合体は、単独でまたは二種以上組み合わせて使用してもよい。
(Ionic polymer containing cation and / or anion)
Next, the ionic polymer (B) containing a cation and / or an anion used in the present invention will be described.
The ionic polymer (B) used in the present invention exhibits a water absorption function by containing an ionic group, thereby improving the hydrophilicity of the separation membrane and consequently improving the membrane permeation rate of carbon dioxide. be able to. As long as the effects of the present invention are not impaired, any ionic polymer may be used without any particular limitation, and various ionic polymers may be used alone or in combination of two or more.
例えば、カチオンとしては、塩型の第1級アミノ基(−N+H2)、第2級アミノ基(−N+HHR)、第3級アミノ基(−N+HRR’)、第四級アンモニウムカチオン(−N+RR’R”)(ここで、R、R’、R”は、同一または異なって炭素数1〜5のアルキル基)が挙げられ、アニオンとしては、カルボキシラートアニオン、スルホネートアニオンなどが挙げられる。イオン性重合体(B)は、これらのイオン性基を、単独でまたは二種以上組み合わせて含んでいてもよい。 For example, as the cation, a salt-form primary amino group (—N + H 2 ), a secondary amino group (—N + HHR), a tertiary amino group (—N + HRR ′), quaternary An ammonium cation (—N + RR′R ″) (wherein R, R ′ and R ″ are the same or different and an alkyl group having 1 to 5 carbon atoms), and the anion includes a carboxylate anion and a sulfonate. And anions. The ionic polymer (B) may contain these ionic groups alone or in combination of two or more.
例えば、カチオンを含有するイオン性重合体(ポリカチオン)としては、例えば、ポリ(4−ビニルピリジン臭化エチル塩)、ポリエチレンイミン塩酸塩、ポリビニルアミン塩酸塩、ポリアリルアミン塩酸塩、ポリメタクリル酸ジエチルアミノエチル臭化エチル塩、アイオネン、ポリビニルベンジルトリアルキルアンモニウム塩化物などが挙げられる。
また、アニオンを含有するイオン性重合体(ポリアニオン)としては、例えば、ポリビニル硫酸、ポリスチレンスルホン酸、ポリアクリル酸、ポリメタクリル酸、スチレン/マレイン酸共重合体、ポリグルタミン酸、ポリビニルリン酸、アルギン酸などが挙げられる。
また、カチオンおよびアニオンの双方を有する両性高分子電解質としては、例えば、メタクリル酸/メタクリル酸ジエチルアミノエチル共重合体、各種タンパク質、ポリヌクレオチドなどが挙げられる。
For example, as an ionic polymer (polycation) containing a cation, for example, poly (4-vinylpyridine ethyl bromide salt), polyethyleneimine hydrochloride, polyvinylamine hydrochloride, polyallylamine hydrochloride, poly (diethylamino) methacrylate Examples thereof include ethyl ethyl bromide, ionene, polyvinyl benzyl trialkyl ammonium chloride and the like.
Examples of the ionic polymer (polyanion) containing an anion include polyvinyl sulfate, polystyrene sulfonic acid, polyacrylic acid, polymethacrylic acid, styrene / maleic acid copolymer, polyglutamic acid, polyvinyl phosphoric acid, and alginic acid. Is mentioned.
Examples of the amphoteric polymer electrolyte having both a cation and an anion include methacrylic acid / diethylaminoethyl methacrylate copolymer, various proteins, and polynucleotides.
二酸化炭素の膜透過速度を向上させる観点から、好ましくは、第四級アンモニウムカチオンを含有するイオン性重合体;カルボキシラートアニオン、スルホネートアニオンのうちいずれか1種を含有するイオン性重合体;であり、さらに好ましくは、製膜原液の粘度安定性などの観点から、第四級アンモニウムカチオン、スルホネートアニオンのうちいずれか1種を含有するイオン性重合体である。 From the viewpoint of improving the membrane permeation rate of carbon dioxide, preferably, an ionic polymer containing a quaternary ammonium cation; an ionic polymer containing any one of a carboxylate anion and a sulfonate anion; More preferably, it is an ionic polymer containing any one of a quaternary ammonium cation and a sulfonate anion from the viewpoint of the viscosity stability of the film-forming stock solution.
第四級アンモニウムカチオンを含有するイオン性重合体は、第四級アンモニウムカチオンを含むモノマーを過酸化物やアゾ系化合物などの重合開始剤とともに水溶液中に添加することで重合し、所望の重合体が得られる。モノマーの具体例としては、3−(メタ)アクリルアミドプロピルトリメチルアンモニウムクロライド、3−(メタ)アクリルアミド−3,3−ジメチルプロピルトリメチルアンモニウムクロライドなど3−(メタ)アクリルアミド−アルキルトリアルキルアンモニウム塩;ビニルベンジルトリメチルアンモニウムクロライドなどビニルベンジルトリアルキルアンモニウム塩;ジアリルジメチルアンモニウムクロライドなどジアリルジアルキルアンモニウム塩;等が例示される。 An ionic polymer containing a quaternary ammonium cation is polymerized by adding a monomer containing a quaternary ammonium cation together with a polymerization initiator such as a peroxide or an azo compound into an aqueous solution to obtain a desired polymer. Is obtained. Specific examples of monomers include 3- (meth) acrylamide-alkyltrialkylammonium salts such as 3- (meth) acrylamidepropyltrimethylammonium chloride, 3- (meth) acrylamide-3,3-dimethylpropyltrimethylammonium chloride; vinylbenzyl Examples include vinylbenzyl trialkylammonium salts such as trimethylammonium chloride; diallyldialkylammonium salts such as diallyldimethylammonium chloride; and the like.
さらに、カチオンに対イオンが存在することで、解離による浸透圧が生まれ、分離膜の吸水力をより高めることができる。カチオン性基の対イオンは特に限定されず、ハロゲン化物イオン、水酸化物イオン、リン酸イオン、カルボン酸イオンなどが例示される。カチオン性基を有するビニルアルコール系共重合体は、1種類のみの対イオンを含有していてもよいし、複数種の対イオンを含有していてもよい。 Furthermore, the presence of a counter ion in the cation creates an osmotic pressure due to dissociation and can further increase the water absorption capacity of the separation membrane. The counter ion of the cationic group is not particularly limited, and examples thereof include halide ions, hydroxide ions, phosphate ions, and carboxylate ions. The vinyl alcohol copolymer having a cationic group may contain only one type of counter ion or may contain a plurality of types of counter ions.
カルボキシラートアニオンを含有するイオン性重合体は、カルボキシル基を含むモノマーを過酸化物やアゾ系化合物などの重合開始剤とともに水溶液中に添加することで重合し、所望の重合体が得られる。モノマーの具体例としては、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、グルタミン酸、アルギン酸等が例示される。また、市販品であるポリアクリル酸等、既にポリマー化されたカルボキシル基含有ポリマーも、該イオン性重合体として用いても良い。 An ionic polymer containing a carboxylate anion is polymerized by adding a monomer containing a carboxyl group to an aqueous solution together with a polymerization initiator such as a peroxide or an azo compound, and a desired polymer is obtained. Specific examples of the monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, glutamic acid, and alginic acid. In addition, already polymerized carboxyl group-containing polymers such as commercially available polyacrylic acid may also be used as the ionic polymer.
