JP2009189934A - Composite body and its manufacturing method - Google Patents
Composite body and its manufacturing method Download PDFInfo
- Publication number
- JP2009189934A JP2009189934A JP2008032215A JP2008032215A JP2009189934A JP 2009189934 A JP2009189934 A JP 2009189934A JP 2008032215 A JP2008032215 A JP 2008032215A JP 2008032215 A JP2008032215 A JP 2008032215A JP 2009189934 A JP2009189934 A JP 2009189934A
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- JP
- Japan
- Prior art keywords
- metal
- composite
- oxide film
- microporous
- porous substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002131 composite material Substances 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 134
- 239000002184 metal Substances 0.000 claims abstract description 134
- 239000011148 porous material Substances 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000010408 film Substances 0.000 claims description 106
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 85
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 82
- 239000001257 hydrogen Substances 0.000 claims description 59
- 229910052739 hydrogen Inorganic materials 0.000 claims description 59
- 239000000758 substrate Substances 0.000 claims description 55
- 239000000377 silicon dioxide Substances 0.000 claims description 41
- 229910052763 palladium Inorganic materials 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 238000007772 electroless plating Methods 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 31
- 150000002431 hydrogen Chemical class 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 27
- 239000003638 chemical reducing agent Substances 0.000 claims description 24
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- -1 silicon alkoxide Chemical class 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052762 osmium Inorganic materials 0.000 claims description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000001263 FEMA 3042 Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 claims description 4
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 4
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 4
- 229960005055 sodium ascorbate Drugs 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 4
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 4
- 229940033123 tannic acid Drugs 0.000 claims description 4
- 235000015523 tannic acid Nutrition 0.000 claims description 4
- 229920002258 tannic acid Polymers 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012466 permeate Substances 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000010030 laminating Methods 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLMKTBGFQGKQEV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO NLMKTBGFQGKQEV-UHFFFAOYSA-N 0.000 description 1
- JKXYOQDLERSFPT-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-octadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO JKXYOQDLERSFPT-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical class C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts 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
- 239000001273 butane Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical class CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- RKMJXTWHATWGNX-UHFFFAOYSA-N decyltrimethylammonium ion Chemical class CCCCCCCCCC[N+](C)(C)C RKMJXTWHATWGNX-UHFFFAOYSA-N 0.000 description 1
- QQJDHWMADUVRDL-UHFFFAOYSA-N didodecyl(dimethyl)azanium Chemical class CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC QQJDHWMADUVRDL-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004868 gas analysis 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
- TXPMUPUOSOZCCS-UHFFFAOYSA-N hexadecyl(trimethyl)phosphanium Chemical class CCCCCCCCCCCCCCCC[P+](C)(C)C TXPMUPUOSOZCCS-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- APSPVJKFJYTCTN-UHFFFAOYSA-N tetramethylazanium;silicate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-][Si]([O-])([O-])[O-] APSPVJKFJYTCTN-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- IKANSXQHJXBNIN-UHFFFAOYSA-N trimethyl(octadecyl)phosphanium Chemical class CCCCCCCCCCCCCCCCCC[P+](C)(C)C IKANSXQHJXBNIN-UHFFFAOYSA-N 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
本発明は、水素を含む混合ガスから水素ガスを選択的に透過分離するのに用いられる複合体およびその製造方法に関する。さらに、本発明は前記複合体を用いて水素ガスを分離する方法に関する。 The present invention relates to a composite used for selectively permeating and separating hydrogen gas from a mixed gas containing hydrogen and a method for producing the same. Furthermore, this invention relates to the method of isolate | separating hydrogen gas using the said composite_body | complex.
