WO2015151756A1 - ガス分離複合体およびその製造方法 - Google Patents
ガス分離複合体およびその製造方法 Download PDFInfo
- Publication number
- WO2015151756A1 WO2015151756A1 PCT/JP2015/057345 JP2015057345W WO2015151756A1 WO 2015151756 A1 WO2015151756 A1 WO 2015151756A1 JP 2015057345 W JP2015057345 W JP 2015057345W WO 2015151756 A1 WO2015151756 A1 WO 2015151756A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas separation
- group
- separation layer
- metal support
- oxide film
- Prior art date
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 261
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims description 95
- 229910052751 metal Inorganic materials 0.000 claims abstract description 122
- 239000002184 metal Substances 0.000 claims abstract description 122
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 126
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 121
- 239000004642 Polyimide Substances 0.000 claims description 73
- 229920001721 polyimide Polymers 0.000 claims description 73
- 239000000463 material Substances 0.000 claims description 43
- 239000008199 coating composition Substances 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 34
- 238000004090 dissolution Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000035699 permeability Effects 0.000 abstract description 23
- 239000007789 gas Substances 0.000 description 276
- 239000010410 layer Substances 0.000 description 130
- 239000010408 film Substances 0.000 description 105
- 125000004432 carbon atom Chemical group C* 0.000 description 96
- -1 diamine compound Chemical class 0.000 description 65
- 150000001875 compounds Chemical class 0.000 description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 40
- 239000002585 base Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 37
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 29
- 229910017604 nitric acid Inorganic materials 0.000 description 29
- 239000012528 membrane Substances 0.000 description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 28
- 125000001424 substituent group Chemical group 0.000 description 28
- 125000003118 aryl group Chemical group 0.000 description 26
- 238000007788 roughening Methods 0.000 description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 description 20
- 238000007747 plating Methods 0.000 description 20
- 125000001931 aliphatic group Chemical group 0.000 description 19
- 238000005868 electrolysis reaction Methods 0.000 description 19
- 239000001569 carbon dioxide Substances 0.000 description 18
- 239000008151 electrolyte solution Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 125000003277 amino group Chemical group 0.000 description 14
- 230000005611 electricity Effects 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000007743 anodising Methods 0.000 description 10
- 125000000732 arylene group Chemical group 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 150000001553 barium compounds Chemical class 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000001641 gel filtration chromatography Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000004149 thio group Chemical group *S* 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- KIMAYOCXRMGROE-UHFFFAOYSA-N 1,3,4,6-tetramethylcyclohexa-3,5-diene-1,2-diamine Chemical compound CC1=C(C)C(N)C(C)(N)C(C)=C1 KIMAYOCXRMGROE-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- SIWNEELMSUHJGO-UHFFFAOYSA-N 2-(4-bromophenyl)-4,5,6,7-tetrahydro-[1,3]oxazolo[4,5-c]pyridine Chemical compound C1=CC(Br)=CC=C1C(O1)=NC2=C1CCNC2 SIWNEELMSUHJGO-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- WONYVCKUEUULQN-UHFFFAOYSA-N 2-methyl-n-(2-methylphenyl)aniline Chemical class CC1=CC=CC=C1NC1=CC=CC=C1C WONYVCKUEUULQN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical class C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical class C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 125000003341 7 membered heterocyclic group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 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
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- MHDLAWFYLQAULB-UHFFFAOYSA-N anilinophosphonic acid Chemical compound OP(O)(=O)NC1=CC=CC=C1 MHDLAWFYLQAULB-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 125000005427 anthranyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002785 azepinyl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 1
- 229940094800 barium oxalate Drugs 0.000 description 1
- OOULUYZFLXDWDQ-UHFFFAOYSA-L barium perchlorate Chemical compound [Ba+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O OOULUYZFLXDWDQ-UHFFFAOYSA-L 0.000 description 1
- ARSLNKYOPNUFFY-UHFFFAOYSA-L barium sulfite Chemical compound [Ba+2].[O-]S([O-])=O ARSLNKYOPNUFFY-UHFFFAOYSA-L 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- HLKMEIITONDPGG-UHFFFAOYSA-L barium(2+);2-hydroxypropanoate Chemical compound [Ba+2].CC(O)C([O-])=O.CC(O)C([O-])=O HLKMEIITONDPGG-UHFFFAOYSA-L 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical group NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940111685 dibasic potassium phosphate Drugs 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- NBAUUSKPFGFBQZ-UHFFFAOYSA-N diethylaminophosphonic acid Chemical compound CCN(CC)P(O)(O)=O NBAUUSKPFGFBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 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
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- ZGJOORCILCWISV-UHFFFAOYSA-L magnesium difluoride pentahydrate Chemical compound O.O.O.O.O.[F-].[F-].[Mg++] ZGJOORCILCWISV-UHFFFAOYSA-L 0.000 description 1
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoric acid amide group Chemical group P(N)(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
- 235000013926 potassium gluconate Nutrition 0.000 description 1
- 229960003189 potassium gluconate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000005554 pyridyloxy group Chemical group 0.000 description 1
- 125000005030 pyridylthio group Chemical group N1=C(C=CC=C1)S* 0.000 description 1
- ZLIBICFPKPWGIZ-UHFFFAOYSA-N pyrimethanil Chemical compound CC1=CC(C)=NC(NC=2C=CC=CC=2)=N1 ZLIBICFPKPWGIZ-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 125000000213 sulfino group Chemical group [H]OS(*)=O 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 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
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
- B01D63/066—Tubular membrane modules with a porous block having membrane coated passages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0471—Surface coating material
- B01D2239/0478—Surface coating material on a layer of the filter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/06—Surface irregularities
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
Definitions
- the present invention relates to a gas separation complex and a method for producing the same.
- a material composed of a polymer compound has gas permeability specific to each material. Based on the property, a desired gas component can be selectively permeated and separated by a membrane composed of a specific polymer compound. As an industrial utilization mode of this gas separation membrane, it is considered to separate and recover it from a large-scale carbon dioxide generation source in a thermal power plant, a cement plant, a steelworks blast furnace, etc. in connection with the problem of global warming. Has been. And this membrane separation technique attracts attention as a means for solving environmental problems that can be achieved with relatively small energy.
- natural gas and biogas gas generated by fermentation and anaerobic digestion of biological waste, organic fertilizer, biodegradable substances, sewage, garbage, energy crops, etc.
- gases containing methane and carbon dioxide are mainly mixed gases containing methane and carbon dioxide.
- a membrane separation method has been studied.
- Such a gas separation membrane needs to be a thin film in order to ensure practical gas permeability.
- the mechanical strength of the gas separation membrane is lowered, so that a defect occurs and the gas separation performance may be lowered. Therefore, in order to satisfy gas permeability, gas separation performance, and mechanical strength, a gas separation membrane is formed on a support layer having gas permeability to form a composite membrane.
- Patent Document 1 describes the use of a porous support as the support layer, and also describes various resins such as polyolefin resins and fluorine-containing resins as the material (claim 1). [0022]). Furthermore, Patent Document 1 describes that the support layer may have a support such as a woven fabric, a non-woven fabric, or a net in order to impart mechanical strength. Various resins such as polyester are described ([0024]).
- a support layer made of an organic material such as a resin is not sufficient in terms of heat resistance
- heat during gas separation membrane formation or gas separation operation Due to the heat at the time, the support layer is deformed or damaged, so that the gas separation membrane cannot be properly supported, and the gas separation performance is deteriorated.
- the present invention has high heat resistance and mechanical strength, and prevents the support layer from being deformed or damaged by heat at the time of gas separation membrane formation or heat at the time of gas separation operation.
- An object of the present invention is to provide a gas separation complex having high gas permeability and gas separation properties by appropriately supporting the layer and a method for producing the gas separation complex.
- the present inventors formed a gas separation layer having a predetermined thickness on a metal support having through holes having a predetermined average opening diameter and an opening ratio. It is found that it has high heat resistance and mechanical strength, prevents the support layer from being deformed or damaged by heat, supports the gas separation layer properly, and has high gas permeability and gas separation property.
- the present invention has been completed. That is, it has been found that the above object can be achieved by the following configuration.
- a metal support having a plurality of through holes in the thickness direction; A gas separation layer laminated on the surface of the metal support, The thickness of the gas separation layer is 0.1-5 ⁇ m, A gas separation composite in which an average opening diameter of through-holes in a metal support is from 0.1 to 30 ⁇ m and an opening ratio is from 0.05 to 10%.
- a method for producing a gas separation composite comprising a separation layer forming step of curing a coating composition coated on the surface of a metal support to form a gas separation layer having a thickness of 0.1 to 5 ⁇ m.
- the gas separation layer is insoluble polyimide,
- the metal support is an aluminum substrate
- an oxide film forming process is performed on the surface of the aluminum base material, and an oxide film forming process for forming an oxide film. After the oxide film forming process, an electrochemical dissolution process is performed to form a through hole.
- the preparatory step includes a metal coating step of coating a part or all of the surface of the aluminum base including at least the inner wall of the through hole with a metal other than aluminum after the through hole forming step [9] or [10] ]
- the surface of the metal support on the side on which the gas separation layer is formed is roughened so that the surface area ratio ⁇ S is 20 to 80%.
- the present invention has high heat resistance and mechanical strength, and the support layer is deformed or damaged by heat during gas separation membrane formation or heat during gas separation operation.
- the support layer is deformed or damaged by heat during gas separation membrane formation or heat during gas separation operation.
- FIG. 2 (A) to 2 (E) are schematic cross-sectional views showing an example of a preferred embodiment of a method for producing a metal support
- FIG. 2 (A) is a schematic cross-sectional view of an aluminum substrate
- FIG. 2B is a schematic cross-sectional view showing a state in which an oxide film is formed on the aluminum base material
- FIG. 2 (D) is a schematic cross-sectional view showing a state where through holes are formed in the aluminum base material and the oxide film after chemical dissolution treatment
- FIG. 2 (D) shows the state after the oxide film is removed after the electrochemical dissolution treatment.
- FIG. 2E is a schematic cross-sectional view showing a state after an electrochemical surface roughening process is performed after the oxide film is removed.
- 3 (A) to 3 (E) are schematic cross-sectional views showing another example of a preferred embodiment of a method for producing a metal support
- FIG. 3 (A) is a schematic view of an aluminum substrate.
- FIG. 3 (B) is a schematic cross-sectional view showing a state in which an oxide film is formed on the aluminum base and an oxide film is formed on the front surface and the back surface.
- FIG. FIG. 3D is a schematic cross-sectional view showing a state in which an electrochemical dissolution process is performed after the film formation process, and through holes are formed in the aluminum base material and the oxide film, and FIG.
- FIG. 3D is an oxidation process after the electrochemical dissolution process.
- FIG. 3E is a schematic cross-sectional view showing a state after the film is removed, and
- FIG. 3E is a schematic cross-sectional view showing a state after an electrochemical roughening treatment is performed after the oxide film is removed.
- FIG. 4 (A) and 4 (B) are schematic cross-sectional views of an aluminum plate produced by another embodiment of the method for producing a metal support, and
- FIG. 4 (A) is a diagram of FIG. 3 (C).
- 4B is a schematic cross-sectional view showing a state where the inner wall of the through hole of the aluminum base shown in FIG. 4 is coated with a metal other than aluminum, and FIG. 4B is shown in FIG. 2D or FIG.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the gas separation composite of the present invention has a metal support having a plurality of through holes in the thickness direction, and a gas separation layer laminated on the surface of the metal support, and the thickness of the gas separation layer is 0.1.
- the average opening diameter of the through holes formed in the metal support is 0.1 to 30 ⁇ m, and the opening ratio is 0.05 to 10%.
- FIG. 1 is a schematic cross-sectional view showing an example of a preferred embodiment of the gas separation complex of the present invention.
- a gas separation complex 100 includes a metal support 10 having a plurality of through holes 5 formed with a predetermined opening ratio and an opening diameter, and a gas separation layer formed on the metal support 10. 102.
- the metal support 10 is a member that supports the gas separation layer 102, and the gas separation layer 102 is laminated on one main surface. Further, the metal support 10 has a plurality of through holes 5 penetrating in the thickness direction.
- the through-hole 5 is a passage for allowing the gas separated by the gas separation layer 102 (the gas that has passed through the gas separation layer 102) to pass through the surface opposite to the gas separation layer 102.
- the average opening diameter of the through holes 5 is 0.1 ⁇ m to 30 ⁇ m.
- the average opening diameter of the through holes 5 is 0.1 ⁇ m to 30 ⁇ m.
- the coating composition By setting the average opening diameter of the through holes 5 to 0.1 ⁇ m or more, it is possible to prevent the gas flow separated by the gas separation layer 102 from being suppressed. Further, by setting the average opening diameter of the through holes 5 to 5 ⁇ m or less, it is possible to prevent the coating composition to be the gas separation layer 102 from entering the through holes 5 when forming the gas separation layer 102.
- a gas separation layer 102 can be formed. Specifically, by setting the average opening diameter of the through holes 5 to 30 ⁇ m or less, the coating composition leaks into the through holes 5 and the gas separation layer 102 is not formed at the positions of the through holes 5, resulting in defects.
- the coating composition can be prevented, and proper gas separation can be ensured.
- the average opening diameter of the through holes 5 is preferably 0.1 ⁇ m to 10 ⁇ m, and more preferably 0.1 ⁇ m to 5 ⁇ m.
- the opening ratio of the through holes 5 on the main surface of the metal support 10 is 0.05% to 10%. If the aperture ratio is less than 0.05%, the gas flow separated by the gas separation layer 102 may be suppressed. On the other hand, if the aperture ratio exceeds 10%, the mechanical strength of the metal support 10 is lowered, and there is a possibility that the metal support 10 may be broken (cracked) when pressed or handled. From the above viewpoint, the opening ratio of the through hole 5 is preferably 0.05% to 5%.
- the average opening diameter of the through-holes was obtained by photographing the surface of the metal support with a magnification of 200 times from directly above using a high-resolution scanning electron microscope (SEM). At least 20 pits (concave / convex) having a continuous medium wave structure were extracted, and the diameter was read to obtain the opening diameter, and the average value of these was calculated as the average opening diameter.
- SEM scanning electron microscope
- the aperture ratio of the through-hole was determined by photographing the surface of the metal support at a magnification of 200 times from directly above using a high-resolution scanning electron microscope (SEM), and a 30 mm ⁇ 30 mm field of view of the obtained SEM photograph (5 ), Binarize with image analysis software, etc., and observe the through-hole part and the non-through-hole part. From the total opening area of the through-hole and the area of the visual field (geometric area), the ratio (opening area / Calculated from the geometric area), and the average value in each field of view (5 locations) was calculated as the aperture ratio.
- SEM scanning electron microscope
- the ratio (X / T) between the average opening diameter (X) of the through holes 5 and the thickness (T) of the gas separation layer 102 described later is preferably 0.02 to 100, preferably 0.02 to More preferably, it is 50. By setting the ratio (X / T) within this range, it is possible to form the gas separation layer 102 having an appropriate thickness free from defects and thick film portions on the metal support 10 having the through holes 5.
- the thickness of the metal support 10 is preferably 5 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, and particularly preferably 5 ⁇ m to 20 ⁇ m. If the thickness of the metal support 10 is less than 5 ⁇ m, the mechanical strength is insufficient, and wrinkles, defects, and the like are likely to occur. Therefore, the gas separation layer 102 may not be properly supported. Moreover, when the thickness of the metal support 10 exceeds 100 ⁇ m, it may be difficult to form the through holes 5 having the average opening diameter.
- the surface area ratio ⁇ S at the interface between the metal support 10 and the gas separation layer 102 is preferably 20% to 80%, and more preferably 60% to 80%.
- the adhesion between the metal support 10 and the gas separation layer 102 can be improved.
- the coating composition can be prevented from penetrating into the through-hole 5 when the coating composition of the gas separation layer 102 is applied.
- the surface of the metal support 10 is roughened before the gas separation layer 102 is formed,
- the surface area ratio ⁇ S on the surface of the metal support 10 may be 20% to 80%.
- the metal used as a raw material of the metal support 10 is not particularly limited, and various metals such as aluminum, stainless steel, steel, and copper can be used. Among these, aluminum (aluminum alloy) is preferable because it is excellent in workability, strength, and flexibility. In this specification, various base materials made of the above-described aluminum or aluminum alloy are collectively used as an aluminum base material.
- the foreign elements that may be contained in the aluminum alloy include silicon, iron, copper, manganese, magnesium, chromium, zinc, bismuth, nickel, titanium, etc., and the content of the foreign elements in the alloy is 10% by mass or less. It is.
- the support is prevented from being deformed or damaged by the heat at the time of gas separation layer formation or the heat at the time of gas separation operation.
- the gas separation layer can be properly supported and the gas separation performance can be prevented from deteriorating.
- gas permeability is required. Therefore, when a metal is used as the material for the support, it is conceivable to form a large number of through holes as gas passages.
- the present inventors when using a metal as a support, simply formed a through hole, the coating composition of the gas separation layer leaked into the through hole, or the pressure during the gas separation operation It has been found that there is a problem that the gas separation layer is damaged or the support is deformed or damaged and the gas separation layer cannot be properly supported. This is probably because the metal support is inferior in elasticity and stretchability compared to the support using an organic material.