スルホネートアニオンを含有するイオン性重合体は、スルホン酸基又はスルホネート基を有するモノマーを過酸化物やアゾ系化合物などの重合開始剤とともに水溶液中に添加することで重合し、所望の重合体が得られる。モノマーの具体例としては、2−アクリルアミド−2−メチルプロパンスルホン酸又はその塩、p−スチレンスルホン酸又はその塩、2−ビニルナフタレンスルホン酸又はその塩、ビニルスルホン酸又はその塩等が例示される。また、市販品であるポリ(2−アクリルアミド−2−メチルプロパンスルホン酸)やポリ(P−スチレンスルホン酸)等、既にポリマー化されたスルホン酸基又はスルホネート基含有ポリマーも、該イオン性重合体として用いても良い。 An ionic polymer containing a sulfonate anion is polymerized by adding a sulfonic acid group or a monomer having a sulfonate group to an aqueous solution together with a polymerization initiator such as a peroxide or an azo compound to obtain a desired polymer. It is done. Specific examples of the monomer include 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, p-styrenesulfonic acid or a salt thereof, 2-vinylnaphthalenesulfonic acid or a salt thereof, vinylsulfonic acid or a salt thereof, and the like. The In addition, commercially available sulfonic acid group or sulfonate group-containing polymers such as poly (2-acrylamido-2-methylpropane sulfonic acid) and poly (P-styrene sulfonic acid) are also included in the ionic polymer. It may be used as
カルボキシラートアニオンあるいはスルホネートアニオンを含有するイオン性重合体には、アニオンの対イオンが存在することで、解離による浸透圧が生まれ、分離膜の吸水力をより高めることができる。カチオン性基の対イオンは、ナトリウムイオン、カリウムイオン、セシウムイオン、ルビジウムイオンなどアルカリ金属イオンが好適なものとして挙げられる。これらのアルカリ金属イオンは、後述するアルカリ金属化合物(C)に由来する金属イオンである。 In an ionic polymer containing a carboxylate anion or a sulfonate anion, the presence of an anion counterion creates an osmotic pressure due to dissociation and can further increase the water absorption of the separation membrane. Suitable examples of the counter ion of the cationic group include alkali metal ions such as sodium ion, potassium ion, cesium ion, and rubidium ion. These alkali metal ions are metal ions derived from an alkali metal compound (C) described later.
分離膜における二酸化炭素選択透過性と、造膜性とを両立させる観点から、ビニルアルコール系重合体(A)とイオン性重合体(B)との質量比は、例えば、(A)/(B)=90/10〜10/90であってもよく、好ましくは85/15〜20/80程度であってもよい。 From the viewpoint of achieving both carbon dioxide selective permeability and membrane-forming properties in the separation membrane, the mass ratio between the vinyl alcohol polymer (A) and the ionic polymer (B) is, for example, (A) / (B ) = 90/10 to 10/90, preferably about 85/15 to 20/80.
(アルカリ金属化合物)
次に、本発明で用いるアルカリ金属化合物(C)について説明する。本発明で用いるアルカリ金属化合物(C)は、アルカリ金属(ナトリウム、カリウム、ルビジウム、セシウム)を含む限り特に限定されず、アルカリ金属イオンそのものであってもよく、アルカリ金属を含む化合物であってもよい。
(Alkali metal compound)
Next, the alkali metal compound (C) used in the present invention will be described. The alkali metal compound (C) used in the present invention is not particularly limited as long as it contains an alkali metal (sodium, potassium, rubidium, cesium), and may be an alkali metal ion itself or a compound containing an alkali metal. Good.
例えば、アルカリ金属イオンは、イオン性重合体(B)の対イオンとして存在してもよい。対イオンとしてアルカリ金属イオンが存在すると、浸透圧が高まり、イオン性重合体の水蒸気への溶解性を大きく高めることが出来る。このようなアルカリ金属イオンは、例えば強塩基性アルカリ金属化合物(例えば、アルカリ金属の水酸化物、アルカリ金属のアルコキシドなど)に由来して生じるイオンであってもよい。 For example, the alkali metal ion may exist as a counter ion of the ionic polymer (B). When an alkali metal ion is present as a counter ion, the osmotic pressure is increased and the solubility of the ionic polymer in water vapor can be greatly increased. Such alkali metal ions may be ions generated from, for example, strongly basic alkali metal compounds (for example, alkali metal hydroxides, alkali metal alkoxides, etc.).
また、アルカリ金属を含む化合物は、該分離膜材料の二酸化炭素に対する親和性を高めるために使用されてもよく、その場合二酸化炭素の膜透過速度を向上させることができる。 Moreover, the compound containing an alkali metal may be used to increase the affinity of the separation membrane material for carbon dioxide, and in that case, the membrane permeation rate of carbon dioxide can be improved.
アルカリ金属化合物としては、強塩基性アルカリ金属化合物[例えば、アルカリ金属の水酸化物(例えば、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム)、アルカリ金属のアルコキシド(例えば、ナトリウムメトキシド、ナトリウムエトキシド、tert−ブトキシナトリウム、tert−ブトキシカリウム)]、アルカリ金属炭酸塩(例えば、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウム)、アルカリ金属重炭酸塩(例えば、炭酸水素ナトリウム、炭酸水素カリウムなど)、アルカリ金属リン酸塩(リン酸ナトリウム、リン酸カリウムなど)、アルカリ金属カルボン酸塩(酢酸ナトリウム、酢酸カリウム、酢酸セシウムなど)、アルカリ金属硫酸塩(硫酸ナトリウム、硫酸カリウム、硫酸セシウムなど)、アルカリ金属ハロゲン化物塩(塩化セシウム、ヨウ化セシウム、塩化カリウム、塩化ナトリウムなど)、アルカリ金属硝酸塩(硝酸ナトリウム、硝酸カリウム、硝酸セシウムなど)などが例示される。 Examples of the alkali metal compound include strongly basic alkali metal compounds [for example, alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide), alkali metal alkoxides (for example, sodium methoxy). Sodium ethoxide, tert-butoxy sodium, tert-butoxy potassium)], alkali metal carbonates (eg, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, Potassium bicarbonate, etc.), alkali metal phosphates (sodium phosphate, potassium phosphate, etc.), alkali metal carboxylates (sodium acetate, potassium acetate, cesium acetate, etc.), alkali metal sulfates (sodium sulfate, potassium sulfate, Sulfuric acid Um, etc.), alkali metal halide salt (cesium chloride, cesium iodide, potassium chloride, sodium chloride, etc.), alkali metal nitrates (sodium nitrate, potassium nitrate, etc. cesium nitrate), and the like.
中でも、膜内が塩基性を帯びる観点から、解離時に弱酸強塩基の塩として振舞えるアルカリ金属カルボン酸塩、アルカリ金属炭酸塩。アルカリ金属重炭酸塩が好ましく用いられ、さらに好ましくはアルカリ金属炭酸塩(特に炭酸セシウム)であってもよい。 Among them, alkali metal carboxylates and alkali metal carbonates that act as salts of weakly acidic strong bases during dissociation from the viewpoint of basicity in the membrane. Alkali metal bicarbonate is preferably used, and more preferably alkali metal carbonate (especially cesium carbonate).