水素ガスは化成品の原料ガス、ガラスや電子材料の処理ガス、ロケットや燃料電池の燃料ガス等非常に多岐に渡って大量に利用されている工業的に重要なガスである。近年は、水素燃料電池の本格的な実用化を目前にして、改めて注目されており、高純度の水素を安価に製造する技術の開発が急務となっている。水素の製造方法としては、天然ガスや精油所のオフガス、ナフサ等の石油系炭化水素のスチームリフォーミング法、或いは、重質油やその他の原料炭化水素の熱分解法が代表的な方法であり、これらによって製造された水素含有ガスを水素分離膜により精製分離して高純度の水素ガスを製造する。 Hydrogen gas is an industrially important gas that is used in a great variety of ways, such as raw material gas for chemical products, processing gas for glass and electronic materials, and fuel gas for rockets and fuel cells. In recent years, attention has been attracted to new hydrogen fuel cells in the near future, and there is an urgent need to develop technology for producing high-purity hydrogen at low cost. Typical methods for hydrogen production include steam reforming of petroleum hydrocarbons such as natural gas, refinery off-gas, and naphtha, or pyrolysis of heavy oil and other feed hydrocarbons. The hydrogen-containing gas produced by these is purified and separated by a hydrogen separation membrane to produce high-purity hydrogen gas.
このような水素分離膜として、無機質材料からなる多孔質支持体の表面にパラジウムを含有する薄膜を形成させてなる水素分離膜（特許文献１）や、金属多孔体の表面にバナジウムおよびパラジウムを含有する薄膜を形成させてなる水素分離膜（特許文献２）が知られている。しかしながら、前者の水素分離膜は高価なパラジウムを多量に使用しなければならず、実用的でない。また、後者の水素分離膜は高温下において合金化し、水素透過性能が低下してしまうため、やはり実用的な面で問題があった。
そのため、パラジウム使用量を低減する目的でＣＶＤ、無電解メッキ等による水素分離膜の薄膜化が試みられていた（特許文献３、４）。
しかしながら、薄膜化した場合、水素脆化、球状剥離等の問題があり（非特許文献１）、水素分離膜の耐久性が低くなるという問題が生じていた。
As such a hydrogen separation membrane, a hydrogen separation membrane (Patent Document 1) in which a thin film containing palladium is formed on the surface of a porous support made of an inorganic material, or vanadium and palladium are contained on the surface of a metal porous body. A hydrogen separation membrane (Patent Document 2) formed by forming a thin film is known. However, the former hydrogen separation membrane must use a large amount of expensive palladium, and is not practical. In addition, the latter hydrogen separation membrane is alloyed at a high temperature, and the hydrogen permeation performance is deteriorated.
For this reason, attempts have been made to reduce the thickness of the hydrogen separation membrane by CVD, electroless plating, or the like in order to reduce the amount of palladium used (Patent Documents 3 and 4).
However, when the film is thinned, there are problems such as hydrogen embrittlement and spherical separation (Non-Patent Document 1), and there is a problem that the durability of the hydrogen separation membrane is lowered.
一方、十分な耐久性を保持する水素分離膜としては、例えば、細孔を有する基材の表面に圧延パラジウム合金膜を付着させた膜が知られている（特許文献５）。この水素分離膜は、耐久性を高くするために、パラジウム合金膜を５μｍもしくはそれ以上の膜厚とする必要があり、高価なパラジウムを大量に使用する必要があり、コスト面から実用化が困難である。 On the other hand, as a hydrogen separation membrane that maintains sufficient durability, for example, a membrane in which a rolled palladium alloy membrane is attached to the surface of a substrate having pores is known (Patent Document 5). This hydrogen separation membrane requires a palladium alloy membrane to have a thickness of 5 μm or more in order to increase durability, and it is necessary to use a large amount of expensive palladium. It is.
以上の問題を解決するために、薄膜化し、かつ十分な耐久性を有する水素分離膜として、多孔質基材、多孔質材とその細孔隙に充填され該細孔隙を閉塞する金属とからなる金属緻密充填材および多孔質保護材が順に成層されてなる複合膜が提案されている（特許文献６）。
しかしながら、この水素分離膜では、三層構造をとっているため、製造が煩雑であるとともに、中間層である金属緻密充填材における金属が金属緻密充填材全体に分布しているため、熱膨張により金属緻密充填材内の金属の劣化が生じやすい。
However, since this hydrogen separation membrane has a three-layer structure, the production is complicated, and the metal in the metal dense filler that is the intermediate layer is distributed throughout the metal dense filler. The metal in the metal dense filler is likely to deteriorate.