- the gas separation composite of the present invention has high heat resistance and mechanical strength, prevents liquid leakage of the coating composition, damage to the gas separation layer, etc., and properly supports the gas separation layer. And has high gas permeability and gas separation.
- the gas separation layer 102 selectively separates a predetermined gas component based on the property of each material and is formed on the metal support 10.
- the thickness of the gas separation layer 102 is 0.1 ⁇ m to 5 ⁇ m. If the thickness of the gas separation layer 102 is less than 0.1 ⁇ m, defects may occur in the gas separation layer and gas separation performance may be reduced. Further, if the thickness of the gas separation layer 102 exceeds 5 ⁇ m, gas permeability may be lowered. From the above viewpoint, the thickness of the gas separation layer 102 is preferably 0.1 ⁇ m to 2 ⁇ m.
- the type of the gas separation layer 102 is not particularly limited, and various known gas separation membranes such as a dissolution diffusion membrane and a facilitated transport membrane can be used. Moreover, there is no limitation in particular also in the kind of gas which the gas separation layer 102 isolate
- the present invention can be suitably used for the gas separation composite 100 having the gas separation layer 102 having a process that involves heating when forming. Furthermore, it can utilize suitably for the gas separation composite body 100 which has the gas separation layer 102 which can improve gas-separation property by heating.
- Examples of the gas separation layer 102 that can improve the gas separation property by heating include insoluble polyimide.
- the gas separation layer 102 containing insoluble polyimide is formed by applying a polyimide compound or polyimide precursor solution (coating solution) to the metal support 10 and drying to form a film containing the polyimide compound or polyimide precursor. Then, a heat treatment at 200 ° C. or higher is performed to insolubilize the polyimide compound constituting the film to form an insoluble polyimide compound, or to close the polyimide precursor constituting the film to form an insoluble polyimide compound. By performing the heat treatment at 200 ° C. or higher, the polyimide compound constituting the film becomes insoluble due to a cross-linked structure.
- a polyimide precursor is a polyamic acid or its derivative (s), and is a compound which ring-closes by heating at 200 degreeC or more and produces
- the content of the insoluble polyimide compound is not particularly limited as long as a desired gas separation performance can be obtained.
- the content of the insoluble polyimide compound is preferably 20% by mass to 100% by mass.
- the “insoluble polyimide compound” means a polyimide compound having a solubility in diacetylamide at 20 ° C. of 20 mg / 100 g or less.
- the insoluble polyimide compound has a solubility in diacetylamide at 20 ° C. of preferably 15 mg / 100 g or less, and more preferably 10 mg / 100 g or less.
- the insoluble polyimide compound may have a solubility in diacetylamide at 20 ° C. of 0 mg / 100 g, but is usually 0.1 mg / 100 g or more.
- the heat treatment time at 200 ° C.
- the heat treatment time is preferably within 10 hours, more preferably within 5 hours, and even more preferably within 2 hours.
- the insoluble polyimide used as the gas separation layer of the gas separation composite of the present invention is preferably a polyimide compound that is insolubilized by heat treatment at 200 ° C. or higher. If it insolubilizes by the heat processing of 200 degreeC or more, there will be no restriction
- the polyimide compound that is insolubilized by heat treatment at 200 ° C. or higher preferably contains a repeating unit represented by the following formula (I).
- This polyimide compound may contain two or more types of repeating units represented by the following formula (I).
- X represents a group having a structure represented by any of the following formulas (I-1) to (I-28).
- * represents a binding site with the carbonyl group of the formula (I).
- X in the formula (I) may be referred to as a mother nucleus, and the mother nucleus X is preferably a group represented by the formula (I-1), (I-2) or (I-4), The group represented by (I-1) or (I-4) is more preferred, and the group represented by (I-1) is particularly preferred.
- X 1 to X 3 represent a single bond or a divalent linking group.
- the divalent linking group —C (R x ) 2 — (R x represents a hydrogen atom or a substituent. When R x is a substituent, they may be linked to each other to form a ring), —O—, —SO 2 —, —C ( ⁇ O) —, —S—, —NR Y — (R Y represents a hydrogen atom, an alkyl group (preferably a methyl group or an ethyl group) or an aryl group (preferably a phenyl group).
- R x represents a substituent
- specific examples thereof include the substituent group Z described below, and an alkyl group (preferably the same as the alkyl group shown in the substituent group Z described below) is preferable.
- An alkyl group having a halogen atom as a substituent is more preferable, and trifluoromethyl is particularly preferable.
- X 3 is connected to one of the two carbon atoms described on the left side and one of the two carbon atoms described on the right side thereof.
- L represents —CH ⁇ CH— or —CH 2.
- R 1 and R 2 represent a hydrogen atom or a substituent.
- substituents include groups listed in the substituent group Z described later.
- R 1 and R 2 may be bonded to each other to form a ring.
- R 1 and R 2 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom.
- the carbon atoms shown in the formulas (I-1) to (I-28) may further have a substituent.
- this substituent include the substituent group Z described later, and among them, an alkyl group or an aryl group is preferable.
- Y represents an arylene group.
- Y is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and still more preferably a phenylene group.
- the arylene group of Y preferably has a substituent, and examples of the substituent include the substituent group Z described later.
- the polyimide compound preferably has both a repeating unit of formula (I) in which Y has a polar group and a repeating unit of formula (I) in which Y does not have a polar group.
- Examples of the polar group that Y may have include a carboxy group, an amino group, a hydroxy group, a sulfone group, a halogen atom, and an alkoxy group.
- the polymer is appropriately densified, and when used in a gas separation membrane, the gas separation selectivity of the membrane can be further improved.
- the ratio of the repeating units represented by the above formula (I) is not particularly limited, and for the purpose of gas separation (recovery rate, purity, etc.) Accordingly, the gas permeability and gas separation selectivity are appropriately adjusted.
- the polyimide compound insolubilized by heat treatment at 200 ° C. or higher used in the present invention is tetracarboxylic dianhydride and diamine (in this specification, “diamine” or “diamine compound” means two or more amino groups. And is preferably a compound having two amino groups).
- Y is a diamine component
- the structure of the portion excluding Y is a tetracarboxylic dianhydride component. That is, the above formula (I) is a repeating unit composed of one tetracarboxylic dianhydride component and one diamine component.
- the amount of the repeating unit of the above formula (I) is preferably 10 mol% or more with respect to the total repeating unit (100 mol%) consisting of one tetracarboxylic dianhydride component and one diamine component, It is more preferably at least mol%, more preferably at least 50 mol%, even more preferably at least 70 mol%, at least 80 mol%, and preferably at 100 mol%. .
- the ratio of the repeating unit of the above formula (I) in the total of the above repeating units is not 100 mol%, the structure of the remaining repeating units is not particularly limited.
- Y in the above formula (I) is a structure derived from substituted or unsubstituted bis (4-aminophenyl) ether, a structure derived from substituted or unsubstituted methylenedianiline, substituted or unsubstituted 4,4 Examples include structures derived from '-diaminodiphenylsulfone and structures derived from substituted or unsubstituted ditolylamine, but the present invention is not limited thereto.
- the molecular weight of the polyimide compound used in the present invention is preferably 10,000 to 1,000,000 as a weight average molecular weight, more preferably 15,000 to 500,000, and still more preferably 20,000 to 200,000. It is.
- the molecular weight and the dispersity are values measured using a GPC (gel filtration chromatography) method, and the molecular weight is a weight average molecular weight in terms of polystyrene.
- the gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. Two to six columns are preferably connected and used.
- the solvent used include ether solvents such as tetrahydrofuran and amide solvents such as N-methylpyrrolidinone.
- the measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and most preferably in the range of 0.5 to 1.5 mL / min. By performing the measurement within this range, the apparatus is not loaded and the measurement can be performed more efficiently.
- the measurement temperature is preferably 10 to 50 ° C, most preferably 20 to 40 ° C. Note that the column and carrier to be used can be appropriately selected according to the physical properties of the polymer compound that is symmetrical to the measurement.
- the polyimide compound insolubilized by heat treatment at 200 ° C. or higher that can be used in the present invention can be synthesized by condensation polymerization of a specific bifunctional acid anhydride (tetracarboxylic dianhydride) and a specific diamine.
- a general book for example, edited by Ikuo Imai and Rikio Yokota, “Latest Polyimide: Fundamentals and Applications”, NTS Corporation, August 25, 2010, p. 3 to 49, Etc.
- At least one tetracarboxylic dianhydride used as a raw material is represented by the following formula (IV). It is preferable that all tetracarboxylic dianhydrides used as raw materials are represented by the following formula (IV).
- tetracarboxylic dianhydrides that can be used in the present invention include the following, but the present invention is not limited thereto.
- At least one of the diamine compounds used as a raw material is an aromatic hydrocarbon having at least two amino groups.
- the aromatic hydrocarbon having at least two amino groups preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably phenylenediamine.
- the aromatic hydrocarbon having at least two amino groups may have a substituent other than the amino group, and examples of the substituent include the substituent group Z described later.
- the aromatic hydrocarbon having at least two amino groups is preferably an aromatic hydrocarbon having two amino groups.
- aromatic hydrocarbon having at least two amino groups described above include, for example, those shown below, but the present invention is not limited thereto.
- the polyimide compound that is insolubilized by heat treatment at 200 ° C. or higher that can be used in the present invention can be obtained by mixing each of the above raw materials in a solvent and subjecting it to condensation polymerization by a conventional method.
- the solvent is not particularly limited, but ester organic solvents such as methyl acetate, ethyl acetate, and butyl acetate; aliphatics such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, and cyclohexanone.
- Ether organic solvents such as ketone, ethylene glycol dimethyl ether, dibutyl butyl ether, tetrahydrofuran, methylcyclopentyl ether, dioxane, amide organic solvents such as N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylimidazolidinone, dimethylacetamide, dimethyl And sulfur-containing organic solvents such as sulfoxide and sulfolane. These organic solvents are appropriately selected as long as it is possible to dissolve tetracarboxylic dianhydride as a reaction substrate, diamine compound, polyamic acid as a reaction intermediate, and polyimide compound as a final product.
- ester type preferably butyl acetate
- aliphatic ketone preferably methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, cyclohexanone
- ether type diethylene glycol monomethyl ether, methyl cyclopentyl) Ether
- amide preferably N-methylpyrrolidone
- sulfur-containing dimethyl sulfoxide, sulfolane
- the polymerization reaction temperature is not particularly limited, and a temperature that can be usually employed in the synthesis of a polyimide compound can be employed. Specifically, it is preferably ⁇ 40 to 60 ° C., more preferably ⁇ 30 to 50 ° C.
- a polyimide compound is obtained by imidizing the polyamic acid produced by the above polymerization reaction by a dehydration ring-closing reaction in the molecule.
- a method for dehydrating and closing a ring a general book (for example, Ikuo Imai, edited by Rikio Yokota, “Latest Polyimide: Fundamentals and Applications”, NTS Inc., August 25, 2010, p. 3) To 49, etc.) can be referred to.
- acetic anhydride or dicyclohexyl is heated in the presence of a basic catalyst such as pyridine, triethylamine or DBU by heating to 120 ° C to 200 ° C for reaction while removing by-product water out of the system.
- a technique such as so-called chemical imidization using a dehydration condensing agent such as carbodiimide and triphenyl phosphite is preferably used.
- the total concentration of tetracarboxylic dianhydride and diamine compound in the polymerization reaction solution of the polyimide compound is not particularly limited, but is preferably 5 to 70% by mass, more preferably 5 to 50% by mass. And more preferably 5 to 30% by mass.
- the polyimide precursor used in the gas separation composite of the present invention is polyamic acid or a derivative thereof, and is not particularly limited as long as it is ring-closed by heat treatment at 200 ° C. or higher to produce an insoluble polyimide. It is preferable that the polyimide precursor can be formed by coating. More specifically, the solubility in dimethylacetamide at 20 ° C. is preferably 500 mg / 100 g or more, and more preferably 1000 to 50000 mg / 100 g.
- the polyimide precursor preferably includes a repeating unit represented by the following formula (II).
- the polyimide compound may contain 2 or more types of repeating units represented by the following formula (II).
- Xa is a tetravalent aliphatic group, a tetravalent aromatic group, or a tetravalent group formed by combining one or more selected from an aliphatic group and an aromatic group.
- a tetravalent group formed by combining one or more selected from aliphatic groups and aromatic groups a plurality of (two or three or more) aromatic groups are linked by a single bond. It is assumed that a tetravalent group formed is included.
- the aliphatic group may be linear or branched, and may be cyclic.
- Xa is a tetravalent aliphatic group
- the carbon number thereof is preferably 3 to 20, more preferably 4 to 18, and still more preferably 6 to 15.
- the carbon number thereof is preferably 4 to 20, more preferably 4 to 18, and still more preferably 5 to 15.
- the carbon number is preferably 4 to 20, and preferably 5 to 15. It is more preferable.
- a tetravalent group formed by combining one or more selected from an aliphatic group and an aromatic group is a tetravalent group having a structure in which two aromatic rings are connected by a single bond or an aliphatic group. It is preferable that X a is more preferably a structure represented by any of the above formulas (I-1) to (I-28).
- R a is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms, more preferably methyl, ethyl, propyl), or an alkyl having 3 to 9 carbon atoms.
- a silyl group preferably an alkylsilyl group having 3 to 6 carbon atoms
- R a are hydrogen atoms.
- R a is an alkylsilyl group, it is preferably a trialkylsilyl group.
- Y a represents a divalent aliphatic group, a divalent aromatic group, or a divalent group formed by combining one or more selected from an aliphatic group and an aromatic group. Show. Here, in “a divalent group formed by combining one or more selected from aliphatic groups and aromatic groups”, plural (two or three or more) aromatic groups are linked by a single bond. It is assumed that a divalent group formed is included.
- the aliphatic group may be linear or branched, and may be cyclic.
- Y a is a divalent aliphatic group, the carbon number thereof is preferably 1-30, and more preferably 2-20.
- Y a is a divalent aromatic group
- the carbon number thereof is preferably 4 to 20, more preferably 4 to 15, still more preferably 5 to 15.
- Y a is more preferably an arylene group, more preferably an arylene group having 6 to 20 carbon atoms, and still more preferably an arylene group having 6 to 15 carbon atoms. More preferably, it is a phenylene group.
- Y a is a divalent group formed by combining one or more selected from an aliphatic group and an aromatic group
- the carbon number is preferably 5 to 30, and preferably 6 to 20. It is more preferable.
- a divalent group formed by combining one or more selected from an aliphatic group and an aromatic group is a divalent group having a structure in which two aromatic rings are connected by a single bond or an aliphatic group. It is preferable that In this case, the carbon number of the structure in which two aromatic rings are linked by a single bond or an aliphatic group is 10 to 30, more preferably 10 to 20, still more preferably 12 to 20, and still more preferably 12 ⁇ 18.
- the aromatic group is preferably an arylene group, more preferably 6 carbon atoms.
- the polyimide precursor used in the present invention is preferably synthesized using tetracarboxylic dianhydride and diamine as raw materials.
- Ya is a diamine component
- the structure of the portion excluding Y is a tetracarboxylic dianhydride component.
- the amount of the repeating unit of the above formula (II) is preferably 10% by mole or more with respect to the total repeating unit (100 mol%) consisting of one tetracarboxylic dianhydride component and one diamine component, It is more preferably at least mol%, more preferably at least 50 mol%, even more preferably at least 70 mol%, at least 80 mol%, and preferably at 100 mol%. .
- the molecular weight of the polyimide precursor used in the present invention is preferably 10,000 to 1,000,000 as a weight average molecular weight, more preferably 15,000 to 500,000, and still more preferably 20,000 to 200,000. 000 is preferred.
- the polyimide precursor can be obtained commercially.
- U-imide varnish (trade name, manufactured by Unitika Co., Ltd.), U-varnish (trade name, manufactured by Ube Industries, Ltd.), Pyre-ML (trade name, manufactured by Industrial Summit Technology) are used as the polyimide precursor in the present invention. Can be used.
- polyimide precursor There is no restriction
- a diamine having a desired structure is dissolved in N-methyl-pyrrolidone or N, N-dimethylacetamide under a nitrogen atmosphere, and a tetracarboxylic dianhydride having a desired structure is added to this solution while stirring.
- the polyimide precursor can be obtained by stirring at 80 ° C. for about 2 hours.
- Substituent group Z An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl) , N-decyl, n-hexadecyl), a cycloalkyl group (preferably a cycloalkyl group having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 10 carbon atoms, such as cyclopropyl, Cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, -Butenyl, 3-pentenyl, etc.), alky
- an aryl group having 6 to 12 carbon atoms such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc.
- amino group amino group, alkylamino group, arylamino group, hetero
- a cyclic amino group preferably an amino group having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzyl Amino, diphenylamino, ditolylamino, etc.
- alkoxy groups preferably having 1 carbon atom
- alkoxy groups preferably having 1 carbon atom
- an alkoxy group having 1 to 20 carbon atoms particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.