また、アルカリ金属の炭酸塩や重炭酸塩の場合、補助添加成分として、アルカリ金属イオンと錯体を形成する多座配位子や、亜砒酸ナトリウム、炭酸アンヒドラーゼ、ホウ酸等を併用することができる。 In the case of alkali metal carbonates or bicarbonates, polydentate ligands that form complexes with alkali metal ions, sodium arsenite, carbonic anhydrase, boric acid, and the like can be used in combination as auxiliary components.
アルカリ金属イオンと錯体を形成する多座配位子としては、従来公知のもの、例えば:12−クラウン−4、15−クラウン−5、18−クラウン−6、ベンゾ−12−クラウン−4、ベンゾ−15−クラウン−5、ベンゾ−18−クラウン−6、ジベンゾ−12−クラウン−4、ジベンゾ−15−クラウン−5、ジベンゾ−18−クラウン−6、ジシクロヘキシル−12−クラウン−4、ジシクロヘキシル−15−クラウン−5、ジシクロヘキシル−18−クラウン−6、n−オクチル−12−クラウン−4、n−オクチル−15−クラウン−5、n−オクチル−18−クラウン−6等の環状ポリエーテル;クリプタンド〔2.1〕、クリプタンド〔2.2〕等の環状ポリエーテルアミン;クリプタンド〔2.1.1〕、クリプタンド〔2.2.2〕、等の双環式ポリエーテルアミンの他、ポルフィリン、フタロシアニン、ポリエチレングリコール、エチレンジアミン四酢酸等を用いることができる。 As the polydentate ligand that forms a complex with an alkali metal ion, conventionally known ones such as: 12-crown-4, 15-crown-5, 18-crown-6, benzo-12-crown-4, benzo -15-crown-5, benzo-18-crown-6, dibenzo-12-crown-4, dibenzo-15-crown-5, dibenzo-18-crown-6, dicyclohexyl-12-crown-4, dicyclohexyl-15 -Cyclic polyethers such as crown-5, dicyclohexyl-18-crown-6, n-octyl-12-crown-4, n-octyl-15-crown-5, n-octyl-18-crown-6; 2.1], cyclic polyether amines such as cryptand [2.2]; cryptand [2.1.1], cryptand [2] 2.2], other bicyclic polyether amines etc. can be used porphyrins, phthalocyanines, polyethylene glycol, ethylene diamine tetraacetic acid and the like.
前記アルカリ金属化合物の添加量については、一定の造膜性が維持されることを前提とすれば特に限定されず、多量に配合することも可能である。該化合物の添加量は、樹脂組成物(固体分換算)の全量に対して、アルカリ金属換算で、20質量%以上90質量%未満が好ましく、25質量%以上85質量%以下がより好ましく、25質量%以上75質量%以下がさらに好ましい。添加量が少なすぎる場合、アルカリ金属化合物による二酸化炭素膜透過速度向上の効果が見込めない恐れがあり、一方で添加量が多すぎる場合、造膜性が損なわれる恐れがある。
なお、アルカリ金属化合物の含有量は、蛍光X線分析により測定した値であってもよい。
The amount of the alkali metal compound added is not particularly limited as long as a certain film-forming property is maintained, and a large amount can be added. The addition amount of the compound is preferably 20% by mass or more and less than 90% by mass, more preferably 25% by mass or more and 85% by mass or less, in terms of alkali metal, with respect to the total amount of the resin composition (in terms of solid content). More preferably, it is at least 75% by mass. If the amount added is too small, the effect of improving the carbon dioxide membrane permeation rate by the alkali metal compound may not be expected. On the other hand, if the amount added is too large, the film forming property may be impaired.
Note that the content of the alkali metal compound may be a value measured by fluorescent X-ray analysis.
また、分離膜における二酸化炭素透過性と、造膜性とを両立させる観点から、イオン性重合体(B)とアルカリ金属化合物(C)(アルカリ金属換算)との質量比は、例えば、(B)/(C)=1/99〜50/50であってもよく、好ましくは5/95〜40/60程度であってもよい。 Moreover, from the viewpoint of achieving both carbon dioxide permeability and membrane-forming property in the separation membrane, the mass ratio of the ionic polymer (B) and the alkali metal compound (C) (in terms of alkali metal) is, for example, (B ) / (C) = 1/99 to 50/50, preferably about 5/95 to 40/60.
(アミン系化合物)
本発明で用いられる樹脂組成物は、先のビニルアルコール系重合体(A)、イオン性重合体(B)、アルカリ金属化合物(C)に加え、さらにアミン系化合物(D)を含んでいてもよい。アミン系化合物は、実質的に、アミノ基またはイミノ基が塩を形成していない、フリーの状態で用いられる。
(Amine compounds)
The resin composition used in the present invention may contain an amine compound (D) in addition to the vinyl alcohol polymer (A), ionic polymer (B) and alkali metal compound (C). Good. The amine-based compound is used in a free state in which the amino group or imino group does not form a salt.
該アミン系化合物は、本発明の効果を発揮することが出来る限り特に限定されず、例えば、アルカノールアミン(モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、エチルモノエタノールアミン、n‐ブチルモノエタノールアミン、ジメチルエタノールアミン、エチルジエタノールアミン、n‐ブチルエタノールアミン、ジーn‐ブチルエタノールアミン、トリイソプロパノールアミン等);ポリアミドアミンデンドリマー類;ポリアリルアミン、ポリ−N−1,2−ジメチルプロピルアリルアミン、ポリ−N−メチルアリルアミン、ポリ−N,N−ジメチルアリルアミン、ポリ−2−ビニルピペリジン、ポリ−4−ビニルピペリジン、ポリビニルアミン、ポリエチレンイミンの構造単位を有するアミン系重合体;アミノ酸類(例えば、グリシン、アラニン、セリン、プロリン、ヒドロキシプロリン、アルギニン、ジメチルアミノグリシン、2,3−ジアミノプロピオン酸等)等の従来公知のものを挙げることができる。これらは、単一成分として用いても良く、複数成分を組み合せて用いても良い。 The amine compound is not particularly limited as long as the effects of the present invention can be exhibited. For example, alkanolamine (monoethanolamine, diethanolamine, triethanolamine, ethylmonoethanolamine, n-butylmonoethanolamine, dimethyl) Ethanolamine, ethyldiethanolamine, n-butylethanolamine, di-n-butylethanolamine, triisopropanolamine, etc.); polyamidoamine dendrimers; polyallylamine, poly-N-1,2-dimethylpropylallylamine, poly-N-methyl Amine-based polymers having structural units of allylamine, poly-N, N-dimethylallylamine, poly-2-vinylpiperidine, poly-4-vinylpiperidine, polyvinylamine, polyethyleneimine; amino Class (e.g., glycine, alanine, serine, proline, hydroxyproline, arginine, dimethylamino glycine, 2,3-diaminopropionic acid and the like) can be mentioned conventionally known, such as those. These may be used as a single component, or may be used in combination of a plurality of components.