本発明は、微細孔酸化物膜中に金属を、微細孔酸化物膜の両端部よりも中心部に多く存在する分布パターンで分布させることにより、薄膜化した金属充填層を積層させた複合体を提供することを目的とする。さらに、複合体を水素分離に用いる場合、水素透過性および耐久性に優れ、なおかつパラジウム等の金属の使用量を大幅に低減しうるため低コストで製造しうる複合体を提供する。 The present invention relates to a composite in which a thin metal-filled layer is laminated by distributing a metal in a microporous oxide film in a distribution pattern that exists more in the center than at both ends of the microporous oxide film. The purpose is to provide. Furthermore, when the composite is used for hydrogen separation, a composite that is excellent in hydrogen permeability and durability and can be manufactured at low cost because the amount of metal such as palladium can be greatly reduced.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、微細孔酸化物膜の細孔内に金属を担持させるに際し、還元剤を含む溶液と、金属源を含む溶液とを一方は微細孔酸化物膜の上表面から、他方は下表面からそれぞれ浸透させる工程を付加することにより、微細孔酸化物膜の細孔内に金属を選択的に充填することができ、それにより複合体に積層された金属充填層を極めて薄膜化できることを見出し、この知見に基づいてさらに研究を進め、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that when a metal is supported in the pores of the microporous oxide film, a solution containing a reducing agent and a solution containing a metal source are used. By adding a step of infiltrating one from the upper surface of the microporous oxide film and from the lower surface of the other, the metal can be selectively filled into the pores of the microporous oxide film. The present inventors have found that the metal-filled layer laminated on the composite can be made extremely thin, and have further advanced research based on this knowledge, and have completed the present invention.
すなわち、本発明は、
［１］ （イ）微細孔酸化物膜の細孔に金属が充填され、前記細孔が前記金属により閉塞されてなる金属充填層が（ロ）多孔質基材の上に積層されてなる複合体であって、充填された金属が微細孔酸化物膜の両端部よりも中心部に多く存在する分布パターンで分布してなる複合体、
［２］ 充填された金属の分布パターンが、微細孔酸化物膜の多孔質基材と接触している面側と接触していない面側との中央もしくはその近辺にピークを有する針状、山型もしくは釣り鐘型パターンである前記［１］に記載の複合体、
［３］ 微細孔酸化物膜の材質がシリカ、アルミナ、ジルコニアまたはチタニアである前記［１］または［２］に記載の複合体、
［４］ 微細孔酸化物膜が界面活性剤を鋳型として合成される規則的細孔構造を有する前記［１］〜［３］のいずれかに記載の複合体、
［５］ 多孔質基材が多孔質セラミックスまたは多孔質金属からなる前記［１］〜［４］のいずれかに記載の複合体、
［６］ 多孔質セラミックスがαアルミナである前記［５］に記載の複合体、
［７］ 微細孔酸化物膜が多孔質基材より小さい平均細孔径を有する前記［１］〜［６］のいずれかに記載の複合体、
［８］ 多孔質基材の細孔が、平均細孔径０．００４〜２０μｍである前記［７］に記載の複合体、
［９］ 微細孔酸化物膜の細孔が、平均細孔径１〜１００ｎｍである前記［７］に記載の複合体、
［１０］ 金属充填層の金属が、無電解メッキ処理の可能な金属である前記［１］〜［９］のいずれかに記載の複合体、
［１１］ 無電解メッキ処理の可能な金属が、遷移金属の単体または合金である前記［１０］に記載の複合体、
［１２］ 遷移金属が、周期表の４族、５族、８族、９族、１０族および１１族の金属からなる群から選ばれる１以上である前記［１１］に記載の複合体、