- an aryloxy group preferably An aryloxy group having
- Heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like. ),
- An acyl group (preferably an acyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), alkoxy A carbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), aryloxy A carbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl), an acyloxy group ( Preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, especially Preferably, it is an acyloxy group having 2 to 10 carbon atoms, such as acet
- alkoxycarbonylamino group preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino
- aryl Oxycarbonylamino group preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino group
- a sulfonylamino group preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.
- a sulfamoyl group Preferably 0-30 carbon atoms, more preferred 0 to 20 carbon atoms, particularly preferably a sulfam
- An alkylthio group preferably an alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio
- an arylthio group preferably An arylthio group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and a heterocyclic thio group (preferably having 1 to 30 carbon atoms).
- heterocyclic thio group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like.
- a sulfonyl group (preferably a sulfonyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), a sulfinyl group (preferably A sulfinyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably having 1 carbon atom) -30, more preferably a ureido group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), a phosphoramide group (preferably having a carbon number) A phosphoric acid amide group having 1 to 30, more preferably 1 to 20 carbon
- the hetero atom may be a non-aromatic hetero ring, and examples of the hetero atom constituting the hetero ring include a nitrogen atom, an oxygen atom and a sulfur atom, preferably 0 to 30 carbon atoms, more preferably 1 to 12 carbon atoms.
- silyl group examples thereof include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl and the like, and a silyl group (preferably).
- Groups such as trimethylsilyl and triphenylsilyl), silyloxy groups (preferably silyloxy groups having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms).
- substituents may be further substituted with any one or more substituents selected from the above substituent group Z.
- substituents when one structural site has a plurality of substituents, these substituents are connected to each other to form a ring, or condensed with a part or all of the above structural sites to form an aromatic group.
- a ring or an unsaturated heterocyclic ring may be formed.
- a compound or a substituent when a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group, or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.
- substituent group Z when the name of each group is only described ( For example, when only “alkyl group” is described), preferred ranges and specific examples of the corresponding group in the substituent group Z are applied.
- Various polymer compounds can be added to the insoluble polyimide used as the gas separation layer of the gas separation composite of the present invention in order to adjust the film properties.
- High molecular compounds include acrylic polymers, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellac, vinyl resins, acrylic resins, rubber resins. Waxes and other natural resins can be used. Two or more of these may be used in combination.
- nonionic surfactants, cationic surfactants, organic fluoro compounds, and the like can be added to adjust liquid properties.
- the surfactant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfonate of higher fatty acid ester, sulfate ester of higher alcohol ether, sulfonate of higher alcohol ether, higher alkyl
- Anionic surfactants such as alkyl carboxylates of sulfonamides, alkyl phosphates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, ethylene oxide adducts of acetylene glycol,
- Nonionic surfactants such as ethylene oxide adducts of glycerin and polyoxyethylene sorbitan fatty acid esters, and other amphoteric boundaries such as alkyl betaines and amide betaines
- a polymer dispersant may be included, and specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacrylamide. Of these, polyvinylpyrrolidone is preferably used.
- the gas separation composite of the present invention may have a layer other than the metal support and the gas separation layer. Moreover, you may have other layers, such as a contact
- the gas separation complex of the present invention can be suitably used as a gas separation recovery method and a gas separation purification method.
- a gas separation purification method for example, hydrogen, helium, carbon monoxide, carbon dioxide, hydrogen sulfide, oxygen, nitrogen, ammonia, sulfur oxides, nitrogen oxides, hydrocarbons such as methane and ethane, unsaturated hydrocarbons such as propylene, tetrafluoroethane, etc.
- It can be used as a gas separation membrane capable of efficiently separating a specific gas from a gas mixture containing a gas such as a perfluoro compound.
- it is suitably used as a gas separation complex for selectively separating carbon dioxide from a gas mixture containing carbon dioxide / hydrocarbon (methane).
- the permeation rate of carbon dioxide at 40 ° C. and 5 MPa is more than 5 GPU.
- it is more than 10 GPU.
- transmission rate of a carbon dioxide Usually, it is 500 GPU or less, 400 GPU or less may be sufficient, and 200 GPU or less may be sufficient.
- the permeation rate ratio between carbon dioxide and methane (R CO2 / R CH4 ) is preferably 15 or more, more preferably 20 or more, still more preferably 25 or more, still more preferably 30 or more, and even more preferably 40 or more. .
- the upper limit of the transmission speed ratio is not particularly limited, but is usually 100 or less.
- R CO2 represents the carbon dioxide permeation rate
- R CH4 represents the methane permeation rate.
- 1 GPU is 1 ⁇ 10 ⁇ 6 cm 3 (STP) / cm 2 ⁇ sec ⁇ cmHg.
- the pressure during the gas separation is preferably 0.5 to 10 MPa, more preferably 1 to 10 MPa. More preferably, it is ⁇ 7 MPa.
- the gas separation temperature is preferably ⁇ 30 to 90 ° C., more preferably 15 to 70 ° C.
- the gas separation composite of the present invention can be used in various known gas separation modules. Examples of modules include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like.
- a gas separation apparatus having means for separating and recovering or separating and purifying gas using the gas separation complex of the present invention or a gas separation module using the same can be provided.
- the gas separation composite of the present invention may be applied to, for example, a gas separation and recovery apparatus as a membrane absorption hybrid method used in combination with an absorbing solution as described in JP-A-2007-297605.
- the aluminum support may be an aluminum base plate having a plurality of through holes in the thickness direction and an aluminum plate having an oxide film having a plurality of through holes in the thickness direction.
- the aspect which removed the oxide film by the oxide film removal process to be performed, ie, the aluminum plate which consists of an aluminum base material which has a some through-hole in the thickness direction may be sufficient.
- the manufacturing method of the aluminum support includes an oxide film forming step in which an oxide film forming process is performed on the surface of the aluminum substrate 1 to form the oxide film 2.
- FIGS. 2 (A) to 2 (E) the manufacturing method of the aluminum support includes an oxide film forming step in which an oxide film forming process is performed on the surface of the aluminum substrate 1 to form the oxide film 2.
- FIG. 2 (A) and FIG. 2 (B)) the electrolytic dissolution treatment after the oxide film forming step to form the through hole 5, the aluminum substrate 3 having the through hole, and the oxide film 4 having the through hole.
- the oxide film 4 having the through holes is removed, and the oxide film removing step for producing the aluminum plate 10 made of the aluminum base material 3 having the through holes (FIGS. 2C and 2C). D)) is preferred.
- the oxide film removing step the surface of the aluminum substrate 3 having through holes is subjected to an electrochemical surface roughening treatment to produce a roughened aluminum plate 10 (FIG. 2 ( D) and FIG. 2 (E)) are preferred.
- the oxide film 2 is formed on one surface of the aluminum base 1 to form the through hole 5.
- the present invention is not limited to this.
- the through holes 5 may be formed by forming the oxide film 2 on both surfaces (front and back surfaces) of the aluminum base 1. That is, an oxide film forming process (FIGS. 3A and 3B) for forming an oxide film 2 by performing an oxide film forming process on the front surface and the back surface of the aluminum substrate 1, and an oxide film forming process A through hole forming step (FIG. 3 (B) and FIG.
- 3) is carried out by performing electrolytic dissolution treatment later to form the through hole 5 and producing the aluminum substrate 10 having the aluminum substrate 3 having the through hole and the oxide film 4 having the through hole. 3 (C)).
- the oxide film removing step for removing the oxide film 4 after the through hole forming step (FIGS. 3C and 3D). It is preferable to have.
- an electrochemical surface roughening treatment is performed on the aluminum base 3 to roughen the surface (FIGS. 3D and 3E). It is preferable to have it.
- the oxide film formation process which the manufacturing method of this invention has is a process of performing an oxide film formation process on the surface of an aluminum base material, and forming an oxide film.
- the aluminum substrate is not particularly limited, and a known aluminum substrate (for example, alloy numbers 1085, 1N30, 3003 and the like described in JIS standard H4000) can be used.
- the oxide film forming process is not particularly limited, and for example, a process similar to a conventionally known anodizing process can be performed.
- As the anodizing treatment for example, conditions and apparatuses described in paragraphs [0063] to [0073] of JP2012-216513A can be appropriately employed.
- the conditions of the anodizing treatment cannot be determined unconditionally because they vary depending on the electrolyte used, but generally the electrolyte concentration is 1 to 80% by mass, the solution temperature is 5 to 70 ° C., and the current density is 0.5. It is appropriate that ⁇ 60 A / dm 2 , voltage 1 to 100 V, and electrolysis time 1 second to 20 minutes, and the amount of oxide film is adjusted.
- an anodizing treatment performed in a sulfuric acid solution is preferable.
- direct current may be applied between the aluminum substrate and the counter electrode, or alternating current may be applied.
- the current density is preferably 1 to 60 A / dm 2 , and more preferably 5 to 40 A / dm 2 .
- anodizing is performed continuously at a high speed, 5-10 A / dm 2 at the beginning of the anodizing treatment is performed so that current is concentrated on a part of the aluminum substrate and so-called “burning” does not occur.
- the anodization is performed by a liquid power feeding method in which power is supplied to the aluminum base material through the electrolytic solution.
- the amount of the oxide film formed by the anodic oxidation treatment is preferably 0.05 to 50 g / m 2 , and more preferably 0.1 to 10 g / m 2 .
- the said through-hole formation process is a process of performing an electrolytic dissolution process after an oxide film formation process, and forming a through-hole.
- the electrolytic dissolution treatment is not particularly limited, and direct current or alternating current can be used, and an acidic solution can be used as the electrolytic solution. Among these, it is preferable to use an electrolytic solution mainly composed of hydrochloric acid or nitric acid.
- the acidic solution as the electrolytic solution includes, in addition to nitric acid and hydrochloric acid, U.S. Pat. Nos. 4,671,859, 4,661,219, 4,618,405, 4,600,482, 4,566,960, 4,566,958, 4,566,959, 4,416,972, 4,374, Electrolytic solutions described in the specifications of Nos. 710, 4,336,113, and 4,184,932 can also be used.
- the concentration of the acidic solution is preferably 0.5 to 2.5% by mass, particularly preferably 0.7 to 2.0% by mass.
- the liquid temperature of the acidic solution is preferably 20 to 80 ° C., more preferably 30 to 60 ° C.
- An aqueous solution mainly composed of hydrochloric acid or nitric acid is an aqueous solution of hydrochloric acid or nitric acid having a concentration of 1 to 100 g / L. It is possible to add at least one hydrochloric acid compound having a hydrochloric acid ion such as 1 g / L to saturation. Moreover, the metal contained in aluminum alloys, such as iron, copper, manganese, nickel, titanium, magnesium, a silica, may melt
- a solution obtained by adding aluminum chloride, aluminum nitrate or the like to an aqueous solution of hydrochloric acid or nitric acid having a concentration of 0.5 to 2% by mass so that aluminum ions are 3 to 50 g / L is preferably used.
- a direct current is mainly used, but when an alternating current is used, the alternating current power wave is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave, etc. are used. Among these, a rectangular wave or a trapezoidal wave is preferable, and a trapezoidal wave is particularly preferable.
- the average opening diameter is easily 0.1 to 30 ⁇ m by an electrochemical dissolution treatment (hereinafter also abbreviated as “nitric acid dissolution treatment”) using an electrolytic solution mainly composed of nitric acid.
- nitric acid dissolution treatment uses direct current, the average current density is 5 A / dm 2 or more, and the amount of electricity is 50 C / dm 2 or more because it is easy to control the dissolution point of through-hole formation. It is preferable that the electrolytic treatment is performed in step (b).
- the average current density is preferably 100 A / dm 2 or less, and the quantity of electricity is preferably 10,000 C / dm 2 or less.
- concentration and temperature of the electrolytic solution in nitric acid electrolysis are not particularly limited, and electrolysis is performed at a high concentration, for example, 30 to 60 ° C. using a nitric acid electrolytic solution having a nitric acid concentration of 15 to 35% by mass, or a nitric acid concentration of 0. Electrolysis can be carried out at a high temperature, for example, at 80 ° C. or higher, using a 7-2 mass% nitric acid electrolyte.
- the average opening diameter is easily 0.1 to 30 ⁇ m even by an electrochemical dissolution treatment (hereinafter also abbreviated as “hydrochloric acid dissolution treatment”) using an electrolytic solution mainly composed of hydrochloric acid.
- a through hole having an average aperture ratio of 0.05 to 10% can be formed.
- the hydrochloric acid dissolution treatment uses direct current, the average current density is 5 A / dm 2 or more, and the amount of electricity is 50 C / dm 2 or more because it is easy to control the dissolution point of through-hole formation. It is preferable that the electrolytic treatment is performed in step (b).
- the average current density is preferably 100 A / dm 2 or less, and the quantity of electricity is preferably 10,000 C / dm 2 or less.
- concentration and temperature of the electrolytic solution in hydrochloric acid electrolysis are not particularly limited, and electrolysis is performed at 30 to 60 ° C. using a hydrochloric acid electrolytic solution having a high concentration, for example, a hydrochloric acid concentration of 10 to 35% by mass, or a hydrochloric acid concentration of 0. Electrolysis can be performed at a high temperature, for example, 80 ° C. or higher, using a 7-2 mass% hydrochloric acid electrolyte.
- the average opening diameter of the through holes can be set to 0.1 ⁇ m or more, and the opening ratio can be adjusted to 0.1% or more.
- the total thickness (t) of the oxide film and the aluminum substrate when the treatment is performed preferably satisfies the following formula (1), and more preferably satisfies the following formula (2). 5 ⁇ Q / t ⁇ 300 (1) 10 ⁇ Q / t ⁇ 300 (2) This is considered to be because, when the above formula (1) is satisfied, the elution of the oxide film and the aluminum base material by the electrolytic dissolution treatment becomes a suitable state with respect to the thickness.
- the total thickness (t) of the oxide film and the aluminum base material when the electrolytic dissolution treatment is performed is basically the aluminum base before the oxide film formation treatment described above is performed. It becomes the same value as the thickness of the material.
- the optional oxide film removing step that the aluminum support manufacturing method may have is a step of removing the oxide film.
- the oxide film can be removed by performing an acid etching process or an alkali etching process described later.
- the dissolution treatment is a treatment for dissolving the oxide film using a solution (hereinafter referred to as “alumina solution”) that preferentially dissolves the oxide film (aluminum oxide) over aluminum.
- alumina solution a solution that preferentially dissolves the oxide film (aluminum oxide) over aluminum.
- alumina solution for example, chromium compound, nitric acid, sulfuric acid, phosphoric acid, zirconium compound, titanium compound, lithium salt, cerium salt, magnesium salt, sodium fluorosilicate, zinc fluoride, manganese compound, molybdenum
- aqueous solution containing at least one selected from the group consisting of a compound, a magnesium compound, a barium compound and a halogen simple substance is preferable.
- examples of the chromium compound include chromium (III) oxide and anhydrous chromium (VI) acid.
- examples of the zirconium-based compound include zircon ammonium fluoride, zirconium fluoride, and zirconium chloride.
- examples of the titanium compound include titanium oxide and titanium sulfide.
- examples of the lithium salt include lithium fluoride and lithium chloride.
- examples of the cerium salt include cerium fluoride and cerium chloride.
- examples of the magnesium salt include magnesium sulfide.
- Examples of the manganese compound include sodium permanganate and calcium permanganate.
- Examples of the molybdenum compound include sodium molybdate.
- magnesium compounds include magnesium fluoride pentahydrate.
- barium compounds include barium oxide, barium acetate, barium carbonate, barium chlorate, barium chloride, barium fluoride, barium iodide, barium lactate, barium oxalate, barium perchlorate, barium selenate, selenite.
- Examples thereof include barium, barium stearate, barium sulfite, barium titanate, barium hydroxide, barium nitrate, and hydrates thereof.
- barium oxide, barium acetate, and barium carbonate are preferable, and barium oxide is particularly preferable.
- halogen alone include chlorine, fluorine, and bromine.
- the alumina solution is preferably an aqueous solution containing an acid.
- the acid include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and a mixture of two or more acids may be used.
- the acid concentration is preferably 0.01 mol / L or more, more preferably 0.05 mol / L or more, and still more preferably 0.1 mol / L or more. There is no particular upper limit, but generally it is preferably 10 mol / L or less, more preferably 5 mol / L or less.
- the dissolution treatment is performed by bringing the aluminum base material on which the oxide film is formed into contact with the above-described alumina solution.
- the method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.
- the dipping method is a treatment in which an aluminum base material on which an oxide film is formed is dipped in the above-described alumina solution. Stirring during the dipping process is preferable because a uniform process is performed.
- the dipping treatment time is preferably 10 minutes or longer, more preferably 1 hour or longer, and further preferably 3 hours or longer and 5 hours or longer.
- the alkali etching treatment is a treatment for dissolving the surface layer by bringing the oxide film into contact with an alkaline solution.
- Examples of the alkali used in the alkaline solution include caustic alkali and alkali metal salts.
- caustic alkali include caustic soda and caustic potash.
- alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate, and potassium silicate; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium aluminate and alumina.