より高いCO2選択性を発現するという観点から、少なくともポリアミドアミンデンドリマーを含むことが好ましく、下記式(1): From the viewpoint of expressing higher CO 2 selectivity, it is preferable that at least a polyamidoamine dendrimer is contained, and the following formula (1):
[式中、A1は炭素数1〜3の二価有機残基を示し、nは0または1の整数を示す。]
で示される基および/または式(2):
[Wherein, A 1 represents a C 1-3 divalent organic residue, and n represents an integer of 0 or 1. ]
And / or formula (2):
[式中、A2は炭素数1〜3の二価有機残基を示し、nは0または1の整数を示す。]
で示される基を、例えば、1〜10meq/g含有するポリアミドアミンデンドリマーを含むことがより好ましく、式(1)で示される基を有するポリアミドアミンデンドリマー(D1)を含むことが特に好ましい。
[Wherein, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and n represents an integer of 0 or 1. ]
More preferably, for example, a polyamidoamine dendrimer containing 1 to 10 meq / g of the group represented by formula (1) is included, and a polyamidoamine dendrimer (D1) having a group represented by formula (1) is particularly preferred.
本発明で用いられるポリアミドアミンデンドリマー(D1)に関して、式(1)、式(2)中、A1、A2で示される炭素数1〜3の二価有機残基としては、たとえば直鎖状または分枝状の炭素数1〜3のアルキレン基が挙げられる。このようなアルキレン基の具体例としては、−CH2−、−CH2−CH2−、−CH2−CH2−CH2−、−CH2−CH(CH3)−などが挙げられ、−CH2−が特に好ましい。また、式(1)または式(2)中、水蒸気が含まれる混合ガスとの親和性が増すことから、n=1であることが好ましい。 Regarding the polyamidoamine dendrimer (D1) used in the present invention, the divalent organic residue having 1 to 3 carbon atoms represented by A 1 and A 2 in the formulas (1) and (2) is, for example, linear Alternatively, branched alkylene groups having 1 to 3 carbon atoms can be mentioned. Specific examples of such alkylene groups, -CH 2 -, - CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) - is like, -CH 2 - is particularly preferred. In Formula (1) or Formula (2), n = 1 is preferable because affinity with a mixed gas containing water vapor increases.
本発明で用いられるポリアミドアミンデンドリマー(D1)は、式(1)で示される基および/または上記式(2)で示される基を、例えば、1〜10meq/g含有してもよい。なお「eq/g」はポリアミドアミンデンドリマー内の官能基の含有率、すなわちポリアミドアミンデンドリマー1g中の官能基の当量数(モル数と称される場合もある)を表し、1meq/gは分子1g中に1ミリ当量の官能基を有することを意味する。これにより、高いCO2選択性を有するガス分離膜を得ることができる。 The polyamidoamine dendrimer (D1) used in the present invention may contain, for example, 1 to 10 meq / g of the group represented by the formula (1) and / or the group represented by the above formula (2). “Eq / g” represents the content of the functional group in the polyamidoamine dendrimer, that is, the equivalent number of functional groups in 1 g of the polyamidoamine dendrimer (sometimes referred to as the number of moles), and 1 meq / g represents 1 g of molecule. It means having 1 milliequivalent functional group in it. Thereby, a gas separation membrane having high CO 2 selectivity can be obtained.
本発明で用いられるポリアミドアミンデンドリマー(D1)は、エチレンジアミンによるアミド化反応で分岐構造を形成し、その分岐数を増やしていくことで、分子内の1級アミンの個数を増すことができる。本発明においては、分岐数に制限されることなく、どの世代のポリアミドアミンデンドリマーでも好適に用いることができるが、1級アミンの含有率が高い下記式(3)〜(8)の中から選択される第0世代ポリアミドアミンデンドリマーが特に好適に用いられる。 The polyamidoamine dendrimer (D1) used in the present invention can increase the number of primary amines in the molecule by forming a branched structure by an amidation reaction with ethylenediamine and increasing the number of branches. In the present invention, any generation of polyamidoamine dendrimers can be suitably used without being limited by the number of branches, but selected from the following formulas (3) to (8) having a high primary amine content. The 0th generation polyamidoamine dendrimer is particularly preferably used.
また、本発明で用いるアミン系化合物(D)は、ポリアミドアミンデンドリマー(D1)に加えて、別のアミン系重合体(D2)を含んでいても良い。アミン系重合体(D2)としては、1級アミノ基を10〜35meq/g含む重合体として、ポリアリルアミン、ポリビニルアミン、ポリエチレンイミン等が挙げられ、それら重合体は一部変性されていても構わない。中でも、水蒸気雰囲気下における膜構造の安定性の観点から、ポリアリルアミンが好適である。 The amine compound (D) used in the present invention may contain another amine polymer (D2) in addition to the polyamide amine dendrimer (D1). Examples of the amine polymer (D2) include polyallylamine, polyvinylamine, polyethyleneimine and the like as polymers containing 10 to 35 meq / g of primary amino groups, and these polymers may be partially modified. Absent. Among these, polyallylamine is preferable from the viewpoint of the stability of the film structure in a water vapor atmosphere.
水蒸気雰囲気下において二酸化炭素を選択的に分離する観点から、ビニルアルコール系重合体(A)及びイオン性重合体(B)の総量と、アミン系化合物(D)との質量比は、例えば、[(A)+(B)]/(D)=100/0〜5/95であってもよく、好ましくは100/0〜10/90であってもよい From the viewpoint of selectively separating carbon dioxide under a water vapor atmosphere, the mass ratio of the total amount of the vinyl alcohol polymer (A) and the ionic polymer (B) to the amine compound (D) is, for example, [ (A) + (B)] / (D) = 100/0 to 5/95, preferably 100/0 to 10/90.
また、ポリアミドアミンデンドリマー(D1)とアミン系重合体(D2)との質量比は、例えば、(D1)/(D2)=100/0〜60/40であってもよく、好ましくは100/0〜70/30であってもよい。 The mass ratio of the polyamide amine dendrimer (D1) and the amine polymer (D2) may be, for example, (D1) / (D2) = 100/0 to 60/40, preferably 100/0. It may be ~ 70/30.
(ガス分離膜)
上記のガス分離膜に用いる各種材料は、水、ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)、N,N−ジメチルアセトアミド(DMAc)などの有機溶媒、およびこれらの混合物、なかでも好ましくは水に溶解混合されて膜形成原液が調整される。そして、樹脂組成物からなるガス分離膜では、この原液がダイからフィルム状に吐出され、またはノズルから中空糸状に形成され、乾燥されたガス分離膜が形成されてもよい。ガス分離膜の膜厚は、0.01〜100μmであることが好ましく、0.05〜20μmであることがより好ましく、0.1〜10μmであることが特に好ましい。
(Gas separation membrane)
The various materials used for the gas separation membrane are water, organic solvents such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N, N-dimethylacetamide (DMAc), and mixtures thereof, preferably water. The film forming stock solution is prepared by dissolving and mixing. And in the gas separation membrane which consists of a resin composition, this undiluted | stock solution may be discharged in the shape of a film from die | dye, or may be formed in the shape of a hollow fiber from a nozzle, and the dried gas separation membrane may be formed. The thickness of the gas separation membrane is preferably 0.01 to 100 μm, more preferably 0.05 to 20 μm, and particularly preferably 0.1 to 10 μm.
(支持膜)
本発明のガス分離膜は、ガス分離膜の強度を向上させる観点から、支持膜を用いてもよい。その場合、ガス分離膜は、樹脂組成物が、支持膜に担持されていている複合膜であってもよい。樹脂組成物と支持膜との複合膜の態をなす場合、実用に供することが可能なものとして好適に使用される。
(Supporting membrane)
The gas separation membrane of the present invention may use a support membrane from the viewpoint of improving the strength of the gas separation membrane. In that case, the gas separation membrane may be a composite membrane in which the resin composition is supported on a support membrane. In the case of forming a composite membrane composed of a resin composition and a support membrane, it is preferably used as one that can be used practically.