［１３］ 遷移金属が、銀、パラジウム、ロジウム、ルテニウム、金、白金、イリジウム、オスミウム、銅、ニッケル、コバルト、鉄、バナジウムおよびチタンからなる群から選ばれる１以上である前記［１１］に記載の複合体、
［１４］ 遷移金属がパラジウムである前記［１１］に記載の複合体、
［１５］ 金属を含む微細孔酸化物膜の膜厚が５μｍ以下の前記［１］〜［１４］のいずれかに記載の複合体、
［１６］ 複合体の製造方法であって、（１）微細孔酸化物膜が多孔質基材上に積層されてなる微細孔複合体（Ａ）を準備する工程、（２）前記微細孔複合体（Ａ）の微細孔酸化物膜側から還元剤を含む溶液を浸透させ、多孔質基材側から金属源を含む溶液を浸透させることにより、前記微細孔複合体（Ａ）の微細孔酸化物膜の細孔内に金属種核を担持させる工程、（３）前記（２）の工程で得られた金属種核を担持する微細孔複合体（Ｂ）を無電解メッキ処理して、微細孔酸化物膜の細孔を金属により閉塞させる工程、を含むことを特徴とする複合体の製造方法、
［１７］ 複合体の製造方法であって、（１）微細孔酸化物膜が多孔質基材上に積層されてなる微細孔複合体（Ａ）を準備する工程、（２）前記微細孔複合体（Ａ）の微細孔酸化物膜表面側から金属源を含む溶液を浸透させ、多孔質基材側から還元剤を含む溶液を浸透させることにより、前記微細孔複合体（Ａ）の微細孔酸化物膜の細孔内に金属種核を担持させる工程、（３）前記（２）の工程で得られた金属種核を担持する微細孔複合体（Ｂ）を無電解メッキ処理して、微細孔酸化物膜の細孔を金属により閉塞させる工程、を含むことを特徴とする複合体の製造方法、
［１８］ 前記（１）の工程が、（１ａ）多孔質基材の表面に界面活性剤および酸化物源からなるゲル薄膜を形成させて多層構造体とする工程、および（１ｂ）該多層構造体を焼成する工程からなる前記［１６］または［１７］に記載の製造方法、
［１９］ 酸化物源がシリカ源であり、該シリカ源が、コロイダルシリカ、ケイ酸ソーダ、テトラアルキルアンモニウムシリケートおよびシリコンアルコキシドからなる群から選ばれる１以上である前記［１６］〜［１８］のいずれかに記載の製造方法、
［２０］ シリカ源が、テトラエチルオルソシリケートである前記［１９］に記載の製造方法、
［２１］ 界面活性剤がカチオン性界面活性剤である前記［１６］〜［２０］のいずれかに記載の製造方法、
［２２］ 還元剤が、アスコルビン酸、アスコルビン酸ナトリウム、水素化ホウ素ナトリウム、水素化ホウ素カリウム、ジメチルアミンボラン、トリメチルアミンボラン、クエン酸、クエン酸ナトリウム、タンニン酸、ジボラン、ヒドラジン、ホルムアルデヒド、グルコースおよび塩化スズからなる群から選ばれる１以上である前記［１６］〜［２１］のいずれかに記載の製造方法、
［２３］ 金属源を含む溶液が、酢酸パラジウム、硝酸パラジウム、塩化パラジウム、塩化パラジウム酸、パラジウムアセチルアセトナートおよびパラジウムヘキサフルオロアセチルアセトナートからなる群から選ばれる１以上である前記［１６］〜［２２］のいずれかに記載の製造方法、
［２４］ 前記［１］〜［１５］のいずれかに記載の複合体からなる水素分離膜、および
［２５］ 水素を含有する混合ガスを、前記［２４］に記載の水素分離膜に接触させて、水素を選択的に透過させることを特徴とする水素分離方法、
に関する。
That is, the present invention
[1] (b) A composite in which a metal-filled layer in which the pores of the microporous oxide film are filled with metal and the pores are closed with the metal is laminated on the porous substrate (b) A composite in which the filled metal is distributed in a distribution pattern that exists more in the center than at both ends of the microporous oxide film,
[2] Needle-like, crests in which the distribution pattern of the filled metal has a peak at or near the center between the surface side in contact with the porous substrate of the microporous oxide film and the surface side not in contact with the porous substrate. The complex according to [1], which is a mold or a bell-shaped pattern,
[3] The composite according to [1] or [2], wherein the material of the microporous oxide film is silica, alumina, zirconia, or titania.