- Alkali metal aluminates such as potassium acid; alkali metal aldones such as sodium gluconate and potassium gluconate; dibasic sodium phosphate, dibasic potassium phosphate, tribasic sodium phosphate, tertiary potassium phosphate, etc.
- An alkali metal hydrogen phosphate is mentioned.
- a caustic alkali solution and a solution containing both a caustic alkali and an alkali metal aluminate are preferable from the viewpoint of high etching rate and low cost.
- an aqueous solution of caustic soda is preferable.
- the concentration of the alkaline solution is preferably from 0.1 to 50% by mass, and more preferably from 0.5 to 10% by mass.
- concentration of aluminum ions is preferably 0.01 to 10% by mass, and more preferably 0.1 to 3% by mass.
- the temperature of the alkaline solution is preferably 10 to 90 ° C.
- the treatment time is preferably 1 to 120 seconds.
- Examples of the method of bringing the oxide film into contact with the alkaline solution include, for example, a method in which an aluminum base material on which an oxide film is formed is passed through a tank containing an alkali solution, and an aluminum base material on which an oxide film is formed is applied to an alkaline solution. Examples thereof include a method of immersing in an enclosed tank and a method of spraying an alkaline solution onto the surface (oxide film) of an aluminum substrate on which an oxide film is formed.
- the optional roughening treatment step that the metal support production method may have is a roughening step that is optionally performed in the method for producing a gas separation composite of the present invention.
- an electrochemical roughening treatment hereinafter also referred to as “electrolytic roughening treatment”
- electrolytic roughening treatment is applied to the aluminum substrate from which the oxide film has been removed, and the surface or back surface of the aluminum substrate is removed. It is a process of roughening.
- the surface area ratio ⁇ S is set to 20% to 80%, and the adhesion to the gas separation layer is improved.
- the coating composition can be prevented from penetrating into the through holes when the coating composition for the gas separation layer is applied.
- electrolytic surface-roughening treatment for example, conditions and apparatuses described in paragraphs [0041] to [0050] of JP2012-216513A can be appropriately employed.
- the surface area ratio ⁇ S can be easily set to 20% to 80% by electrochemical surface roughening treatment (hereinafter, also referred to as “nitric acid electrolysis”) using an electrolytic solution mainly composed of nitric acid. it can.
- nitric acid electrolysis uses an alternating current for the reason that it is possible to form a uniform and high-density recess, and the peak current density is 30 A / dm 2 or more, the average current density is 13 A / dm 2 or more, and
- the electrolytic treatment is preferably performed under the condition that the amount of electricity is 150 c / dm 2 or more.
- the peak current density is preferably 100 A / dm 2 or less, the average current density is preferably 40 A / dm 2 or less, and the amount of electricity is preferably 400 c / dm 2 or less.
- concentration and temperature of the electrolytic solution in nitric acid electrolysis are not particularly limited, and electrolysis is performed at a high concentration, for example, 30 to 60 ° C. using a nitric acid electrolytic solution having a nitric acid concentration of 15 to 35% by mass, or a nitric acid concentration of 0. Electrolysis can be carried out at a high temperature, for example, at 80 ° C. or higher, using a 7-2 mass% nitric acid electrolyte.
- the surface area ratio ⁇ S can be set to 20% to 80% by an electrochemical surface roughening treatment (hereinafter also abbreviated as “hydrochloric acid electrolysis”) using an electrolytic solution mainly composed of hydrochloric acid.
- hydrochloric acid electrolysis for the reason that uniform and high-density recesses can be formed, an alternating current is used, the peak current density is 30 A / dm 2 or more, the average current density is 13 A / dm 2 or more, and The electrolytic treatment is preferably performed under the condition that the amount of electricity is 150 c / dm 2 or more.
- the peak current density is preferably 100 A / dm 2 or less, the average current density is preferably 40 A / dm 2 or less, and the amount of electricity is preferably 400 c / dm 2 or less.
- the method for producing a metal support used in the gas separation composite of the present invention is because the average opening diameter of the through holes formed by the electrolytic dissolution treatment described above can be suitably adjusted to a small range of about 0.1 to 20 ⁇ m. It is preferable that after the through hole forming step described above, a metal coating step of covering at least part or all of the surface of the aluminum substrate including the inner wall of the through hole with a metal other than aluminum is provided. For the same reason, the metal support manufacturing method includes a metal coating step of coating at least part or all of the surface of the aluminum substrate including the inner wall of the through-hole with a metal other than aluminum after the oxide film removing step described above. It is preferable to have.
- “at least part or all of the surface of the aluminum substrate including the inner wall of the through hole is coated with a metal other than aluminum” means that at least the entire surface of the aluminum substrate including the inner wall of the through hole is penetrated. This means that the inner wall of the hole is covered, and the surface other than the inner wall may not be covered, or may be partially or entirely covered.
- the metal coating process will be described below with reference to FIGS. 4 (A) and 4 (B).
- FIG. 4 (A) and 4 (B) are schematic cross-sectional views of an aluminum plate produced by another embodiment of the method for producing a metal support.
- the aluminum plate 10 shown in FIG. 4A has a first metal layer 6 and a second metal made of a metal other than aluminum (for example, zinc, copper, nickel, etc.) or an alloy on the inner wall of the through-hole 5. It is an aspect which has the layer 7, and can produce it, for example by giving the below-mentioned substitution process and plating process to the inner wall of the through-hole of the aluminum base material shown in FIG.3 (C).
- the 1st metal layer 6 and 2nd metal which consist of a metal or alloy other than aluminum in the surface and back surface of the aluminum base material 3 which has a through-hole, and the inner wall of a through-hole. It is an aspect having the layer 7, and can be produced, for example, by subjecting the aluminum base material shown in FIG. 2D or FIG.
- the replacement treatment is a treatment in which zinc or a zinc alloy is subjected to replacement plating on a part or all of the surface of the aluminum substrate including at least the inner wall of the through hole.
- the displacement plating solution include a mixed solution of 120 g / L of sodium hydroxide, 20 g / L of zinc oxide, 2 g / L of crystalline ferric chloride, 50 g / L of Rossell salt, and 1 g / L of sodium nitrate.
- Commercially available Zn or Zn alloy plating solution may also be used.
- Substar Zn-1, Zn-2, Zn-3, Zn-8, Zn-10, Zn-111 manufactured by Okuno Pharmaceutical Co., Ltd. Zn-222, Zn-291, etc. can be used.
- the immersion time of the aluminum substrate in such a displacement plating solution is preferably 15 seconds to 40 seconds, and the immersion temperature is preferably 15 seconds to 40 seconds.
- ⁇ Plating treatment> When the zinc film is formed by replacing the surface of the aluminum base material with zinc or a zinc alloy by the above-described replacement treatment, for example, the zinc film is replaced with nickel by electroless plating described later, and then described later. It is preferable to perform a plating treatment for depositing various metals by electrolytic plating.
- the nickel plating solution used for the electroless plating treatment As the nickel plating solution used for the electroless plating treatment, commercially available products can be widely used. Examples thereof include an aqueous solution containing 30 g / L of nickel sulfate, 20 g / L of sodium hypophosphite, and 50 g / L of ammonium citrate. Examples of the nickel alloy plating solution include a Ni—P alloy plating solution in which a phosphorus compound is a reducing agent and a Ni—B plating solution in which a boron compound is a reducing agent.
- the immersion time in such a nickel plating solution or nickel alloy plating solution is preferably 15 seconds to 10 minutes, and the immersion temperature is preferably 30 ° C. to 90 ° C.
- a plating solution for electroplating Cu includes, for example, Cu 60 to 110 g / L, sulfuric acid 160 to 200 g / L and hydrochloric acid 0.1 to 0.15 mL / L to pure water. Furthermore, plating solutions containing Top Lucina SF Base WR 1z 5 to 5.0 mL / L, Top Lucina SF-B 0.5 to 2.0 mL / L, and Top Lucina SF Leveler 3.0 to 10 mL / L as additives are also listed. It is done.
- the immersion time in such a copper plating solution is not particularly limited because it depends on the thickness of the Cu film, but for example, when a 2 ⁇ m Cu film is applied, it is preferable to immerse for about 5 minutes at a current density of 2 A / dm,
- the immersion temperature is preferably 20 ° C. to 30 ° C.
- the method for producing a metal support used in the gas separation composite of the present invention is because the average opening diameter of the through holes formed by the electrolytic dissolution treatment described above can be suitably adjusted to a small range of about 0.1 to 20 ⁇ m.
- the boehmite treatment is preferably performed after the through-hole forming step described above or after the oxide film removing step described above and further after forming an oxide film by performing an anodizing treatment.
- the boehmite treatment uses a reaction in which aluminum reacts with high-temperature water or superheated steam to form a pseudo-boehmite hydrated oxide film.
- water at 100 to 400 ° C. for example, pure water
- Water, deionized water can be adjusted to pH 7-12 and a hydrated oxide film can be formed by immersing the aluminum substrate.
- washing treatment it is preferable to carry out water washing after completion of the above-described processes.
- pure water, well water, tap water, or the like can be used.
- a nip device may be used to prevent the processing liquid from being brought into the next process.
- the support preparation step is a step of preparing a metal support having a large number of through holes having an average opening diameter of 0.1 to 30 ⁇ m and an opening ratio of 0.05 to 10%.
- the metal support having such a through hole is manufactured by, for example, the above-described method for manufacturing a metal support.
- the metal support may be long (web-shaped) or cut sheet-shaped.
- it is preferable that the metal support body is given the roughening process process. By performing the roughening treatment so that the surface area ratio ⁇ S is 20% to 80%, the adhesion with the gas separation layer is improved. Further, since the surface tension is increased, when the gas separation layer is formed, the coating composition can be prevented from penetrating into the through holes when the coating composition for the gas separation layer is applied.
- the coating step is a step of coating a coating composition to be a gas separation layer on the surface of the metal support so that the thickness after curing is 0.1 to 5 ⁇ m. What is necessary is just to select a coating composition suitably according to the material of a gas separation layer. Moreover, as a coating composition, you may contain a crosslinking agent, antioxidant, surfactant, a solvent other than the material used for formation of a gas separation layer. For example, when insoluble polyimide is used as the gas separation layer, the coating composition preferably contains a polyimide compound and / or a polyimide precursor, a solvent, and the like.
- a coating method of the coating composition in a coating process Various well-known methods can be utilized. Specific examples include curtain flow coaters, extrusion die coaters, air doctor coaters, blade coaters, rod coaters, knife coaters, squeeze coaters, reverse roll coaters, bar coaters, and the like.
- the viscosity of the coating composition at the time of coating is not particularly limited, but the thin film gas separation layer can be easily formed without liquid repelling, etc., and the point that liquid leakage to the through hole of the coating composition can be suppressed, etc. Therefore, it is preferably 0.5 to 100 cP.
- the separation layer forming step is a step of curing the coating composition film applied to the surface of the metal support to form a gas separation layer having a thickness of 0.1 to 5 ⁇ m.
- a drying step, a curing step, and the like may be appropriately performed according to the type of gas separation layer (coating composition) to be formed.
- a drying process is a process of drying the film
- the curing step is a step of curing the coating film or the dried coating film to form a gas separation layer.
- a method capable of curing may be appropriately selected according to the material for forming the gas separation layer, such as heat curing, ultraviolet irradiation, and electron beam irradiation.
- insoluble polyimide when used as the gas separation layer, in the curing step, it is preferably heated to 200 ° C. or more to be insolubilized and cured.
- the heat treatment temperature in the curing step when forming the insoluble polyimide is appropriately adjusted according to the heat resistance of the metal support used, but is preferably 200 from the viewpoint of the degree of crosslinking and the thermal decomposition temperature of the polyimide. It is ⁇ 400 ° C., more preferably 200 to 350 ° C., and further preferably 220 to 300 ° C.
- the heat treatment time is preferably 0.2 hours or longer, more preferably 0.5 hours or longer in order to sufficiently insolubilize the polyimide compound. From the viewpoint of production efficiency, the heat treatment time is preferably within 10 hours, more preferably within 5 hours, and even more preferably within 2 hours.
- the coating composition may be dried and cured at the same time. Moreover, you may perform drying and / or hardening of a coating composition in inert atmosphere, such as nitrogen atmosphere, as needed.
- Example 1 ⁇ Production of metal support> The following treatment was applied to the surface of an aluminum substrate (JIS H-4160, alloy number: 1N30-H, aluminum purity: 99.30%) having a thickness of 12 ⁇ m and a width of 200 mm to obtain an aluminum support (metal support).
- JIS H-4160 alloy number: 1N30-H, aluminum purity: 99.30% having a thickness of 12 ⁇ m and a width of 200 mm
- A1 Oxide film formation process (oxide film formation process) A solution having a sulfuric acid concentration of 170 g / L and an aluminum concentration of 5% or less was used for the aluminum base material, and the aluminum base material was used as an anode, and a DC current density of 25 A / dm 2 and a DC voltage of 15 V were set to 16 at 52 ° C. The film was applied for 2 seconds to form an oxide film (film amount: 2.4 g / m 2 ). Then, water washing by spraying was performed.
- Electrolytic dissolution treatment (through hole forming step) Next, using an electrolytic solution (nitric acid concentration: 1%, aluminum concentration: 4.5 g / L) kept at 50 ° C., electrolytic treatment is performed under the condition that the total amount of electricity is 100 C / dm 2 with the aluminum base material as the anode. And through holes were formed in the aluminum substrate and the oxide film. The electrolytic treatment was performed with a DC power source. Current density was 25A / dm 2. Then, the aluminum base material which has a through-hole with an average opening diameter of 1.0 micrometer was produced by performing water washing by spraying and making it dry.
- Electrolytic treatment In a copper sulfate plating solution adjusted to 25 ° C., an aluminum substrate is used as a cathode, and electrolytic treatment is performed under the condition that the total amount of electricity is 300 ° C./dm 2 , and the average opening diameter of the through holes becomes 0.1 ⁇ m. Thus, a Cu layer was formed to produce an aluminum support.
- the average opening diameter and the opening ratio of the through holes of the produced aluminum support were measured by the following methods, the average opening diameter was 0.1 ⁇ m and the opening ratio was 0.05%.
- the average aperture diameter is a medium-wave structure in which the surface of the metal support is photographed at a magnification of 200 times from directly above using a high-resolution scanning electron microscope (SEM), and the surroundings are arranged in a ring shape in the obtained SEM photograph. At least 20 pits (irregularities) were extracted, the diameter was read to obtain the opening diameter, and the average value of these was calculated as the average opening diameter.
- the aperture ratio was measured for a 30 mm ⁇ 30 mm field of view (5 locations) of the obtained SEM photograph by photographing the surface of the metal support at a magnification of 200 times from directly above using a high resolution scanning electron microscope (SEM).
- N-methylpyrrolidone manufactured by Tokyo Chemical Industry Co., Ltd., product number: M0418
- 6FDA manufactured by Tokyo Chemical Industry Co., Ltd., product number: H14348
- 54.97 g (0.124 mol) was added to a three-necked flask at 40 ° C.
- polyimide P-01, weight average molecular weight: 112,000.
- polyimide (P-01) In a brown vial, 4 g of polyimide (P-01), 44 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 024-15635), methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., product number: 139-02086) 2 4 g was mixed and stirred for 60 minutes to prepare a coating composition.
- the obtained coating composition was coated on the aluminum support and dried at 70 ° C. for 2 hours using a blower dryer. Thereafter, heat treatment was performed at 250 ° C. for 1 hour using an inert oven (manufactured by Ikeda Rika Co., Ltd., STPH-201H) to insolubilize the membrane and form an insoluble polyimide as a gas separation layer.
- the thickness of the gas separation layer was 0.1 ⁇ m.
- Examples 2 to 3 The total electric quantity and current density, which are the processing conditions in the (b1) electrolytic dissolution treatment, are changed to the values shown in Table 1 below, and the dimensions of the through-holes formed without performing the (d1) metal coating treatment are changed.
- An aluminum support was produced in the same manner as in Example 1 except that the values shown in Table 2 were changed, and a gas separation composite was produced.
- Examples 4 to 6 The total electric quantity and current density, which are the processing conditions in the (b1) electrolytic dissolution treatment, are changed to the values shown in Table 1 below, and the dimensions of the through-holes formed without performing the (d1) metal coating treatment are changed.
- An aluminum support was prepared by changing the values shown in Table 2 below, and the thickness of the gas separation layer formed on the aluminum support was changed to the values shown in Table 2 below. Similarly, a gas separation complex was produced.
- Example 7 An aluminum support was prepared by the same method as in Example 4 except that the electrolytic surface-roughening treatment shown in the following (d1) was performed after the removal treatment of the oxide film (c2), and the gas separation composite was obtained. Produced.
- Electrolytic surface roughening treatment was continuously performed on the aluminum base material after the oxide film removal treatment using an alternating voltage of 60 Hz.
- the electrolytic solution at this time was a nitric acid 10 g / L aqueous solution (containing 4.5 g / L of aluminum ions) at a temperature of 50 ° C.
- the AC power supply waveform is the waveform shown in FIG. 5, the time TP until the current value reaches a peak from zero is 0.8 msec, the duty ratio is 1: 1, a trapezoidal rectangular wave AC is used, with the carbon electrode as the counter electrode An electrochemical roughening treatment was performed. Ferrite was used for the auxiliary anode.