樹脂組成物とともに支持膜を用いる場合、ガス分離膜は、樹脂組成物からなるシートと支持膜とが積層されている膜であってもよいし;樹脂組成物が、支持膜に対して含浸または塗布された膜であってもよい。
また、樹脂組成物が支持膜に対して塗布される場合、例えば、上記の原液が支持膜上に吐出され乾燥されてガス分離膜を形成してもよい。
When the support membrane is used together with the resin composition, the gas separation membrane may be a membrane in which a sheet made of the resin composition and the support membrane are laminated; the resin composition is impregnated into the support membrane or It may be a coated film.
Moreover, when a resin composition is apply | coated with respect to a support film, for example, said undiluted | stock solution may be discharged on a support film, and may be dried, and a gas separation film may be formed.
支持膜を構成する高分子としては特に限定されず、例えば、ポリスルホン、ポリエーテルスルホン、ポリアミド、ポリイミド、ポリアクリロニトリル、ポリスチレン、ポリフッ化ビニリデン、ポリ塩化ビニル、ポリメタクリル酸メチルなどが挙げられる。
支持膜の形状としては、フィルム、中空糸、多孔質膜など各種の形状であってよい。孔の大きさ、膜厚などは、気体透過量と膜の機械的強度を考慮して適宜選択することができる。
支持膜が多孔質膜である場合、支持膜は、例えば、所定の分画分子量を有する限外ろ過膜であってもよい。その分画分子量としては、例えば、1万〜50万程度であってもよく、好ましくは10万〜40万程度であってもよい。
The polymer constituting the support membrane is not particularly limited, and examples thereof include polysulfone, polyethersulfone, polyamide, polyimide, polyacrylonitrile, polystyrene, polyvinylidene fluoride, polyvinyl chloride, and polymethyl methacrylate.
The shape of the support membrane may be various shapes such as a film, a hollow fiber, and a porous membrane. The size of the hole, the film thickness, and the like can be appropriately selected in consideration of the gas permeation amount and the mechanical strength of the film.
When the support membrane is a porous membrane, the support membrane may be, for example, an ultrafiltration membrane having a predetermined molecular weight cut off. The molecular weight cut off may be, for example, about 10,000 to 500,000, and preferably about 100,000 to 400,000.
本発明のガス分離膜は、混合ガスが有する水蒸気や圧力に対して、必要な耐水性あるいは耐圧性を確保するため、架橋剤を適宜配合しても良い。架橋剤としては、ポリアミドアミンエピクロロヒドリン樹脂;エポキシ基、アルデヒド基、ハロゲン原子などの官能基を2個以上有する化合物;チタン系架橋剤;ジルコニウム系架橋剤などが好適なものとして挙げられる。 In the gas separation membrane of the present invention, a crosslinking agent may be appropriately blended in order to ensure necessary water resistance or pressure resistance against water vapor and pressure of the mixed gas. Preferred examples of the crosslinking agent include polyamidoamine epichlorohydrin resins; compounds having two or more functional groups such as epoxy groups, aldehyde groups, and halogen atoms; titanium-based crosslinking agents; zirconium-based crosslinking agents.
(その他)
本発明のガス分離膜には、これまでに列記した各種化合物の他にも、発明の効果を損なわない限り、その他の添加剤が含有されていても良い。例えば、酸化防止剤、保水剤、紫外線吸収剤、さらには、二酸化炭素の膜透過速度をより向上する観点から、二酸化炭素と水蒸気間の反応速度をより高められる反応触媒を添加剤(例えば、アミンが配位された亜鉛錯体)などが挙げられる。
(Other)
The gas separation membrane of the present invention may contain other additives in addition to the various compounds listed so far as long as the effects of the invention are not impaired. For example, an antioxidant, a water retention agent, an ultraviolet absorber, and a reaction catalyst capable of further increasing the reaction rate between carbon dioxide and water vapor from the viewpoint of further improving the membrane permeation rate of carbon dioxide as an additive (for example, amine) A zinc complex in which is coordinated.
こうして得られた本発明のガス分離膜は、特定のガス種、特に二酸化炭素を選択的に分離する性能が優れており、火力発電所、製鉄所、セメント工場、天然ガス田等で好適に使用することができる。
特に、本発明のガス分離膜を用いる場合、水蒸気を含む40℃以上(好ましくは60℃以上)の混合ガスから炭酸ガスを効率よく分離することが可能である。
The gas separation membrane of the present invention thus obtained has excellent performance for selectively separating specific gas species, particularly carbon dioxide, and is suitably used in thermal power plants, steelworks, cement factories, natural gas fields, etc. can do.
In particular, when the gas separation membrane of the present invention is used, carbon dioxide gas can be efficiently separated from a mixed gas containing water vapor at 40 ° C. or higher (preferably 60 ° C. or higher).
以下、実施例及び比較例を挙げて本発明を詳細に説明するが、本発明は、これらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.
[透過速度および二酸化炭素選択性の測定]
二酸化炭素の透過速度Q(CO2)(m3/m2・s・Pa)およびヘリウムの透過速度Q(He)(m3/m2・s・Pa)を以下のようにして測定し、二酸化炭素選択性α(CO2/He)を求めた。
組成をCO2/He=80/20(ml/min)、温度を85℃、相対湿度を80RH%に設定したガスを実施例および比較例で得られたガス分離膜に供給し、透過側にスウィープガスとしてアルゴンを10ml/min供給した等圧法によって、該分離膜の透過速度を測定した。
Q(CO2)=(CO2透過流量)/(膜面積)・(CO2供給分圧−CO2透過分圧)
Q(He)=(He透過流量)/(膜面積)・(He供給分圧−He透過分圧)
α=Q(CO2)/Q(He)
[Measurement of permeation rate and carbon dioxide selectivity]
The carbon dioxide permeation rate Q (CO 2 ) (m 3 / m 2 · s · Pa) and the helium permeation rate Q (He) (m 3 / m 2 · s · Pa) were measured as follows. Carbon dioxide selectivity α (CO 2 / He) was determined.
A gas having a composition of CO 2 / He = 80/20 (ml / min), a temperature of 85 ° C., and a relative humidity of 80 RH% was supplied to the gas separation membranes obtained in the examples and comparative examples, and the permeation side The permeation rate of the separation membrane was measured by an isobaric method in which argon was supplied at 10 ml / min as a sweep gas.