[4] The composite according to any one of [1] to [3], wherein the microporous oxide film has a regular pore structure synthesized using a surfactant as a template,
[5] The composite according to any one of [1] to [4], wherein the porous substrate is made of porous ceramics or porous metal.
[6] The composite according to [5], wherein the porous ceramic is α-alumina,
[7] The composite according to any one of [1] to [6], wherein the microporous oxide film has an average pore diameter smaller than that of the porous substrate.
[8] The composite according to [7], wherein the pores of the porous substrate have an average pore diameter of 0.004 to 20 μm,
[9] The composite according to [7], wherein the pores of the microporous oxide film have an average pore diameter of 1 to 100 nm,
[10] The composite according to any one of [1] to [9], wherein the metal in the metal-filled layer is a metal that can be electrolessly plated.
[11] The composite according to [10], wherein the metal capable of electroless plating is a single element or an alloy of a transition metal,
[12] The composite according to [11], wherein the transition metal is one or more selected from the group consisting of Group 4, Group 5, Group 8, Group 9, Group 10, and Group 11 metals of the Periodic Table,
[13] The above [11], wherein the transition metal is one or more selected from the group consisting of silver, palladium, rhodium, ruthenium, gold, platinum, iridium, osmium, copper, nickel, cobalt, iron, vanadium and titanium. Complex of,
[14] The composite according to [11], wherein the transition metal is palladium,
[15] The composite according to any one of [1] to [14], wherein the film thickness of the microporous oxide film containing a metal is 5 μm or less,
[16] A method for producing a composite, wherein (1) a step of preparing a microporous composite (A) in which a microporous oxide film is laminated on a porous substrate, (2) the microporous composite Microporous oxidation of the microporous composite (A) by infiltrating a solution containing a reducing agent from the microporous oxide film side of the body (A) and permeating a solution containing a metal source from the porous substrate side A step of supporting metal seed nuclei in the pores of the material film, (3) a fine pore composite (B) supporting the metal seed nuclei obtained in the step (2) is subjected to electroless plating treatment, A method for producing a composite, comprising a step of closing pores of a porous oxide film with a metal,
[17] A method for producing a composite, wherein (1) a step of preparing a microporous composite (A) in which a microporous oxide film is laminated on a porous substrate, (2) the microporous composite By infiltrating the solution containing the metal source from the surface of the microporous oxide film of the body (A) and infiltrating the solution containing the reducing agent from the porous substrate side, the micropores of the microporous composite (A) A step of supporting metal seed nuclei in the pores of the oxide film, (3) electroless plating treatment of the fine pore composite (B) supporting the metal seed nuclei obtained in the step (2), A method for producing a composite, comprising a step of closing pores of a microporous oxide film with a metal,
[18] The step (1) includes (1a) forming a multilayered structure by forming a gel thin film comprising a surfactant and an oxide source on the surface of the porous substrate, and (1b) the multilayer structure. The production method according to the above [16] or [17], comprising a step of firing the body,
[19] The above [16] to [18], wherein the oxide source is a silica source, and the silica source is one or more selected from the group consisting of colloidal silica, sodium silicate, tetraalkylammonium silicate and silicon alkoxide. The production method according to any one of the above,
[20] The production method according to [19], wherein the silica source is tetraethyl orthosilicate.
[21] The production method according to any one of [16] to [20], wherein the surfactant is a cationic surfactant.