- the electrolytic cell used was the one shown in FIG.
- the current density is 50 A / dm 2 at the peak value of the current, and 22.6 A / dm 2 on the average value, and the amount of electricity is 250 C / dm 2 in terms of the total amount of electricity when the aluminum foil is the anode. there were. Then, water washing by spraying was performed.
- the surface area ratio ⁇ S of the aluminum support surface after roughening was 20%.
- Example 8 (E1) The same method as in Example 7 except that the treatment conditions for the electrolytic surface roughening treatment were changed so that the total amount of electricity was 185 C / dm 2 and the surface area ratio ⁇ S of the aluminum support was 60%. Thus, an aluminum support was produced to produce a gas separation composite.
- Example 9 The same method as in Example 7 except that the treatment conditions of the electrolytic surface-roughening treatment were changed so that the total amount of electricity was 185 C / dm 2 and the surface area ratio ⁇ S of the aluminum support was 80%. Thus, an aluminum support was produced to produce a gas separation composite.
- Liquid leak test The front and back surfaces of the produced gas separation composite were observed with an SEM to evaluate the presence or absence of liquid leakage. Liquid leakage occurred when the gas separation layer was not formed at the position of the through hole and when the gas separation layer was formed in the through hole. An area of 0.5 ⁇ 0.5 mm was observed to evaluate the presence or absence of liquid leakage.
- the thickness of the gas separation layer is 0.1 to 5 ⁇ m
- the average opening diameter of the through holes formed in the metal support is 0.1 to 30 ⁇ m
- the opening ratio is 0.05 to
- the gas separation composites of Examples 1 to 6 of the present invention which is 10%, do not cause liquid leakage even when heated when forming the gas separation layer, and are excellent in pressure resistance. It can be seen that the gas separation layer can be properly supported. Therefore, it turns out that it has high gas-separation property. Moreover, it turns out that it has high gas permeability. On the other hand, in the gas separation composites of Comparative Examples 1 to 3, the gas separation layer was damaged when the gas separation layer was formed or during the gas separation operation. Therefore, proper gas separation cannot be performed.
- the gas separation composite of Comparative Example 4 has a gas separation layer formed in the through-hole, the gas separation property is inferior and proper gas separation cannot be performed. Further, in comparison with Examples 3 to 5 and Example 6, from the viewpoint of pressure resistance, the ratio X / T between the thickness T of the gas separation layer and the average opening diameter X of the through holes is 0.02 to It can be seen that 100 is preferable.
- the surface area ratio ⁇ S of the metal support is preferably 20 to 80% and more preferably 60 to 80% from the viewpoint of adhesion. From the above results, the effect of the present invention is clear.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
また、このような気体分離膜を有する複合膜を用いてガス分離操作を行う際には、高圧で高温の原料ガス(混合ガス)を供給される。
しかしながら、樹脂等の有機材料からなる支持層は耐熱性の観点で十分ではないため、樹脂等の有機材料からなる支持層を用いる複合膜においては、気体分離膜形成時の熱や、ガス分離操作時の熱によって、支持層が変形したり損傷して、気体分離膜を適正に支持できず、気体分離性能が低下してしまうという問題があった。
すなわち、以下の構成により上記目的を達成することができることを見出した。
金属支持体の表面に積層されるガス分離層とを有し、
ガス分離層の厚さが0.1~5μmであり、
金属支持体の貫通孔の平均開口径が0.1~30μmであり、開口率が0.05~10%であるガス分離複合体。
[2] 金属支持体がアルミニウム基材である[1]に記載のガス分離複合体。
[3] ガス分離層の材料が不溶性ポリイミドである[1]または[2]に記載のガス分離複合体。
[4] ガス分離層の厚さTと貫通孔の平均開口径Xとの比率X/Tが、0.02~100である[1]~[3]のいずれかに記載のガス分離複合体。
[5] 金属支持体とガス分離層との界面における表面積比ΔSが、20~80%である[1]~[4]のいずれかに記載のガス分離複合体。
[6] 金属支持体の厚みが、5~100μmである[1]~[5]のいずれかに記載のガス分離複合体。
[7] 厚み方向に複数の貫通孔を有し、貫通孔の平均開口径が0.1~30μmであり、開口率が0.05~10%である金属支持体を準備する準備工程と、
金属支持体の表面に、ガス分離層となる塗布組成物を塗布する塗布工程と、
金属支持体の表面に塗布した塗布組成物を硬化して、厚さ0.1~5μmのガス分離層を形成する分離層形成工程とを有するガス分離複合体の製造方法。
[8] ガス分離層が不溶性ポリイミドであり、
分離層形成工程において、塗布した塗布組成物を200℃以上に加熱して不溶化する工程を有する[7]に記載のガス分離複合体の製造方法。
[9] 金属支持体がアルミニウム基材であり、
準備工程が、アルミニウム基材の表面に酸化膜形成処理を施し、酸化膜を形成する酸化膜形成工程と、酸化膜形成工程の後に、電気化学的溶解処理を施し、貫通孔を形成する貫通孔形成工程と、を有する[7]または[8]に記載のガス分離複合体の製造方法。
[10] さらに、準備工程が、貫通孔形成工程の後に、酸化膜を除去する酸化膜除去工程を有する[9]に記載のガス分離複合体の製造方法。
[11] 準備工程が、貫通孔形成工程の後に、少なくとも貫通孔の内壁を含むアルミニウム基材の表面の一部または全部をアルミニウム以外の金属で被覆する金属被覆工程を有する[9]または[10]に記載のガス分離複合体の製造方法。
[12] 準備工程の後であって、塗布工程の前に、金属支持体の、ガス分離層を形成する側の面を粗面化して、表面積比ΔSを20~80%とする粗面化工程を有する[7]~[11]のいずれかに記載のガス分離複合体の製造方法。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本発明のガス分離複合体は、厚み方向に複数の貫通孔を有する金属支持体と、金属支持体の表面に積層されるガス分離層とを有し、ガス分離層の厚さが0.1~5μmであり、金属支持体に形成される貫通孔の平均開口径が0.1~30μmであり、開口率が0.05~10%である。
次に、本発明のガス分離複合体の構成について、図1を用いて説明する。
図1に示すように、ガス分離複合体100は、所定の開口率、開口径で形成された複数の貫通孔5を有する金属支持体10と、金属支持体10上に形成されるガス分離層102とを具備するものである。
金属支持体10は、ガス分離層102を支持する部材であり、一方の主面にガス分離層102が積層される。また、金属支持体10は、厚さ方向に貫通する複数の貫通孔5を有する。貫通孔5は、ガス分離層102が分離したガス(ガス分離層102を透過したガス)をガス分離層102とは反対側の面側に通過させるための通路である。
貫通孔5の平均開口径を0.1μm以上とすることにより、ガス分離層102が分離したガスの流れを抑制することを防止できる。また、貫通孔5の平均開口径を5μm以下とすることにより、ガス分離層102を形成する際に、ガス分離層102となる塗布組成物が貫通孔5に浸入することを防止して、適正なガス分離層102を形成することができる。
具体的には、貫通孔5の平均開口径を30μm以下とすることで、塗布組成物が貫通孔5内に液漏れして貫通孔5の位置にガス分離層102が形成されず欠陥となることを防止でき、適正なガス分離性を確保することができる。あるいは、塗布組成物が貫通孔5に浸入して貫通孔5内にもガス分離層が形成され膜厚が厚くなることを防止でき、適正なガス透過性を確保することができる。
また、貫通孔5の平均開口径を30μm以下とすることにより、ガス分離操作の際など、加圧された際に、ガス分離層102が破れて(割れて)しまうことを防止できる。
上記観点から、貫通孔5の平均開口径は、0.1μm~10μmが好ましく、0.1μm~5μmがより好ましい。
開口率が0.05%未満では、ガス分離層102が分離したガスの流れを抑制してしまうおそれがある。また、開口率が10%超では、金属支持体10の機械的強度が低下して、加圧された際やハンドリングの際等に、破れて(割れて)しまうおそれがある。
上記観点から、貫通孔5の開口率は、0.05%~5%であるのが好ましい。
また、貫通孔の開口率は、高分解能走査型電子顕微鏡(SEM)を用いて金属支持体の表面を真上から倍率200倍で撮影し、得られたSEM写真の30mm×30mmの視野(5箇所)について、画像解析ソフト等で2値化して貫通孔部分と非貫通孔部分を観察し、貫通孔の開口面積の合計と視野の面積(幾何学的面積)とから、比率(開口面積/幾何学的面積)から算出し、各視野(5箇所)における平均値を開口率として算出した。
金属支持体10の厚さが5μm未満では、機械的強度が不足して、しわや欠陥等が発生しやすくなるため、適正にガス分離層102を支持することができないおそれがある。また、金属支持体10の厚さが100μm超では、上記平均開口径の貫通孔5を形成するのが困難になる場合がある。
ここで、金属支持体10とガス分離層102との界面における表面積比ΔSを上記範囲とするためには、ガス分離層102を形成する前に、金属支持体10の表面を粗面化して、金属支持体10表面の表面積比ΔSを20%~80%とすればよい。
ΔS=(Sx-S0)/S0×100(%)・・・(i)
中でも、加工性、強度および可撓性にも優れる理由から、アルミニウム(アルミニウム合金)であるのが好ましい。
本明細書においては、上述したアルミニウムまたはアルミニウム合金からなる各種の基材をアルミニウム基材と総称して用いる。上記アルミニウム合金に含まれてもよい異元素には、ケイ素、鉄、銅、マンガン、マグネシウム、クロム、亜鉛、ビスマス、ニッケル、チタン等があり、合金中の異元素の含有量は10質量%以下である。
ここで、ガス分離層の支持体としては、ガス透過性が必要となる。そのため、支持体の素材として金属を用いる場合には、ガスの通路として多数の貫通孔を形成することが考えられる。
しかしながら、本発明者らは、支持体として金属を用いる場合には、単に貫通孔を形成したのみでは、ガス分離層の塗布組成物が貫通孔中に液漏れしたり、ガス分離操作時の圧力によりガス分離層が損傷したり、支持体が変形あるいは損傷して、ガス分離層を適正に支持することができないという問題があることを見出した。これは、有機材料を用いた支持体と比較して、金属支持体では弾性や伸縮性に劣るのが一因と考えられる。
ガス分離層102は、その素材ごとの性質に基づいて、所定の気体成分を選択的に透過させて分離するものであり、金属支持体10上に形成される。
ガス分離層102の厚さは、0.1μm~5μmである。ガス分離層102の厚さが0.1μm未満では、ガス分離層に欠陥が生じて気体分離性が低下するおそれがある。また、ガス分離層102の厚さが5μm超では、ガス透過性が低下するおそれがある。
上記観点から、ガス分離層102の厚さは、0.1μm~2μmであるのが好ましい。
さらに、加熱することで気体分離性を向上できるガス分離層102を有するガス分離複合体100に好適に利用可能である。
不溶性ポリイミドを含むガス分離層102は、ポリイミド化合物又はポリイミド前駆体の溶液(塗布液)を、金属支持体10に塗布し、乾燥して、ポリイミド化合物又はポリイミド前駆体を含有してなる膜を形成した後に、200℃以上の熱処理を行って、膜を構成するポリイミド化合物を不溶化して不溶性ポリイミド化合物とし、又は膜を構成するポリイミド前駆体を閉環して不溶性ポリイミド化合物とすることで形成される。
200℃以上の熱処理を行うことで、膜を構成するポリイミド化合物は架橋構造をとるなどして不溶性となる。これにより、ガス分離性能がより向上し、また、トルエン等のガス中に含まれる不純物成分に対する耐性も向上する。
なお、ポリイミド前駆体とは、ポリアミック酸又はその誘導体であり、200℃以上の加熱により閉環し、ポリイミド化合物を生成する化合物である。
本発明は、支持体として耐熱性の高い金属支持体を用いるので、ガス分離層102として、200℃以上の熱処理を伴う不溶性ポリイミドを用いる場合に好適に利用可能である。
また、上記200℃以上での熱処理の時間は、ポリイミド化合物を十分に不溶化するために、0.2時間以上とすることが好ましく、0.5時間以上とすることがより好ましい。また、製造効率の観点から上記熱処理の時間を10時間以内とすることが好ましく、5時間以内とすることがより好ましく、2時間以内とすることがさらに好ましい。
本発明のガス分離複合体のガス分離層として用いる、不溶性ポリイミドは、200℃以上の熱処理により不溶化するポリイミド化合物であるのが好ましい。200℃以上の熱処理によって不溶化するものであれば特に制限はない。この不溶化は、熱処理による脱炭酸反応で分子間、もしくは分子内に架橋構造が形成されることにより引き起こされると推定される。200℃以上の熱処理により不溶化するポリイミド化合物は塗布成膜できることが好ましい。より詳細には、200℃以上の熱処理により不溶化するポリイミド化合物は、ジメチルアセトアミドに対する20℃における溶解度が、500mg/100g以上であることが好ましく、1000~50000mg/100gであることがより好ましい。
200℃以上の熱処理により不溶化するポリイミド化合物は、下記式(I)で表される繰り返し単位を含むことが好ましい。このポリイミド化合物は、下記式(I)で表される繰り返し単位を2種以上含んでいてもよい。
本発明に用いる200℃以上の熱処理により不溶化するポリイミド化合物は、後述するように、テトラカルボン酸二無水物とジアミン(本明細書において「ジアミン」又は「ジアミン化合物」とは、アミノ基を2以上有する化合物を意味し、好ましくはアミノ基を2つ有する化合物である)を原料として合成される。上記式(I)の繰り返し単位を例にとれば、Yがジアミン成分であり、Yを除いた部分の構造がテトラカルボン酸二無水物成分である。すなわち、上記式(I)は、テトラカルボン酸二無水物成分1つとジアミン成分1つからなる繰り返し単位である。テトラカルボン酸二無水物成分1つとジアミン成分1つからなる繰り返し単位の総和(100モル%)に対して、上記式(I)の繰り返し単位の量は10モル%以上であることが好ましく、30モル%以上であることがより好ましく、50モル%以上であることがさらに好ましく、さらに70モル%以上であってもよく、80モル%以上であってもよく、100モル%であることも好ましい。
上記の繰り返し単位の総和に占める上記式(I)の繰り返し単位の割合が100モル%でない場合、残部の繰り返し単位の構造に特に制限はない。例えば、上記式(I)におけるYを、置換又は無置換のビス(4-アミノフェニル)エーテルに由来する構造、置換又は無置換のメチレンジアニリンに由来する構造、置換又は無置換の4,4′-ジアミノジフェニルスルホンに由来する構造、置換又は無置換のジトリルアミンに由来する構造に置き換えた構造が挙げられるが、本発明はこれらに限定されるものではない。
本発明に用いうる200℃以上の熱処理により不溶化するポリイミド化合物は、特定の2官能酸無水物(テトラカルボン酸二無水物)と特定のジアミンとを縮合重合させることで合成することができる。その方法としては一般的な書籍(例えば、今井淑夫、横田力男編著、「最新ポリイミド~基礎と応用~」、株式会社エヌ・ティー・エス、2010年8月25日、p.3~49、など)に記載の手法を適宜選択することができる。