Q (CO 2 ) = (CO 2 permeation flow rate) / (membrane area) · (CO 2 supply partial pressure−CO 2 permeation partial pressure)
Q (He) = (He permeation flow rate) / (membrane area) · (He supply partial pressure−He permeation partial pressure)
α = Q (CO 2 ) / Q (He)
(実施例1)
ビニルアルコール系重合体(A)として重合度1700、けん化度98.6モル%の重合体、イオン性重合体(B)としてポリアクリル酸(和光純薬社製、分子量5000)、カルボキシラートアニオンの対イオンとして水酸化ナトリウム、アルカリ金属化合物(C)として炭酸セシウムを表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して乾燥させ複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
(Example 1)
As a vinyl alcohol polymer (A), a polymer having a polymerization degree of 1700 and a saponification degree of 98.6 mol%, an ionic polymer (B) having polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 5000), a carboxylate anion Sodium hydroxide as the counter ion and cesium carbonate as the alkali metal compound (C) were blended in the proportions shown in Table 1, and ion-exchanged water was added to prepare a membrane forming stock solution having a solid content concentration of 7.5% by mass. This solution is cast on an ultrafiltration membrane (made by Millipore, trade name Biomax) made of polyethersulfone with a molecular weight cut off of 300,000 and dried to produce a composite membrane, and the membrane permeation rate of carbon dioxide Q (CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
(実施例2)
ビニルアルコール系重合体(A)として重合度1100、けん化度98.6モル%の重合体、イオン性重合体(B)としてポリ(2−アクリルアミド−2−メチルプロパンスルホン酸)(シグマアルドリッチジャパン社製、分子量200万、略称:ポリAMPS)、スルホネートアニオンの対イオンとして水酸化ナトリウム、アルカリ金属化合物(C)として炭酸セシウムを表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
(Example 2)
As the vinyl alcohol polymer (A), a polymer having a polymerization degree of 1100 and a saponification degree of 98.6 mol%, and as the ionic polymer (B), poly (2-acrylamido-2-methylpropanesulfonic acid) (Sigma-Aldrich Japan) Manufactured, molecular weight 2 million, abbreviation: polyAMPS), sodium hydroxide as sulfonate anion counterion, cesium carbonate as alkali metal compound (C) in the proportions shown in Table 1, added with ion exchange water and solid A film-forming stock solution having a partial concentration of 7.5% by mass was prepared. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
(実施例3)
ビニルアルコール系重合体(A)として重合度1100、けん化度98.6モル%の重合体、イオン性重合体(B)として3−(メタクリルアミド)プロピルトリメチルアンモニウムクロライドの高分子重合体(略称:ポリMAPTAC)、アルカリ金属化合物(C)として炭酸カリウム、さらにアミン系化合物(D)として第0世代ポリアミドアミンデンドリマー(シグマアルドリッチジャパン社製、分子量516、式(1)で表される基の含有率:7.75meq/g)を表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
(Example 3)
As the vinyl alcohol polymer (A), a polymer having a polymerization degree of 1100 and a saponification degree of 98.6 mol%, and as the ionic polymer (B), a polymer polymer of 3- (methacrylamide) propyltrimethylammonium chloride (abbreviation: abbreviation: PolyMAPTAC), potassium carbonate as the alkali metal compound (C), and the 0th generation polyamide amine dendrimer (Sigma Aldrich Japan, molecular weight 516, content of the group represented by the formula (1) as the amine compound (D) : 7.75 meq / g) was blended at the rate shown in Table 1, and ion-exchanged water was added to prepare a membrane-forming stock solution having a solid content concentration of 7.5% by mass. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
なお、MAPTACの高分子量化については、以下に示すとおりに作製した。還流冷却管、攪拌翼を備え付けた四つ口セパラブルフラスコに、水1048g、前記ビニルアルコール系重合体(A)を110g仕込み、攪拌下95℃まで加熱して該ポリビニルアルコールを溶解した後、室温まで冷却した。該水溶液に1/2規定の硫酸を添加してpHを3.0に調製した。別に、MAPTAC178.4gを溶解し、これを先に調製した水溶液に攪拌下添加した後、該水溶液中に窒素をバブリングしつつ70℃まで加温し、さらに70℃で30分間窒素のバブリングを続けることで、窒素置換した。窒素置換後、上記水溶液に過硫酸カリウム(KPS)の2.5%水溶液88.8mLを1.5時間かけて逐次的に添加してMAPTACの重合を開始させ、進行させた後、系内温度を75℃に1時間維持して重合をさらに進行させ、ついで冷却して、固形分濃度20%のビニルアルコール系重合体(A)とポリMAPTACの混合水溶液を得た。 In addition, about high molecular weight of MAPTAC, it produced as shown below. A four-necked separable flask equipped with a reflux condenser and a stirring blade was charged with 1048 g of water and 110 g of the vinyl alcohol polymer (A) and heated to 95 ° C. with stirring to dissolve the polyvinyl alcohol. Until cooled. 1/2 N sulfuric acid was added to the aqueous solution to adjust the pH to 3.0. Separately, 178.4 g of MAPTAC was dissolved and added to the previously prepared aqueous solution with stirring. Then, the solution was heated to 70 ° C. while bubbling nitrogen into the aqueous solution, and continued to be bubbled with nitrogen at 70 ° C. for 30 minutes. Thus, nitrogen substitution was performed. After nitrogen substitution, 88.8 mL of a 2.5% aqueous solution of potassium persulfate (KPS) was sequentially added to the above aqueous solution over 1.5 hours to initiate and proceed the polymerization of MAPTAC, and then the system temperature was increased. Was maintained at 75 ° C. for 1 hour to further proceed polymerization, and then cooled to obtain a mixed aqueous solution of a vinyl alcohol polymer (A) having a solid content concentration of 20% and polyMAPTAC.
(実施例4)
ビニルアルコール系重合体(A)として重合度3500、けん化度88.0モル%の重合体、イオン性重合体(B)としてポリアクリル酸(和光純薬社製、分子量5000)、カルボキシラートアニオンの対イオンとして水酸化セシウム、アルカリ金属化合物(C)として炭酸セシウムを表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
Example 4
As a vinyl alcohol polymer (A), a polymer having a polymerization degree of 3500 and a saponification degree of 88.0 mol%, an ionic polymer (B) having a polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 5000), a carboxylate anion Cesium hydroxide as a counter ion and cesium carbonate as an alkali metal compound (C) were blended in the proportions shown in Table 1, and ion-exchanged water was added to prepare a film-forming stock solution having a solid content concentration of 7.5% by mass. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
(実施例5)
ビニルアルコール系重合体(A)として重合度1700、けん化度98.6モル%の重合体、イオン性重合体(B)としてポリアクリル酸(和光純薬社製、分子量5000)、カルボキシラートアニオンの対イオンとして水酸化カリウム、アルカリ金属化合物(C)として炭酸カリウム、さらにアミン化合物(D)として第0世代ポリアミドアミンデンドリマー(シグマアルドリッチジャパン社製、分子量516)、及びポリアリルアミン(日東紡社製、銘柄PAA−25)を表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
(Example 5)
As a vinyl alcohol polymer (A), a polymer having a polymerization degree of 1700 and a saponification degree of 98.6 mol%, an ionic polymer (B) having polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 5000), a carboxylate anion Potassium hydroxide as counter ion, potassium carbonate as alkali metal compound (C), and 0th generation polyamide amine dendrimer (Sigma Aldrich Japan, molecular weight 516) and polyallylamine (manufactured by Nittobo Co., Ltd.) as amine compound (D) Brand PAA-25) was blended in the proportions shown in Table 1, and ion-exchanged water was added to prepare a membrane-forming stock solution having a solid content concentration of 7.5% by mass. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