[22] The reducing agent is ascorbic acid, sodium ascorbate, sodium borohydride, potassium borohydride, dimethylamine borane, trimethylamine borane, citric acid, sodium citrate, tannic acid, diborane, hydrazine, formaldehyde, glucose and chloride. The production method according to any one of the above [16] to [21], which is one or more selected from the group consisting of tin,
[23] The above-mentioned [16] to [16], wherein the solution containing a metal source is one or more selected from the group consisting of palladium acetate, palladium nitrate, palladium chloride, palladium chloride acid, palladium acetylacetonate and palladium hexafluoroacetylacetonate. 22], the production method according to any one of
[24] A hydrogen separation membrane comprising the composite according to any one of [1] to [15], and [25] a mixed gas containing hydrogen is brought into contact with the hydrogen separation membrane according to [24]. A hydrogen separation method characterized by selectively permeating hydrogen,
About.
本発明の複合体は、それを構成する金属充填層において、充填された金属が微細孔酸化物膜中の狭い範囲に分布しているため、水素分離に特化して用いる場合、パラジウム（Ｐｄ）充填層厚の低減、すなわちパラジウム使用量の大幅な低減が可能となる。また、金属を微細孔酸化物膜中に充填することにより、膜表面からのはがれや損傷に高い耐性を有し、充填金属を基材中で微細化することにより水素脆性を大幅に緩和することができる。さらに、保護材を積層する必要がないため、製造が簡便である。 In the composite of the present invention, since the filled metal is distributed in a narrow range in the microporous oxide film in the metal packed layer constituting the composite, palladium (Pd) is used when specialized for hydrogen separation. The packed layer thickness can be reduced, that is, the amount of palladium used can be greatly reduced. In addition, by filling the metal in the microporous oxide film, it has high resistance to peeling and damage from the film surface, and greatly reducing hydrogen embrittlement by miniaturizing the filled metal in the substrate. Can do. Furthermore, since it is not necessary to laminate protective materials, manufacturing is simple.
以下に、まず本発明の複合体について説明する。 Below, the composite_body | complex of this invention is demonstrated first.
本発明の複合体は、（イ）微細孔酸化物膜の細孔に金属が充填され、前記細孔が前記金属により閉塞されてなる金属充填層が（ロ）多孔質基材の上に積層されてなる複合体であって、充填された金属が微細孔酸化物膜の両端部よりも中心部に多く存在する分布パターンで分布してなることを特徴とする。 In the composite of the present invention, (b) a metal-filled layer in which the pores of the microporous oxide film are filled with a metal and the pores are closed with the metal is (b) laminated on a porous substrate. It is a composite that is formed, and is characterized in that the filled metal is distributed in a distribution pattern that exists more in the center than at both ends of the microporous oxide film.
本発明の微細孔酸化物膜としては、マクロ細孔酸化物膜、メソ細孔酸化物膜、マイクロ細孔酸化物膜等が挙げられ、好ましくはメソ細孔酸化物膜である。これらの微細孔酸化物膜の材質（酸化物）としては、シリカ、アルミナ、ジルコニアまたはチタニア等が挙げられる。また、前記微細孔酸化物膜中の細孔の平均細孔径は、多孔質基材の細孔径よりも小さいものが好ましく、通常１〜１００ｎｍ、より好ましくは２〜１０ｎｍ程度であり、かつ細孔容積は０．０５〜１．４ｃｃ／ｇ程度である。ここで、細孔径とは、細孔の垂直断面の最大寸法をいう。また、細孔容積とは微細孔酸化物膜の細孔からなる空隙部の容積であり、通常のガス吸着測定装置により測定できる。また、微細孔酸化物膜の膜厚は、通常、５μｍ以下、特に１μｍ以下が好ましい。 Examples of the microporous oxide film of the present invention include a macroporous oxide film, a mesoporous oxide film, and a microporous oxide film, and a mesoporous oxide film is preferable. Examples of the material (oxide) of these microporous oxide films include silica, alumina, zirconia, and titania. Further, the average pore diameter of the pores in the microporous oxide film is preferably smaller than the pore diameter of the porous substrate, and is usually about 1 to 100 nm, more preferably about 2 to 10 nm. The volume is about 0.05 to 1.4 cc / g. Here, the pore diameter means the maximum dimension of the vertical cross section of the pore. Further, the pore volume is the volume of the void portion composed of the pores of the microporous oxide film, and can be measured with a normal gas adsorption measuring device. The thickness of the microporous oxide film is usually 5 μm or less, and particularly preferably 1 μm or less.