上記溶媒としては、特に限定されるものではないが、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル系有機溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン等の脂肪族ケトン、エチレングリコールジメチルエーテル、ジブチルブチルエーテル、テトラヒドロフラン、メチルシクロペンチルエーテル、ジオキサン等のエーテル系有機溶剤、N-メチルピロリドン、2-ピロリドン、ジメチルホルムアミド、ジメチルイミダゾリジノン、ジメチルアセトアミド等のアミド系有機溶剤、ジメチルスルホキシド、スルホラン等の含硫黄系有機溶剤などが挙げられる。これらの有機溶剤は反応基質であるテトラカルボン酸二無水物、ジアミン化合物、反応中間体であるポリアミック酸、さらに最終生成物であるポリイミド化合物を溶解させることを可能とする範囲で適切に選択されるものであるが、好ましくは、エステル系(好ましくは酢酸ブチル)、脂肪族ケトン(好ましくは、メチルエチルケトン、メチルイソブチルケトン、ジアセトンアルコール、シクロペンタノン、シクロヘキサノン)、エーテル系(ジエチレングリコールモノメチルエーテル、メチルシクロペンチルエーテル)、アミド系(好ましくはN-メチルピロリドン)、含硫黄系(ジメチルスルホキシド、スルホラン)が好ましい。また、これらは、1種又は2種以上を組み合わせて用いることができる。
本発明のガス分離複合体に用いられるポリイミド前駆体は、ポリアミック酸又はその誘導体であって、200℃以上の熱処理によって閉環し、不溶性ポリイミドを生成するものであれば特に制限はない。ポリイミド前駆体は塗布成膜できることが好ましい。より詳細には、ジメチルアセトアミドに対する20℃における溶解度が、500mg/100g以上であることが好ましく、1000~50000mg/100gであることがより好ましい。
ポリイミド前駆体は、下記式(II)で表される繰り返し単位を含むことが好ましい。ポリイミド化合物は、下記式(II)で表される繰り返し単位を2種以上含んでいてもよい。
Xaが4価の脂肪族基である場合、その炭素数は3~20であることが好ましく、4~18であることがより好ましく、6~15であることがさらに好ましい。
Xaが4価の芳香族基である場合、その炭素数は4~20であることが好ましく、4~18であることがより好ましく、5~15であることがさらに好ましい。
Xaが脂肪族基及び芳香族基から選ばれる1種又は2種以上を組み合わせてなる4価の基である場合、その炭素数は、4~20であることが好ましく、5~15であることがより好ましい。また、脂肪族基及び芳香族基から選ばれる1種又は2種以上を組み合わせてなる4価の基は、2つの芳香環が単結合又は脂肪族基で連結された構造を有する4価の基であることが好ましい。
Xaは、より好ましくは上記式(I-1)~(I-28)のいずれかで表される構造の気である。
Yaが2価の脂肪族基である場合、その炭素数は1~30であることが好ましく、2~20であることがより好ましい。
Yaが2価の芳香族基である場合、その炭素数は4~20であることが好ましく、より4~15であることがさらに好ましく、5~15であることがさらに好ましい。Yaが2価の芳香族基である場合、Yaはアリーレン基であることがさらに好ましく、より好ましくは炭素数6~20のアリーレン基であり、さらに好ましくは炭素数6~15のアリーレン基、さらに好ましくはフェニレン基である。
Yaが脂肪族基及び芳香族基から選ばれる1種又は2種以上を組み合わせてなる2価の基である場合、その炭素数は、5~30であることが好ましく、6~20であることがより好ましい。また、脂肪族基及び芳香族基から選ばれる1種又は2種以上を組み合わせてなる2価の基は、2つの芳香環が単結合又は脂肪族基で連結された構造を有する2価の基であることが好ましい。この場合、2つの芳香環が単結合又は脂肪族基で連結された構造の好ましい炭素数は10~30であり、より好ましくは10~20、さらに好ましくは12~20であり、さらに好ましくは12~18である。Yaが脂肪族基及び芳香族基から選ばれる1種又は2種以上を組み合わせてなる2価の基である場合、当該芳香族基はアリーレン基であることが好ましく、より好ましくは炭素数6~20のアリーレン基であり、さらに好ましくは炭素数6~15のアリーレン基、さらに好ましくはフェニレン基である。
ポリイミド前駆体の合成方法に特に制限はない。例えば、窒素雰囲気下で所望の構造のジアミンをN-メチル-ピロリドンもしくはN,N-ジメチルアセトアミドに溶解し、この溶液を攪拌しながら所望の構造のテトラカルボン酸二無水物を加え、温水浴等を用いて80℃で2時間程度撹拌することで、ポリイミド前駆体を得ることができる。
アルキル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10のアルキル基であり、例えばメチル、エチル、iso-プロピル、tert-ブチル、n-オクチル、n-デシル、n-ヘキサデシル)、シクロアルキル基(好ましくは炭素数3~30、より好ましくは炭素数3~20、特に好ましくは炭素数3~10のシクロアルキル基であり、例えばシクロプロピル、シクロペンチル、シクロヘキシルなどが挙げられる。)、アルケニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10のアルケニル基であり、例えばビニル、アリル、2-ブテニル、3-ペンテニルなどが挙げられる。)、アルキニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10のアルキニル基であり、例えばプロパルギル、3-ペンチニルなどが挙げられる。)、アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12のアリール基であり、例えばフェニル、p-メチルフェニル、ナフチル、アントラニルなどが挙げられる。)、アミノ基(アミノ基、アルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基を含み、好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~10のアミノ基であり、例えばアミノ、メチルアミノ、ジメチルアミノ、ジエチルアミノ、ジベンジルアミノ、ジフェニルアミノ、ジトリルアミノなどが挙げられる。)、アルコキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10のアルコキシ基であり、例えばメトキシ、エトキシ、ブトキシ、2-エチルヘキシロキシなどが挙げられる。)、アリールオキシ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12のアリールオキシ基であり、例えばフェニルオキシ、1-ナフチルオキシ、2-ナフチルオキシなどが挙げられる。)、ヘテロ環オキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12のヘテロ環オキシ基であり、例えばピリジルオキシ、ピラジルオキシ、ピリミジルオキシ、キノリルオキシなどが挙げられる。)、
なお、本発明において、1つの構造部位に複数の置換基があるときには、それらの置換基は互いに連結して環を形成していたり、上記構造部位の一部又は全部と縮環して芳香族環もしくは不飽和複素環を形成していたりしてもよい。
本明細書において、単に置換基としてしか記載されていないものは、特に断わりのない限りこの置換基群Zを参照するものであり、また、各々の基の名称が記載されているだけのとき(例えば、「アルキル基」と記載されているだけのとき)は、この置換基群Zの対応する基における好ましい範囲、具体例が適用される。
本発明のガス分離複合体のガス分離層として用いられる不溶性ポリイミドには、膜物性を調整するため、各種高分子化合物を添加することもできる。高分子化合物としては、アクリル系重合体、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、ポリカーボネート樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、シェラック、ビニル系樹脂、アクリル系樹脂、ゴム系樹脂、ワックス類、その他の天然樹脂等が使用できる。また、これらは2種以上併用してもかまわない。
また、液物性調整のためにノニオン性界面活性剤、カチオン性界面活性剤や、有機フルオロ化合物などを添加することもできる。
二酸化炭素とメタンとの透過速度比(RCO2/RCH4)は15以上であることが好ましく、より好ましくは20以上、さらに好ましくは25以上、さらに好ましくは30以上、さらに好ましくは40以上である。透過速度比の上限に特に制限はないが、通常は100以下である。なお、RCO2は二酸化炭素の透過速度、RCH4はメタンの透過速度を示す。
なお、1GPUは1×10-6cm3(STP)/cm2・sec・cmHgである。
また、二酸化炭素とメタンガスとを含む混合ガスをガス分離する場合において、二酸化炭素とメタンガスの混合比に特に制限はないが、二酸化炭素:メタンガス=1:99~99:1(体積比)であることが好ましく、二酸化炭素:メタンガス=5:95~90:10であることがより好ましい。
また、本発明のガス分離複合体、あるいは、これを用いたガス分離モジュールを用いて、ガスを分離回収又は分離精製させるための手段を有するガス分離装置をとすることができる。本発明のガス分離複合体は、例えば、特開2007-297605号公報に記載のような吸収液と併用した膜吸収ハイブリッド法としての気体分離回収装置に適用してもよい。
次に、金属支持体の製造方法の一例として、アルミニウム基材を用いた金属支持体(以下、「アルミニウム支持体」ともいう)の製造方法の一例を説明する。この金属支持体の製造方法は、本発明における準備工程の一例である。
ここで、本発明においてアルミニウム支持体は、厚み方向に複数の貫通孔を有するアルミニウム基材および厚み方向に複数の貫通孔を有する酸化膜を有するアルミニウム板であってもよく、このアルミニウム板から後述する酸化膜除去工程により酸化膜を除去した態様、すなわち、厚み方向に複数の貫通孔を有するアルミニウム基材からなるアルミニウム板であってもよい。
アルミニウム支持体の製造方法は、図2(A)~図2(E)に示すように、アルミニウム基材1の表面に対して酸化膜形成処理を施し、酸化膜2を形成する酸化膜形成工程(図2(A)および図2(B))と、酸化膜形成工程の後に電解溶解処理を施して貫通孔5を形成し、貫通孔を有するアルミニウム基材3および貫通孔を有する酸化膜4を有するアルミニウム板10を作製する貫通孔形成工程(図2(B)および図2(C))とを有する製造方法である。
また、貫通孔形成工程の後に、貫通孔を有する酸化膜4を除去し、貫通孔を有するアルミニウム基材3からなるアルミニウム板10を作製する酸化膜除去工程(図2(C)および図2(D))を有しているのが好ましい。
同様に、酸化膜除去工程の後に、貫通孔を有するアルミニウム基材3に電気化学的粗面化処理を施し、表面を粗面化したアルミニウム板10を作製する粗面化処理工程(図2(D)および図2(E))を有しているのが好ましい。
すなわち、アルミニウム基材1の表面および裏面に対して酸化膜形成処理を施し、酸化膜2を形成する酸化膜形成工程(図3(A)および図3(B))と、酸化膜形成工程の後に電解溶解処理を施して貫通孔5を形成し、貫通孔を有するアルミニウム基材3および貫通孔を有する酸化膜4を有するアルミニウム板10を作製する貫通孔形成工程(図3(B)および図3(C))とを有する製造方法であってもよい。
また、図2(A)~図2(E)に示す例と同様に、貫通孔形成工程の後に、酸化膜4を除去する酸化膜除去工程(図3(C)および図3(D))を有しているのが好ましい。
同様に、酸化膜除去工程の後に、アルミニウム基材3に電気化学的粗面化処理を施し、表面を粗面化する粗面化処理工程(図3(D)および図3(E))を有しているのが好ましい。
本発明の製造方法が有する酸化膜形成工程は、アルミニウム基材の表面に酸化膜形成処理を施し、酸化膜を形成する工程である。
上記酸化膜形成処理は特に限定されず、例えば、従来公知の陽極酸化処理と同様の処理を施すことができる。
陽極酸化処理としては、例えば、特開2012-216513号公報の[0063]~[0073]段落に記載された条件や装置を適宜採用することができる。
硫酸を含有する電解液中で陽極酸化処理を行う場合には、アルミニウム基材と対極との間に直流を印加してもよく、交流を印加してもよい。アルミニウム基材に直流を印加する場合においては、電流密度は、1~60A/dm2であるのが好ましく、5~40A/dm2であるのがより好ましい。連続的に高速で陽極酸化処理を行う場合には、アルミニウム基材の一部に電流が集中していわゆる「焼け」が生じないように、陽極酸化処理の開始当初は、5~10A/dm2の低電流密度で電流を流し、陽極酸化処理が進行するにつれ、30~50A/dm2またはそれ以上に電流密度を増加させるのが好ましい。連続的に陽極酸化処理を行う場合には、アルミニウム基材に、電解液を介して給電する液給電方式により行うのが好ましい。
上記貫通孔形成工程は、酸化膜形成工程の後に電解溶解処理を施し、貫通孔を形成する工程である。
上記電解溶解処理は特に限定されず、直流または交流を用い、酸性溶液を電解液に用いることができる。中でも、塩酸または硝酸を主体とする電解液を用いるのが好ましい。
また、塩酸または硝酸を主体とする水溶液には、鉄、銅、マンガン、ニッケル、チタン、マグネシウム、シリカ等のアルミニウム合金中に含まれる金属が溶解していてもよい。好ましくは、塩酸または硝酸の濃度0.5~2質量%の水溶液にアルミニウムイオンが3~50g/Lとなるように、塩化アルミニウム、硝酸アルミニウム等を添加した液を用いることが好ましい。
本発明においては、硝酸を主体とする電解液を用いた電気化学的溶解処理(以下、「硝酸溶解処理」とも略す。)により、容易に、平均開口径が0.1~30μmであり、平均開口率が0.05~10%となる貫通孔を形成することができる。
ここで、硝酸溶解処理は、貫通孔形成の溶解ポイントを制御しやすい理由から、直流電流を用い、平均電流密度を5A/dm2以上とし、かつ、電気量を50C/dm2以上とする条件で施す電解処理であるであるのが好ましい。なお、平均電流密度は100A/dm2以下であるのが好ましく、電気量は10000C/dm2以下であるのが好ましい。
また、硝酸電解における電解液の濃度や温度は特に限定されず、高濃度、例えば、硝酸濃度15~35質量%の硝酸電解液を用いて30~60℃で電解を行ったり、硝酸濃度0.7~2質量%の硝酸電解液を用いて高温、例えば、80℃以上で電解を行ったりすることできる。
本発明においては、塩酸を主体とする電解液を用いた電気化学的溶解処理(以下、「塩酸溶解処理」とも略す。)によっても、容易に、平均開口径が0.1~30μmであり、平均開口率が0.05~10%となる貫通孔を形成することができる。
ここで、塩酸溶解処理は、貫通孔形成の溶解ポイントを制御しやすい理由から、直流電流を用い、平均電流密度を5A/dm2以上とし、かつ、電気量を50C/dm2以上とする条件で施す電解処理であるであるのが好ましい。なお、平均電流密度は100A/dm2以下であるのが好ましく、電気量は10000C/dm2以下であるのが好ましい。
また、塩酸電解における電解液の濃度や温度は特に限定されず、高濃度、例えば、塩酸濃度10~35質量%の塩酸電解液を用いて30~60℃で電解を行ったり、塩酸濃度0.7~2質量%の塩酸電解液を用いて高温、例えば、80℃以上で電解を行ったりすることできる。
5≦Q/t≦300 ・・・(1)
10≦Q/t≦300 ・・・(2)
これは、上記式(1)を満たすことにより、電解溶解処理による酸化膜およびアルミニウム基材の溶出が、厚みに対して好適な状態になるためであると考えられる。
なお、本発明の製造方法においては、電解溶解処理を施す際の酸化膜およびアルミニウム基材の合計の厚み(t)とは、基本的には、上述した酸化膜形成処理を施す前のアルミニウム基材の厚みと同じ値となる。
アルミニウム支持体の製造方法が有していてもよい任意の酸化膜除去工程は、酸化膜を除去する工程である。
上記酸化膜除去工程は、例えば、後述する酸エッチング処理やアルカリエッチング処理を施すことにより酸化膜を除去することができる。
上記溶解処理は、アルミニウムよりも酸化膜(酸化アルミニウム)を優先的に溶解させる溶液(以下、「アルミナ溶解液」という。)を用いて酸化膜を溶解させる処理である。
ジルコニウム系化合物としては、例えば、フッ化ジルコンアンモニウム、フッ化ジルコニウム、塩化ジルコニウムが挙げられる。
チタン化合物としては、例えば、酸化チタン、硫化チタンが挙げられる。
リチウム塩としては、例えば、フッ化リチウム、塩化リチウムが挙げられる。
セリウム塩としては、例えば、フッ化セリウム、塩化セリウムが挙げられる。
マグネシウム塩としては、例えば、硫化マグネシウムが挙げられる。
マンガン化合物としては、例えば、過マンガン酸ナトリウム、過マンガン酸カルシウムが挙げられる。
モリブデン化合物としては、例えば、モリブデン酸ナトリウムが挙げられる。
マグネシウム化合物としては、例えば、フッ化マグネシウム五水和物が挙げられる。
バリウム化合物としては、例えば、酸化バリウム、酢酸バリウム、炭酸バリウム、塩素酸バリウム、塩化バリウム、フッ化バリウム、ヨウ化バリウム、乳酸バリウム、シュウ酸バリウム、過塩素酸バリウム、セレン酸バリウム、亜セレン酸バリウム、ステアリン酸バリウム、亜硫酸バリウム、チタン酸バリウム、水酸化バリウム、硝酸バリウム、あるいはこれらの水和物等が挙げられる。
上記バリウム化合物の中でも、酸化バリウム、酢酸バリウム、炭酸バリウムが好ましく、酸化バリウムが特に好ましい。
ハロゲン単体としては、例えば、塩素、フッ素、臭素が挙げられる。
酸濃度としては、0.01mol/L以上であるのが好ましく、0.05mol/L以上であるのがより好ましく、0.1mol/L以上であるのが更に好ましい。上限は特にないが、一般的には10mol/L以下であるのが好ましく、5mol/L以下であるのがより好ましい。
浸せき処理の時間は、10分以上であるのが好ましく、1時間以上であるのがより好ましく、3時間以上、5時間以上であるのが更に好ましい。
アルカリエッチング処理は、上記酸化膜をアルカリ溶液に接触させることにより、表層を溶解させる処理である。
金属支持体の製造方法が有していてもよい任意の粗面化処理工程は、本発明のガス分離複合体の製造方法において任意に実施される粗面化工程である。
粗面化処理工程は、酸化膜を除去したアルミニウム基材に対して電気化学的粗面化処理(以下、「電解粗面化処理」とも略す。)を施し、アルミニウム基材の表面ないし裏面を粗面化する工程である。
このような電解粗面化処理を施すことにより、表面積比ΔSを20%~80%として、ガス分離層との密着性が向上する。また、表面張力が上がるため、ガス分離層を形成する際において、ガス分離層の塗布組成物を塗布した際に、塗布組成物が貫通孔へ浸透するのを防止できる。
上記電解粗面化処理としては、例えば、特開2012-216513号公報の[0041]~[0050]段落に記載された条件や装置を適宜採用することができる。
本発明においては、硝酸を主体とする電解液を用いた電気化学的粗面化処理(以下、「硝酸電解」とも略す。)により、容易に表面積比ΔSを20%~80%とすることができる。
ここで、硝酸電解は、均一で密度の高い凹部形成が可能となる理由から、交流電流を用い、ピーク電流密度を30A/dm2以上とし、平均電流密度を13A/dm2以上とし、かつ、電気量を150c/dm2以上とする条件で施す電解処理であるであるのが好ましい。なお、ピーク電流密度は100A/dm2以下であるのが好ましく、平均電流密度は40A/dm2以下であるのが好ましく、電気量は400c/dm2以下であるのが好ましい。
また、硝酸電解における電解液の濃度や温度は特に限定されず、高濃度、例えば、硝酸濃度15~35質量%の硝酸電解液を用いて30~60℃で電解を行ったり、硝酸濃度0.7~2質量%の硝酸電解液を用いて高温、例えば、80℃以上で電解を行ったりすることできる。
本発明においては、塩酸を主体とする電解液を用いた電気化学的粗面化処理(以下、「塩酸電解」とも略す。)によっても、表面積比ΔSを20%~80%とすることができる。
ここで、塩酸電解においては、均一で密度の高い凹部形成が可能となる理由から、交流電流を用い、ピーク電流密度を30A/dm2以上とし、平均電流密度を13A/dm2以上とし、かつ、電気量を150c/dm2以上とする条件で施す電解処理であるであるのが好ましい。なお、ピーク電流密度は100A/dm2以下であるのが好ましく、平均電流密度は40A/dm2以下であるのが好ましく、電気量は400c/dm2以下であるのが好ましい。