(実施例6)
ビニルアルコール系重合体(A)として重合度1700、けん化度88.0モル%の重合体、イオン性重合体(B)としてポリ(2−アクリルアミド−2−メチルプロパンスルホン酸)(シグマアルドリッチジャパン社製、分子量200万、略称:ポリAMPS)、スルホネートアニオンの対イオンとして水酸化カリウム、アルカリ金属化合物(C)として炭酸カリウムを表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
(Example 6)
As the vinyl alcohol polymer (A), a polymer having a polymerization degree of 1700 and a saponification degree of 88.0 mol%, and as the ionic polymer (B), poly (2-acrylamido-2-methylpropanesulfonic acid) (Sigma-Aldrich Japan) Manufactured, molecular weight 2 million, abbreviation: polyAMPS), potassium hydroxide as the counter ion of the sulfonate anion, potassium carbonate as the alkali metal compound (C) in the proportions shown in Table 1, added with ion exchange water and solid A film-forming stock solution having a partial concentration of 7.5% by mass was prepared. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
(実施例7)
ビニルアルコール系重合体(A)として重合度1700、けん化度98.6モル%の重合体、イオン性重合体(B)としてポリアクリル酸(和光純薬社製、分子量5000)、カルボキシラートアニオンの対イオンとして水酸化セシウム、アルカリ金属化合物(C)として炭酸セシウムを表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
(Example 7)
As a vinyl alcohol polymer (A), a polymer having a polymerization degree of 1700 and a saponification degree of 98.6 mol%, an ionic polymer (B) having polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 5000), a carboxylate anion Cesium hydroxide as a counter ion and cesium carbonate as an alkali metal compound (C) were blended in the proportions shown in Table 1, and ion-exchanged water was added to prepare a film-forming stock solution having a solid content concentration of 7.5% by mass. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
(実施例8)
ビニルアルコール系重合体(A)として重合度1700、けん化度98.6モル%の重合体、イオン性重合体(B)として3−(メタクリルアミド)プロピルトリメチルアンモニウムクロライド)の高分子重合体(略称:ポリMAPTAC)、アルカリ金属化合物(C)として炭酸セシウムを表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
なお、MAPTACの高分子量化については、前記実施例3と同様に作製した。
(Example 8)
A polymer having a polymerization degree of 1700 and a saponification degree of 98.6 mol% as the vinyl alcohol polymer (A), and a polymer of 3- (methacrylamido) propyltrimethylammonium chloride) as the ionic polymer (B) (abbreviation) : PolyMAPTAC) and cesium carbonate as an alkali metal compound (C) were blended in the proportions shown in Table 1, and ion-exchanged water was added to prepare a membrane-forming stock solution having a solid content concentration of 7.5% by mass. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
In addition, about high molecular weight of MAPTAC, it produced similarly to the said Example 3.
(実施例9)
ビニルアルコール系重合体(A)として重合度1100、けん化度98.6モル%の重合体、イオン性重合体(B)としてポリアクリル酸(和光純薬社製、分子量5000)、カルボキシラートアニオンの対イオンとして水酸化ナトリウム、アルカリ金属化合物(C)として炭酸ナトリウム、さらにアミン化合物(D)として第0世代ポリアミドアミンデンドリマー(シグマアルドリッチジャパン社製、分子量516)、及びポリアリルアミン(日東紡社製、銘柄PAA−15C、第1級アミンの含有率:17.5meq/g)を表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
Example 9
As a vinyl alcohol polymer (A), a polymer having a polymerization degree of 1100 and a saponification degree of 98.6 mol%, an ionic polymer (B) having polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 5000), a carboxylate anion Sodium hydroxide as counter ion, sodium carbonate as alkali metal compound (C), and 0th generation polyamide amine dendrimer (Sigma Aldrich Japan, molecular weight 516) and polyallylamine (manufactured by Nittobo Co., Ltd.) as amine compound (D) Brand PAA-15C, primary amine content: 17.5 meq / g) is blended in the proportions shown in Table 1, and ion-exchanged water is added to form a membrane-forming stock solution having a solid content concentration of 7.5% by mass. Produced. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
(実施例10)
ビニルアルコール系重合体(A)として重合度1100、けん化度98.6モル%の重合体、イオン性重合体(B)としてポリ(P−スチレンスルホン酸)(和光純薬社製、20wt%水溶液、略称:ポリPSS)、スルホネートアニオンの対イオンとして水酸化ナトリウム、アルカリ金属化合物(C)として炭酸カリウムを表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
(Example 10)
A polymer having a polymerization degree of 1100 and a saponification degree of 98.6 mol% as the vinyl alcohol polymer (A), and poly (P-styrenesulfonic acid) (made by Wako Pure Chemical Industries, 20 wt% aqueous solution) as the ionic polymer (B) , Abbreviated: polyPSS), sodium hydroxide as the counter ion of the sulfonate anion, and potassium carbonate as the alkali metal compound (C) in the proportions shown in Table 1, and ion exchange water is added to obtain a solid content concentration of 7.5 A mass% stock solution was prepared. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
(比較例1)
ビニルアルコール系重合体(A)として重合度1100、けん化度98.6モル%の重合体、アルカリ金属化合物(C)として炭酸セシウム、以上2成分のみを表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
(Comparative Example 1)
As a vinyl alcohol polymer (A), a polymer having a polymerization degree of 1100, a saponification degree of 98.6 mol%, an alkali metal compound (C) as cesium carbonate, and the above two components alone are blended in the proportions shown in Table 1, Ion exchange water was added to prepare a membrane forming stock solution having a solid content concentration of 7.5% by mass. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
(比較例2)
ビニルアルコール系重合体(A)として重合度1700、けん化度98.6モル%の重合体、アルカリ金属化合物(C)として炭酸カリウム、以上2成分のみを表1に示すとおりの割合で配合し、イオン交換水を加えて固形分濃度7.5質量%の製膜原液を作製した。この溶液を分画分子量30万、ポリエーテルスルホンを素材とした限外ろ過膜(ミリポア社製、商品名バイオマックス)上に流延して複合膜を作製し、二酸化炭素の膜透過速度Q(CO2)、及び二酸化炭素選択性αを求めた。得られた結果を表1にまとめて示す。
(Comparative Example 2)
As a vinyl alcohol polymer (A), a polymer having a polymerization degree of 1700, a saponification degree of 98.6 mol%, an alkali metal compound (C) as potassium carbonate, and the above two components alone are blended in the proportions shown in Table 1, Ion exchange water was added to prepare a membrane forming stock solution having a solid content concentration of 7.5% by mass. This solution was cast on an ultrafiltration membrane (trade name Biomax, manufactured by Millipore) using a molecular weight cut off of 300,000 and polyethersulfone as a raw material to produce a composite membrane. CO 2 ) and carbon dioxide selectivity α were determined. The obtained results are summarized in Table 1.
表1に示すように、比較例1および2では、ビニルアルコール系重合体とイオン性重合体とアルカリ金属化合物が共存していないため、分離対象となる混合ガスに水蒸気が含まれている場合、二酸化炭素膜透過速度Q(CO2)が小さく、また二酸化炭素選択性αも十分ではない。
一方、実施例1〜10では、分離対象となる混合ガスに水蒸気が含まれている場合であっても、いずれも二酸化炭素膜透過速度Q(CO2)が大きく、さらに70%以上もの二酸化炭素選択性αを示している。
アミン系化合物を含む実施例では、その二酸化炭素膜透過速度Q(CO2)を高め、特に二酸化炭素選択性αを90%以上に向上することができる。
As shown in Table 1, in Comparative Examples 1 and 2, since the vinyl alcohol polymer, the ionic polymer, and the alkali metal compound do not coexist, when the mixed gas to be separated contains water vapor, The carbon dioxide membrane permeation rate Q (CO 2 ) is small, and the carbon dioxide selectivity α is not sufficient.