本発明の多孔質基材は、金属充填層を支持し、複合体全体として機械的強度を付与するものであれば特に制限はないが、耐熱性の観点から好ましくは多孔質セラミックスや多孔質金属からなるものが挙げられる。多孔質とは、細孔を有し、かつ前記細孔が連通して通気性があるものを意味する。
前記多孔質セラミックスとしては、酸化物、窒化物または炭化物等が挙げられ、具体的にはアルミナ、ジルコニア、チタニア、ニオビア、セリア、シリカ、コージェライト、ムライト、窒化ケイ素、炭化ケイ素、酸化ニッケル、酸化コバルト、酸化鉄、酸化クロム、酸化マンガン、酸化亜鉛、酸化タングステンまたは酸化モリブデン等が挙げられ、中でもアルミナ、シリカ、ジルコニア、コージェライト、ムライト、窒化ケイ素、炭化ケイ素等が好ましく挙げられるが、これらに限らず、種々の多孔質体を用いることができ、微細孔酸化物膜の構成材料と同じ種類のものであってよい。これらの多孔質セラミックスは単独で用いてもよく、２以上を混合して用いてもよい。
前記多孔質金属については、その構造上からは、金属不織布、金属粉焼結多孔体、金属穿孔体等が、その物性上からは耐熱性や耐食性を有する金属や合金、例えばニッケルやステンレス鋼等がそれぞれ挙げられる。これらの多孔質金属は単独で用いてもよく、２以上を混合して用いてもよい。
また、多孔質基材の形態は、本発明の目的を阻害しない限り特に限定されないが、通常管状、板状である。前記多孔質基材の孔径は、本発明の目的を阻害しない限り特に限定されないが、通常、０．００４〜２０μｍであり、好ましくは０．００４〜２μｍである。
The porous substrate of the present invention is not particularly limited as long as it supports the metal-filled layer and imparts mechanical strength to the entire composite, but is preferably a porous ceramic or porous metal from the viewpoint of heat resistance. The thing which consists of is mentioned. The term “porous” means a material having pores and having the breathability through the communication of the pores.
Examples of the porous ceramics include oxides, nitrides or carbides. Specifically, alumina, zirconia, titania, niobia, ceria, silica, cordierite, mullite, silicon nitride, silicon carbide, nickel oxide, oxide Examples include cobalt, iron oxide, chromium oxide, manganese oxide, zinc oxide, tungsten oxide, and molybdenum oxide. Among them, alumina, silica, zirconia, cordierite, mullite, silicon nitride, silicon carbide, and the like are preferable. Not limited to this, various porous bodies can be used, and they may be the same type as the constituent material of the microporous oxide film. These porous ceramics may be used alone or in combination of two or more.
For the porous metal, from the viewpoint of its structure, a metal nonwoven fabric, a metal powder sintered porous body, a metal perforated body, and the like, from the viewpoint of its physical properties, metals and alloys having heat resistance and corrosion resistance, such as nickel and stainless steel, etc. Respectively. These porous metals may be used alone or in combination of two or more.
The form of the porous substrate is not particularly limited as long as the object of the present invention is not impaired, but is usually tubular or plate-like. The pore diameter of the porous substrate is not particularly limited as long as the object of the present invention is not impaired, but is usually 0.004 to 20 μm, preferably 0.004 to 2 μm.