本発明のガス分離複合体に用いられる金属支持体の製造方法は、上述した電解溶解処理により形成された貫通孔の平均開口径を0.1~20μm程度の小さい範囲に好適に調整できる理由から、上述した貫通孔形成工程の後に、少なくとも貫通孔の内壁を含むアルミニウム基材の表面の一部または全部をアルミニウム以外の金属で被覆する金属被覆工程を有しているのが好ましい。
同様の理由から、金属支持体の製造方法は、上述した酸化膜除去工程の後に、少なくとも貫通孔の内壁を含むアルミニウム基材の表面の一部または全部をアルミニウム以外の金属で被覆する金属被覆工程を有しているのが好ましい。
ここで、「少なくとも貫通孔の内壁を含むアルミニウム基材の表面の一部または全部をアルミニウム以外の金属で被覆する」とは、貫通孔の内壁を含むアルミニウム基材の全表面のうち、少なくとも貫通孔の内壁については被覆されていることを意味しており、内壁以外の表面は、被覆されていなくてもよく、一部または全部が被覆されていてもよい。
以下に、図4(A)および図4(B)を用いて、金属被覆工程を説明する。
ここで、図4(A)に示すアルミニウム板10は、貫通孔5の内壁にアルミニウム以外の金属(例えば、亜鉛、銅、ニッケルなど)または合金からなる第1の金属層6および第2の金属層7を有する態様であり、図3(C)に示すアルミニウム基材の貫通孔の内壁に、例えば、後述する置換処理およびめっき処理を施すことにより作製することができる。
また、図4(B)に示すアルミニウム10は、貫通孔を有するアルミニウム基材3の表面および裏面ならびに貫通孔の内壁にアルミニウム以外の金属または合金からなる第1の金属層6および第2の金属層7を有する態様であり、図2(D)または図3(D)に示すアルミニウム基材に対して、例えば、後述する置換処理およびめっき処理を施すことにより作製することができる。
上記置換処理は、少なくとも貫通孔の内壁を含むアルミニウム基材の表面の一部または全部に、亜鉛または亜鉛合金を置換めっきする処理である。
置換めっき液としては、例えば、水酸化ナトリウム120g/L、酸化亜鉛20g/L、結晶性塩化第二鉄2g/L、ロッセル塩50g/L、硝酸ナトリウム1g/Lの混合溶液などが挙げられる。
また、市販のZnまたはZn合金めっき液を使用してもよく、例えば、奥野製薬工業株式会社製サブスターZn-1、Zn-2、Zn-3、Zn-8、Zn-10、Zn-111、Zn-222、Zn-291等を使用することができる。
このような置換めっき液へのアルミニウム基材の浸漬時間は15秒~40秒であるのが好ましく、浸漬温度は15秒~40秒であるのが好ましい。
上述した置換処理により、アルミニウム基材の表面に亜鉛または亜鉛合金を置換めっきして亜鉛皮膜を形成させた場合は、例えば、後述する無電解めっきにより亜鉛皮膜をニッケルに置換させた後、後述する電解めっきにより各種金属を析出させる、めっき処理を施すのが好ましい。
無電解めっき処理に用いるニッケルめっき液としては、市販品が幅広く使用でき、例えば、硫酸ニッケル30g/L、次亜リン酸ソーダ20g/L、クエン酸アンモニウム50g/Lを含む水溶液などが挙げられる。
また、ニッケル合金めっき液としては、りん化合物が還元剤となるNi-P合金めっき液やホウ素化合物が還元剤となるNi-Bメッキ液などが挙げられる。
このようなニッケルめっき液やニッケル合金めっき液への浸漬時間は15秒~10分であるのが好ましく、浸漬温度は30℃~90℃であるのが好ましい。
電解めっき処理として、例えば、Cuを電気めっきする場合のめっき液は、例えば、硫酸Cu60~110g/L、硫酸160~200g/Lおよび塩酸0.1~0.15mL/Lを純水に加え、さらに奥野製薬株式会社製トップルチナSFベースWR1z5~5.0mL/L、トップルチナSF-B0.5~2.0mL/L及びトップルチナSFレベラー3.0~10mL/Lを添加剤として加えためっき液が挙げられる。
このような銅めっき液への浸漬時間は、Cu膜の厚さによるため特に限定されないが、例えば、2μmのCu膜をつける場合は、電流密度2A/dmで約5分間浸漬するのが好ましく、浸漬温度は20℃~30℃であるのが好ましい。
本発明のガス分離複合体に用いられる金属支持体の製造方法は、上述した電解溶解処理により形成された貫通孔の平均開口径を0.1~20μm程度の小さい範囲に好適に調整できる理由から、上述した貫通孔形成工程の後や、上述した酸化膜除去工程の後であって更に陽極酸化処理を施して酸化膜を形成した後に、ベーマイト処理を施すのが好ましい。
ここで、ベーマイト処理は、アルミニウムが高温の水や過熱水蒸気と反応して擬ベーマイト質の水和酸化皮膜を生成する反応を用いたものであり、例えば、100~400℃の水(例えば、純水、脱イオン水)をpH7~12に調整し、アルミニウム基材を浸漬することによって水和酸化皮膜を生成することができる。
本発明においては、上述した各処理の工程終了後には水洗を行うのが好ましい。水洗には、純水、井水、水道水等を用いることができる。処理液の次工程への持ち込みを防ぐためにニップ装置を用いてもよい。
次に、本発明のガス分離複合体の製造方法について説明する。
本発明のガス分離複合体の製造方法は、以下の工程を順番に実施する。
(支持体準備工程)所定の貫通孔が形成された金属支持体を準備する工程
(塗布工程)金属支持体の表面に、ガス分離層となる塗布組成物を塗布する工程
(分離層形成工程)塗布組成物を硬化してガス分離層を形成する工程
以下に上記各工程について詳述する。
支持体準備工程は、平均開口径が0.1~30μmであり、開口率が0.05~10%の貫通孔を多数有する金属支持体を準備する工程である。このような貫通孔を有する金属支持体は、例えば、上記金属支持体の製造方法により製造される。なお、金属支持体は、長尺な(ウェブ状の)ものであってもよいし、カットシート状のものであってもよい。
また、上記のとおり、金属支持体は、粗面化処理工程が施されているのが好ましい。粗面化処理を施して、表面積比ΔSを20%~80%とすることで、ガス分離層との密着性が向上する。また、表面張力が上がるため、ガス分離層を形成する際において、ガス分離層の塗布組成物を塗布した際に、塗布組成物が貫通孔へ浸透するのを防止できる。
塗布工程は、上記金属支持体の表面に、ガス分離層となる塗布組成物を、硬化後の厚さが0.1~5μmとなるように塗布する工程である。
塗布組成物は、ガス分離層の材料に応じて適宜選択すればよい。また、塗布組成物としては、ガス分離層の形成に使用する材料以外にも、架橋剤、酸化防止剤、界面活性剤、溶剤等を含有してもよい。
例えば、ガス分離層として不溶性ポリイミドを用いる場合には、塗布組成物は、ポリイミド化合物および/またはポリイミド前駆体、溶剤等を含有するのが好ましい。
具体的には、カーテンフローコーター、エクストルージョンダイコーター、エアードクターコーター、ブレードコーター、ロッドコーター、ナイフコーター、スクイズコーター、リバースロールコーター、バーコーター等が例示される。
分離層形成工程は、金属支持体の表面に塗布した塗布組成物の膜を硬化させて、厚さ0.1~5μmのガス分離層を形成する工程である。
分離層形成工程おいては、形成するガス分離層(塗布組成物)の種類に応じて、適宜、乾燥工程、硬化工程等を行えばよい。
乾燥工程は、塗布した塗布組成物の膜(塗布膜)を乾燥して、塗布組成物中の溶剤等を揮発させる工程である。
乾燥工程は、公知の方法で行えばよい。一例として、温風による乾燥が例示される。
また、温風の風速は、塗布膜を迅速に乾燥させることができるともに塗布膜が崩れない速度を、適宜、設定すればよい。また、温風の温度は、金属支持体の変形などが生じず、かつ、塗布膜を迅速に乾燥させることができる温度を、適宜、設定すればよい。
硬化工程は、塗布膜、あるいは、乾燥した塗布膜を硬化して、ガス分離層を形成する工程である。
硬化工程における処理は、加熱硬化、紫外線照射、電子線照射等、ガス分離層の形成材料に応じて、硬化が可能な方法を、適宜、選択すればよい。
なお、不溶性ポリイミドを形成する際の硬化工程における熱処理温度は、使用する金属支持体の耐熱性にあわせて適宜に調節されるが、架橋の程度とポリイミドの熱分解温度の観点から、好ましくは200~400℃であり、より好ましくは200~350℃であり、さらに好ましくは220~300℃である。
また、上記熱処理の時間は、ポリイミド化合物を十分に不溶化するために、0.2時間以上とすることが好ましく、0.5時間以上とすることがより好ましい。また、製造効率の観点から上記熱処理の時間を10時間以内とすることが好ましく、5時間以内とすることがより好ましく、2時間以内とすることがさらに好ましい。
また、塗布組成物の乾燥および/または硬化は、必要に応じて、窒素雰囲気等の不活性雰囲気で行ってもよい。
<金属支持体の作製>
厚さ12μm、幅200mmのアルミニウム基材(JIS H-4160、合金番号:1N30-H、アルミニウム純度:99.30%)の表面に、以下に示す処理を施し、アルミニウム支持体(金属支持体)を作製した。
上記アルミニウム基材に硫酸濃度が170g/Lで、アルミニウム濃度5%以下の溶液を用い、アルミニウム基材を陽極として、52℃の条件下で、直流電流密度25A/dm2、直流電圧15Vを16秒間印加して、酸化膜(皮膜量:2.4g/m2)を形成した。その後、スプレーによる水洗を行った。
次いで、50℃に保温した電解液(硝酸濃度:1%、アルミニウム濃度4.5g/L)を用いて、アルミニウム基材を陽極として、電気量総和が100C/dm2の条件下で電解処理を施し、アルミニウム基材および酸化膜に貫通孔を形成させた。なお、電解処理は、直流電源で行った。電流密度は、25A/dm2とした。
その後、スプレーによる水洗を行い、乾燥させることにより、平均開口径1.0μmの貫通孔を有するアルミニウム基材を作製した。
次いで、電解溶解処理後のアルミニウム基材を、カセイソーダ濃度5質量%、アルミニウムイオン濃度0.5質量%の水溶液(液温:35℃)中に10秒間浸漬させることにより、酸化膜を溶解し、除去した。
その後、スプレーによる水洗を行い、乾燥させた。
さらに、硫酸水溶液(硫酸濃度:300g/L、液温:60℃)中に120秒間浸漬させることにより、スマットを溶解し、除去した。
その後、スプレーによる水洗を行い、乾燥させた。
次に、金属被覆処理として、以下の置換処理、めっき処理および電界めっき処理を行った。
25℃に調整したサブスター ZN-111(奥野製薬工業株式会社製)に1分間浸漬し、ジンケート処理を行った。続いて、硝酸水溶液に浸漬してジンケート皮膜を除去した後、再度、25℃に調整したサブスター ZN-111に1分間浸漬した。
50℃に調整したホウ素系Ni-Bめっき液に1分30秒浸漬して0.02μmのニッケル層を形成した。
25℃に調整した硫酸Cuめっき液中で、アルミニウム基材を陰極として、電気量総和が300℃/dm2の条件下で電解処理を施して、貫通孔の平均開口径が0.1μmとなるようにCu層を形成し、アルミニウム支持体を作製した。
また、開口率は、高分解能走査型電子顕微鏡(SEM)を用いて金属支持体の表面を真上から倍率200倍で撮影し、得られたSEM写真の30mm×30mmの視野(5箇所)について、画像解析ソフト等で2値化して貫通孔部分と非貫通孔部分を観察し、貫通孔の開口面積の合計と視野の面積(幾何学的面積)とから、比率(開口面積/幾何学的面積)から算出し、各視野(5箇所)における平均値を開口率として算出した。
作製したアルミニウム支持体の表面に、以下に示す塗布組成物を塗布および/または硬化して、ガス分離複合体を作製した。
三口フラスコにN-メチルピロリドン(東京化成工業株式会社製、製品番号:M0418)123mL、6FDA(東京化成工業株式会社製、製品番号:H1438)54.97g(0.124mol)を加えて40℃で溶解させ、窒素気流下で攪拌しているところに、2,3,5,6-テトラメチルフェニレンジアミン(東京化成工業株式会社製、製品番号:T1457)3.056g(0.0186mol)、3,5-ジアミノ安息香酸(DABA)(東京化成工業株式会社製、製品番号:D0294)16.04g(0.1055mol)をN-メチルピロリドン84.0mLに溶解した溶液を30分かけて系内を40℃に保ちつつ滴下した。反応液を40℃で2.5時間攪拌した後、ピリジン(東京化成工業株式会社製、製品番号:Q0034)2.94g(0.037mol)、無水酢酸(和光純薬株式会社製、製品番号:018-00286)31.58g(0.31mol)をそれぞれ加えて、さらに80℃で3時間攪拌した。その後、反応液にアセトン676.6mLを加え、希釈した。ステンレス容器にメタノール1.15L、アセトン230mLを加えて攪拌しているところに、反応液のアセトン希釈液を滴下した。得られたポリマー結晶を吸引ろ過し、60℃で送風乾燥させて51.3gのポリイミド(P-01、重量平均分子量:112,000)を得た。
褐色バイヤル瓶に、ポリイミド(P-01)4g、メチルエチルケトン(和光純薬株式会社製、製品番号:024-15635)44g、メチルイソブチルケトン(和光純薬株式会社製、製品番号:139-02086)2.4gを混合して60分撹拌し、塗布組成物を調製した。
得られた塗布組成物を上記アルミニウム支持体上に塗布し、送風乾燥機を用いて70℃で2時間乾燥した。その後、イナートオーブン(株式会社池田理化製、STPH-201H)を用いて、250℃で1時間、加熱処理を行い、膜を不溶化し、ガス分離層として不溶性ポリイミドを形成した。ガス分離層の厚さは、0.1μmとした。
上記(b1)電解溶解処理における処理条件である電気量総和および電流密度を下記表1に示す値に変更して、上記(d1)金属被覆処理を行わずに、形成される貫通孔の寸法を下記表2に示す値に変更した以外は、実施例1と同様の方法により、アルミニウム支持体を作製して、ガス分離複合体を作製した。
上記(b1)電解溶解処理における処理条件である電気量総和および電流密度を下記表1に示す値に変更して、上記(d1)金属被覆処理を行わずに、形成される貫通孔の寸法を下記表2に示す値に変更してアルミニウム支持体を作製し、また、アルミニウム支持体上に形成されるガス分離層の厚さを下記表2に示す値に変更した以外は、実施例1と同様にして、ガス分離複合体を作製した。
上記(b1)電解溶解処理における処理条件である電気量総和および電流密度を下記表1に示す値に変更して、上記(d1)金属被覆処理を行わずに、形成される貫通孔の寸法を下記表2に示す値に変更してアルミニウム支持体を作製し、また、アルミニウム支持体上に形成されるガス分離層の厚さを下記表2に示す値に変更した以外は、実施例1と同様の方法により、アルミニウム支持体を作製して、ガス分離複合体を作製した。
上記(c2)酸化膜の除去処理の後に、下記(d1)示す電解粗面化処理を施した以外は、実施例4と同様の方法により、アルミニウム支持体を作製して、ガス分離複合体を作製した。
次いで、酸化膜の除去処理後のアルミニウム基材に対して、60Hzの交流電圧を用いて連続的に電気化学的な粗面化処理を施した。このときの電解液は、硝酸10g/L水溶液(アルミニウムイオンを4.5g/L含む。)、温度50℃であった。交流電源波形は図5に示した波形であり、電流値がゼロからピークに達するまでの時間TPが0.8msec、duty比1:1、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的粗面化処理を行った。補助アノードにはフェライトを用いた。使用した電解槽は図6に示すものを使用した。電流密度は電流のピーク値で50A/dm2であり、かつ、平均値で22.6A/dm2であり、また、電気量はアルミニウム箔が陽極時の電気量の総和で250C/dm2であった。その後、スプレーによる水洗を行った。
粗面化後のアルミニウム支持体表面の表面積比ΔSは20%であった。
上記(e1)電解粗面化処理の処理条件を変更して、電気量の総和を185C/dm2とし、アルミニウム支持体の表面積比ΔSを60%とした以外は、実施例7と同様の方法により、アルミニウム支持体を作製して、ガス分離複合体を作製した。
上記(e1)電解粗面化処理の処理条件を変更して、電気量の総和を185C/dm2とし、アルミニウム支持体の表面積比ΔSを80%とした以外は、実施例7と同様の方法により、アルミニウム支持体を作製して、ガス分離複合体を作製した。
実施例1~6および比較例1~4において作製したガス分離複合体の液漏れの有無、耐圧性、ガス透過性を評価した。
作製したガス分離複合体の表面および裏面をSEMで観察して、液漏れの有無を評価した。貫通孔の位置でガス分離層が形成されていないもの、および、貫通孔内にガス分離層が形成されているものを液漏れとした。
0.5×0.5mmの領域を観察して、液漏れの有無を評価した。
作製したガス分離複合体を直径47mmに切り取り、透過試験サンプルを作成した。GTRテック株式会社製ガス透過率測定装置を用い、二酸化炭素(CO2)、メタン(CH4)が20:80(体積比)の混合ガスをガス供給側の全圧力が5MPa(CO2の分圧:1MPa)、流量500mL/min、40℃となるように調整し供給した後、ガス分離複合体の表面および裏面をSEMで観察して、ガス分離層の破れ(破損)の有無を評価した。
0.5×0.5mmの領域を観察して、破れが発生した個所の数を測定した。
A:破れが発見されなかった。
B:破れが数か所、発見された。
C:破れが多数、発見された。
作製したガス分離複合体を直径47mmに切り取り、透過試験サンプルを作成した。GTRテック株式会社製ガス透過率測定装置を用い、二酸化炭素(CO2)、メタン(CH4)が20:80(体積比)の混合ガスをガス供給側の全圧力が5MPa(CO2の分圧:1MPa)、流量500mL/min、40℃となるように調整し供給した。透過してきたガスをガスクロマトグラフィーにより分析した。ガス分離膜のガス透過性は、ガス透過率(Permeance)としてガス透過速度を算出することにより比較した。
A:ガス透過速度が5GPU以上
B:ガス透過速度が0.1GPU以上5GPU未満
C:ガス透過速度が0.1GPU未満
なお、比較例1および比較例3は、液漏れ試験において、液漏れ個所が多数発見されたため、ガス透過性の試験を行うことができなかった。
また、比較例2は、ガス透過性試験によって、ガス分離層が破損してしまったため、適正な評価ができなかった。
結果を表2に示す。
作製したガス分離複合体のガス分離層の表面にカッターナイフで基盤目状に縦11本、横11本の切込みを入れて合計100個の正方形の升目を刻み、その面に日東電工株式会社製のポリエステル粘着テープ(No.31B)を貼り付けた。30分経過後に垂直方向にテープを剥がし、剥がれた升目の数を数えた。同じ試験を3回行って平均を算出し下記の基準で評価した。
AA:剥がれはなかった。
A:1~5升の剥がれがあった。
B:6~10升の剥がれがあった。
C:11升以上の剥がれがあった。
結果を表3に示す。
これに対して、比較例1~3のガス分離複合体は、ガス分離層形成の際、あるいは、ガス分離操作の際に、ガス分離層が破損している。そのため、適正なガス分離を行うことができない。また、比較例4のガス分離複合体は、貫通孔内にガス分離層が形成されているため、ガス透過性に劣り適正なガス分離を行うことができない。
また、実施例3~5と、実施例6との対比から、耐圧性の観点で、ガス分離層の厚さTと貫通孔の平均開口径Xとの比率X/Tは、0.02~100であるのが好ましいことがわかる。
以上の結果から、本発明の効果は明らかである。
2 酸化膜
3 貫通孔を有するアルミニウム基材
4 貫通孔を有する酸化膜
5 貫通孔
6 第1の金属層
7 第2の金属層
10 金属支持体
11 アルミニウム基材
12 ラジアルドラムローラ
13a、13b 主極
14 電解処理液
15 電解液供給口
16 スリット
17 電解液通路
18 補助陽極
19a、19b サイリスタ
20 交流電源
21 主電解槽
22 補助陽極槽
100 ガス分離複合体
102 ガス分離層
Claims (12)
- 厚み方向に複数の貫通孔を有する金属支持体と、
前記金属支持体の表面に積層されるガス分離層とを有し、
前記ガス分離層の厚さが0.1~5μmであり、
前記金属支持体の前記貫通孔の平均開口径が0.1~30μmであり、開口率が0.05~10%であるガス分離複合体。 - 前記金属支持体がアルミニウム基材である請求項1に記載のガス分離複合体。
- 前記ガス分離層の材料が不溶性ポリイミドである請求項1または2に記載のガス分離複合体。
- 前記ガス分離層の厚さTと前記貫通孔の平均開口径Xとの比率X/Tが、0.02~100である請求項1~3のいずれか1項に記載のガス分離複合体。