On the other hand, in Examples 1 to 10, even when the mixed gas to be separated contains water vapor, the carbon dioxide membrane permeation rate Q (CO 2 ) is high, and more than 70% of carbon dioxide. The selectivity α is shown.
In an embodiment including an amine compound, the carbon dioxide membrane permeation rate Q (CO 2 ) can be increased, and in particular, the carbon dioxide selectivity α can be improved to 90% or more.
本発明に係るガス分離膜は、混合ガス、特に水蒸気の含まれる混合ガスから、二酸化炭素を選択的に分離する性能が優れており、石炭ガス化火力発電より産生される水性シフトガスからの二酸化炭素の分離、天然ガス田より産生される天然ガスからの二酸化炭素の分離、石炭火力発電より排出される排ガスからの二酸化炭素の分離などにおいて有用である。 The gas separation membrane according to the present invention has excellent performance for selectively separating carbon dioxide from a mixed gas, particularly a mixed gas containing water vapor, and carbon dioxide from an aqueous shift gas produced from coal gasification thermal power generation. It is useful for separation of carbon dioxide from natural gas produced from natural gas fields, separation of carbon dioxide from exhaust gas discharged from coal-fired power generation, and the like.
以上、本発明の好ましい実施態様を例示的に説明したが、当業者であれば、特許請求の範囲に開示した本発明の範囲および精神から逸脱することなく多様な修正、付加および置換ができることが理解可能であろう。 Although the preferred embodiments of the present invention have been described above by way of example, those skilled in the art can make various modifications, additions and substitutions without departing from the scope and spirit of the present invention disclosed in the claims. It will be understandable.
Claims (10)
任意で、前記カチオンの対イオンは、ハロゲン化物イオン、水酸化物イオン、リン酸イオン、カルボン酸イオンからなる群から選択される少なくとも一種であってもよく、前記アニオンの対イオンは、アルカリ金属イオンであってもよいことを特徴とする請求項1記載のガス分離膜。 The ionic polymer (B) contains a quaternary ammonium cation as a cation; and / or a carboxylate anion and / or a sulfonate anion as an anion;
Optionally, the counter ion of the cation may be at least one selected from the group consisting of halide ion, hydroxide ion, phosphate ion, and carboxylate ion, and the counter ion of the anion may be an alkali metal. The gas separation membrane according to claim 1, which may be ions.
[式中、A1は炭素数1〜3の二価有機残基を示し、nは0または1の整数を示す。]
で示される基および/または式(2):
[式中、A2は炭素数1〜3の二価有機残基を示し、nは0または1の整数を示す。]
で示される基を含有するポリアミドアミンデンドリマー(D1)を含むことを特徴とする請求項5記載のガス分離膜。 The amine compound (D) is represented by the formula (1):
[Wherein, A 1 represents a C 1-3 divalent organic residue, and n represents an integer of 0 or 1. ]
And / or formula (2):
[Wherein, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and n represents an integer of 0 or 1. ]
The gas separation membrane according to claim 5, comprising a polyamidoamine dendrimer (D1) containing a group represented by the formula:
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008068238A (en) * | 2006-09-15 | 2008-03-27 | Research Institute Of Innovative Technology For The Earth | Gas separation membrane and its utilization |
JP2010155207A (en) * | 2008-12-26 | 2010-07-15 | Kuraray Co Ltd | Ethylene-vinyl alcohol polymer composite-membrane for use in gas separation membrane |
WO2010143647A1 (en) * | 2009-06-09 | 2010-12-16 | 国立大学法人山口大学 | Hollow fiber membrane and manufacturing method therefor |
WO2011102326A1 (en) * | 2010-02-16 | 2011-08-25 | 財団法人地球環境産業技術研究機構 | Gas separation composite membrane |
JP2011183379A (en) * | 2010-02-10 | 2011-09-22 | Fujifilm Corp | Gas separation membrane, manufacturing method therefor, gas separation method using the same, module, and separator |
JP2012192316A (en) * | 2011-03-15 | 2012-10-11 | Research Institute Of Innovative Technology For The Earth | Gas separation composite membrane |
JP2013027806A (en) * | 2011-07-27 | 2013-02-07 | Fujifilm Corp | Carbon dioxide separation membrane, support for carbon dioxide separation membrane, and method of manufacturing them |
JP2013027841A (en) * | 2011-07-29 | 2013-02-07 | Fujifilm Corp | Carbon dioxide separation member, method for manufacturing the same, and carbon dioxide separation module |
JP2013049048A (en) * | 2011-08-01 | 2013-03-14 | Renaissance Energy Research:Kk | Co2-facilitated transport membrane, and method for manufacturing same |
JP2013107076A (en) * | 2008-01-24 | 2013-06-06 | Renaissance Energy Research:Kk | Carbon dioxide separation apparatus |
JP2014014803A (en) * | 2012-07-11 | 2014-01-30 | Fujifilm Corp | Method of producing complex for carbon dioxide separation, complex for carbon dioxide separation, module for carbon dioxide separation, carbon dioxide separation apparatus, and carbon dioxide separation method |
-
2014
- 2014-03-28 JP JP2014069838A patent/JP6223255B2/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008068238A (en) * | 2006-09-15 | 2008-03-27 | Research Institute Of Innovative Technology For The Earth | Gas separation membrane and its utilization |
JP2013107076A (en) * | 2008-01-24 | 2013-06-06 | Renaissance Energy Research:Kk | Carbon dioxide separation apparatus |
JP2010155207A (en) * | 2008-12-26 | 2010-07-15 | Kuraray Co Ltd | Ethylene-vinyl alcohol polymer composite-membrane for use in gas separation membrane |
WO2010143647A1 (en) * | 2009-06-09 | 2010-12-16 | 国立大学法人山口大学 | Hollow fiber membrane and manufacturing method therefor |
JP2011183379A (en) * | 2010-02-10 | 2011-09-22 | Fujifilm Corp | Gas separation membrane, manufacturing method therefor, gas separation method using the same, module, and separator |
WO2011102326A1 (en) * | 2010-02-16 | 2011-08-25 | 財団法人地球環境産業技術研究機構 | Gas separation composite membrane |
JP2012192316A (en) * | 2011-03-15 | 2012-10-11 | Research Institute Of Innovative Technology For The Earth | Gas separation composite membrane |
JP2013027806A (en) * | 2011-07-27 | 2013-02-07 | Fujifilm Corp | Carbon dioxide separation membrane, support for carbon dioxide separation membrane, and method of manufacturing them |
JP2013027841A (en) * | 2011-07-29 | 2013-02-07 | Fujifilm Corp | Carbon dioxide separation member, method for manufacturing the same, and carbon dioxide separation module |
JP2013049048A (en) * | 2011-08-01 | 2013-03-14 | Renaissance Energy Research:Kk | Co2-facilitated transport membrane, and method for manufacturing same |
JP2014014803A (en) * | 2012-07-11 | 2014-01-30 | Fujifilm Corp | Method of producing complex for carbon dioxide separation, complex for carbon dioxide separation, module for carbon dioxide separation, carbon dioxide separation apparatus, and carbon dioxide separation method |
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