- 前記金属支持体と前記ガス分離層との界面における表面積比ΔSが、20~80%である請求項1~4のいずれか1項に記載のガス分離複合体。
- 前記金属支持体の厚みが、5~100μmである請求項1~5のいずれか1項に記載のガス分離複合体。
- 厚み方向に複数の貫通孔を有し、前記貫通孔の平均開口径が0.1~30μmであり、開口率が0.05~10%である金属支持体を準備する準備工程と、
前記金属支持体の表面に、ガス分離層となる塗布組成物を塗布する塗布工程と、
前記金属支持体の表面に塗布した前記塗布組成物を硬化して、厚さ0.1~5μmの前記ガス分離層を形成する分離層形成工程とを有するガス分離複合体の製造方法。 - 前記ガス分離層が不溶性ポリイミドであり、
前記分離層形成工程において、塗布した前記塗布組成物を200℃以上に加熱して不溶化する工程を有する請求項7に記載のガス分離複合体の製造方法。 - 前記金属支持体がアルミニウム基材であり、
前記準備工程が、アルミニウム基材の表面に酸化膜形成処理を施し、酸化膜を形成する酸化膜形成工程と、前記酸化膜形成工程の後に、電気化学的溶解処理を施し、前記貫通孔を形成する貫通孔形成工程と、を有する請求項7または8に記載のガス分離複合体の製造方法。 - さらに、前記準備工程が、前記貫通孔形成工程の後に、前記酸化膜を除去する酸化膜除去工程を有する請求項9に記載のガス分離複合体の製造方法。
- 前記準備工程が、前記貫通孔形成工程の後に、少なくとも前記貫通孔の内壁を含む前記アルミニウム基材の表面の一部または全部をアルミニウム以外の金属で被覆する金属被覆工程を有する請求項9または10に記載のガス分離複合体の製造方法。
- 前記準備工程の後であって前記塗布工程の前に、前記金属支持体の、前記ガス分離層を形成する側の面を粗面化して、表面積比ΔSを20~80%とする粗面化工程を有する請求項7~11のいずれか1項に記載のガス分離複合体の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016511501A JP6324491B2 (ja) | 2014-03-31 | 2015-03-12 | ガス分離複合体およびその製造方法 |
EP15772812.2A EP3127600A4 (en) | 2014-03-31 | 2015-03-12 | Gas separation composite and method for manufacturing same |
US15/280,331 US10105640B2 (en) | 2014-03-31 | 2016-09-29 | Gas separation composite and method of producing same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-073176 | 2014-03-31 | ||
JP2014073176 | 2014-03-31 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/280,331 Continuation US10105640B2 (en) | 2014-03-31 | 2016-09-29 | Gas separation composite and method of producing same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015151756A1 true WO2015151756A1 (ja) | 2015-10-08 |
Family
ID=54240088
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/057345 WO2015151756A1 (ja) | 2014-03-31 | 2015-03-12 | ガス分離複合体およびその製造方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US10105640B2 (ja) |
EP (1) | EP3127600A4 (ja) |
JP (1) | JP6324491B2 (ja) |
WO (1) | WO2015151756A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017128105A (ja) * | 2016-01-14 | 2017-07-27 | 東京応化工業株式会社 | 積層体 |
WO2017150099A1 (ja) * | 2016-02-29 | 2017-09-08 | 富士フイルム株式会社 | 複合体 |
CN110201555A (zh) * | 2019-07-08 | 2019-09-06 | 浙江长兴求是膜技术有限公司 | 一种树脂高强度粘结的中空纤维复合膜及其灌封方法 |
TWI708684B (zh) * | 2016-01-14 | 2020-11-01 | 日商東京應化工業股份有限公司 | 積層體之製造方法、及積層體 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6071920B2 (ja) * | 2014-02-12 | 2017-02-01 | 富士フイルム株式会社 | ガス分離複合膜、ガス分離モジュール、ガス分離装置、ガス分離方法、及びガス分離複合膜の製造方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004057993A (ja) * | 2002-07-31 | 2004-02-26 | Dainippon Printing Co Ltd | 水素製造用フィルタの製造方法 |
JP2007113080A (ja) * | 2005-10-21 | 2007-05-10 | Aisin Takaoka Ltd | 被膜付きアルミニウム材 |
JP2009273977A (ja) * | 2008-05-13 | 2009-11-26 | Dainippon Printing Co Ltd | 水素選択透過膜およびその製造方法 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3565981A (en) * | 1967-05-09 | 1971-02-23 | Du Pont | Process for preparing a composite moisture-permeable sheet material |
US3721596A (en) * | 1969-11-24 | 1973-03-20 | G Drake | Fluid separation and method and apparatus for forming same |
DE3671046D1 (de) | 1985-11-25 | 1990-06-13 | Alusuisse Lonza Services Ag | Verfahren zur herstellung einer teildurchlaessigen membran. |
WO1988010141A1 (en) * | 1987-06-25 | 1988-12-29 | Atlas Copco Aktiebolag | A process for production of a semi-permeable membrane, a membranemanufactured by said process and the use of such a membrane for gas or liquid separation |
NL8800796A (nl) * | 1988-03-29 | 1989-10-16 | X Flow Bv | Werkwijze voor de chemische analyse van bestanddelen van een lichaamsvloeistof, alsmede een testinrichting en testpakket voor een dergelijke analyse. |
CH678402A5 (ja) * | 1989-03-08 | 1991-09-13 | Fraunhofer Ges Forschung | |
EP0674937A3 (en) * | 1994-03-30 | 1995-11-22 | Corning Inc | Non-porous polymer membrane on an inorganic porous support. |
DE10039595B4 (de) * | 2000-08-12 | 2006-06-01 | Umicore Ag & Co. Kg | Verfahren zur Herstellung einer Metallverbundmembran, damit hergestellte Metallverbundmembran und deren Verwendung |
US20020056371A1 (en) * | 2000-09-27 | 2002-05-16 | Hawkeye Enterprises, Llc | Membrane system and method for separation of gases |
CA2519769A1 (en) * | 2003-03-21 | 2004-10-07 | Worcester Polytechnic Institute | Composite gas separation modules having intermediate porous metal layers |
US7727596B2 (en) * | 2004-07-21 | 2010-06-01 | Worcester Polytechnic Institute | Method for fabricating a composite gas separation module |
US7662218B2 (en) * | 2004-10-20 | 2010-02-16 | Dai Nippon Printing Co., Ltd. | Filter for purifying hydrogen and method for manufacture thereof |
US20060090649A1 (en) * | 2004-10-29 | 2006-05-04 | Wei Liu | High separation area membrane module |
US7169213B2 (en) * | 2004-10-29 | 2007-01-30 | Corning Incorporated | Multi-channel cross-flow porous device |
JP2007098324A (ja) * | 2005-10-06 | 2007-04-19 | Toyota Motor Corp | 支持体付水素分離膜およびそれを備えた燃料電池 |
EP1995053B1 (en) * | 2006-02-20 | 2013-05-01 | Daicel Chemical Industries, Ltd. | Porous film and layered product including porous film |
EP2142490A1 (de) * | 2007-04-24 | 2010-01-13 | CeramTec AG | Verfahren zur herstellung eines metallisierten bauteils, bauteil sowie einen träger zur auflage des bauteils bei der metallisierung |
JP2009255035A (ja) * | 2008-03-26 | 2009-11-05 | Ngk Insulators Ltd | セラミックフィルタ |
US8747752B2 (en) * | 2009-03-03 | 2014-06-10 | Oridion Medical (1987) Ltd. | Drying substances, preparation and use thereof |
JP5848154B2 (ja) | 2012-02-17 | 2016-01-27 | 富士フイルム株式会社 | ガス分離複合膜、その製造方法、それを用いたガス分離モジュール、及びガス分離装置、並びにガス分離方法 |
JP2014054631A (ja) * | 2013-10-03 | 2014-03-27 | Dainippon Printing Co Ltd | 水素精製フィルタ |
NO20131634A1 (no) * | 2013-12-09 | 2015-06-10 | Biowater Technology AS | Fremgangsmåte for biologisk rensing av vann |
-
2015
- 2015-03-12 WO PCT/JP2015/057345 patent/WO2015151756A1/ja active Application Filing
- 2015-03-12 EP EP15772812.2A patent/EP3127600A4/en not_active Withdrawn
- 2015-03-12 JP JP2016511501A patent/JP6324491B2/ja active Active
-
2016
- 2016-09-29 US US15/280,331 patent/US10105640B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004057993A (ja) * | 2002-07-31 | 2004-02-26 | Dainippon Printing Co Ltd | 水素製造用フィルタの製造方法 |
JP2007113080A (ja) * | 2005-10-21 | 2007-05-10 | Aisin Takaoka Ltd | 被膜付きアルミニウム材 |
JP2009273977A (ja) * | 2008-05-13 | 2009-11-26 | Dainippon Printing Co Ltd | 水素選択透過膜およびその製造方法 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017128105A (ja) * | 2016-01-14 | 2017-07-27 | 東京応化工業株式会社 | 積層体 |
TWI708684B (zh) * | 2016-01-14 | 2020-11-01 | 日商東京應化工業股份有限公司 | 積層體之製造方法、及積層體 |
WO2017150099A1 (ja) * | 2016-02-29 | 2017-09-08 | 富士フイルム株式会社 | 複合体 |
CN108698360A (zh) * | 2016-02-29 | 2018-10-23 | 富士胶片株式会社 | 复合体 |
CN108698360B (zh) * | 2016-02-29 | 2021-03-23 | 富士胶片株式会社 | 复合体 |
CN110201555A (zh) * | 2019-07-08 | 2019-09-06 | 浙江长兴求是膜技术有限公司 | 一种树脂高强度粘结的中空纤维复合膜及其灌封方法 |
Also Published As
Publication number | Publication date |
---|---|
JP6324491B2 (ja) | 2018-05-16 |
US20170014754A1 (en) | 2017-01-19 |
JPWO2015151756A1 (ja) | 2017-04-13 |
EP3127600A4 (en) | 2017-04-12 |
US10105640B2 (en) | 2018-10-23 |
EP3127600A1 (en) | 2017-02-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10105640B2 (en) | Gas separation composite and method of producing same | |
JP6037804B2 (ja) | ガス分離膜 | |
WO2015041250A1 (ja) | ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 | |
JP6038058B2 (ja) | ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 | |
JP5972774B2 (ja) | ガス分離複合膜及びその製造方法 | |
WO2015053102A1 (ja) | ガス分離膜およびガス分離膜モジュール | |
JP2009082850A (ja) | 新規ガス分離膜およびその製造方法ならびにそれを用いるガス処理方法 | |
JP2014024939A (ja) | ポリイミド樹脂の製造方法、ガス分離膜、ガス分離モジュール、及びガス分離装置、並びにガス分離方法 | |
WO2017130604A1 (ja) | ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 | |
US10226743B2 (en) | Gas separation composite membrane, gas separation module, gas separation device, gas separation method, and method of producing gas separation composite membrane | |
US10537859B2 (en) | Gas separation membrane, gas separation module, gas separation device, gas separation method, and polyimide compound | |
WO2015033772A1 (ja) | ガス分離複合膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 | |
JP6355058B2 (ja) | ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 | |
WO2017145747A1 (ja) | ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 | |
WO2017175598A1 (ja) | ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 | |
JP6282585B2 (ja) | 半透膜およびその製造方法、半透膜を用いた濃度差発電方法 | |
WO2018043149A1 (ja) | ガス分離膜、ガス分離モジュール、ガス分離装置、ガス分離方法及びポリイミド化合物 | |
WO2017179393A1 (ja) | ガス分離膜、ガス分離モジュール、ガス分離装置、ガス分離方法、ガス分離膜用組成物及びガス分離膜の製造方法 | |
WO2017145905A1 (ja) | ポリイミド化合物、ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 | |
JP2017185462A (ja) | ガス分離膜、ガス分離モジュール、ガス分離装置、及びガス分離方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15772812 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016511501 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015772812 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015772812 Country of ref document: EP |