本発明の複合体は、前記微細孔酸化物膜の細孔に金属が充填され、該細孔が該金属により閉塞されてなる金属充填層を含む。また、微細孔酸化物膜の細孔に充填された金属は、微細孔酸化物膜の両端部よりも中心部に多く存在する分布パターンで分布している。微細孔酸化物膜の両端部よりも中心部に多く存在する分布パターンとしては、特に限定されず、微細孔酸化物膜の多孔質基材と接触している面側（Ａ面ともいう）と接触していない面側（Ｂ面ともいう）との中央もしくはその近辺に多く存在すれば、竿状、柱状、棒状等の形状の分布パターンであってもよいが、微細孔酸化物膜のＡ面とＢ面との中央もしくはその近辺にピークを有する針状、山型もしくは釣り鐘型パターンであるのが好ましい。
このように、微細孔酸化物膜内で充填金属を、Ａ面とＢ面との中央もしくはその近辺にピークを有する針状、山型もしくは釣り鐘型パターンで分布させることにより、金属を含む微細孔酸化物膜全体をより薄膜化することができる。薄膜化によりガス（例えば水素）の透過速度も上昇するため、膜面積を小さくすることができ、金属の使用量を少なくすることができる。
The composite of the present invention includes a metal-filled layer in which the pores of the microporous oxide film are filled with a metal and the pores are closed with the metal. Further, the metal filled in the pores of the microporous oxide film is distributed in a distribution pattern that exists more in the center than at both ends of the microporous oxide film. There is no particular limitation on the distribution pattern that exists more in the center than at both ends of the microporous oxide film, and the surface side that is in contact with the porous substrate of the microporous oxide film (also referred to as A-plane) As long as it is present at the center of the non-contact surface side (also referred to as the B surface) or in the vicinity thereof, it may be a distribution pattern having a shape such as a bowl, a column, or a rod. It is preferably a needle-like, mountain-shaped or bell-shaped pattern having a peak at the center of the surface and the B surface or in the vicinity thereof.
Thus, the fine metal-containing fine pores are distributed in the fine pore oxide film by distributing the filled metal in a needle-like, mountain-shaped or bell-shaped pattern having a peak at or near the center between the A surface and the B surface. The entire oxide film can be made thinner. Since the permeation speed of gas (for example, hydrogen) is increased by thinning, the film area can be reduced and the amount of metal used can be reduced.
微細孔酸化物膜の細孔に充填されうる金属としては、無電解メッキ処理の可能な金属であれば、特に限定されず、例えば、遷移金属の単体または合金が挙げられ、遷移金属としては、周期表の４族、５族、８族、９族、１０族または１１族の金属が挙げられる。具体的には、銀、パラジウム、ロジウム、ルテニウム、金、白金、イリジウム、オスミウム、銅、ニッケル、コバルト、鉄、バナジウムまたはチタン等が挙げられる。合金としては、例えばパラジウムと、銀、銅、ニッケル等の金属とからなるもの等が挙げられる。これらの金属は単独で用いてもよく、２以上を混合して用いてもよい。また、金属としては、水素選択透過性金属であるものが好ましい。 The metal that can be filled in the pores of the microporous oxide film is not particularly limited as long as it is a metal that can be electrolessly plated, and includes, for example, a transition metal alone or an alloy. Examples include metals of Group 4, Group 5, Group 8, Group 9, Group 10, or Group 11 of the periodic table. Specific examples include silver, palladium, rhodium, ruthenium, gold, platinum, iridium, osmium, copper, nickel, cobalt, iron, vanadium, and titanium. Examples of the alloy include an alloy made of palladium and a metal such as silver, copper, or nickel. These metals may be used alone or in combination of two or more. The metal is preferably a hydrogen selective permeable metal.
本発明の複合体は上記の通り、微細孔酸化物膜の細孔に金属が充填されているとともに、該金属により細孔が閉塞されており、しかも該金属が微細孔酸化物膜の両端部よりも中心部に多く存在する分布パターンで分布しているものであるが、このような複合体は次のようにして製造することができる。すなわち、本発明の複合体は、（１）微細孔酸化物膜が多孔質基材上に積層されてなる微細孔複合体（Ａ）を準備する工程、（２）前記微細孔複合体（Ａ）の微細孔酸化物膜側から還元剤を含む溶液を浸透させ、多孔質基材側から金属源を含む溶液を浸透させることにより、前記微細孔複合体（Ａ）の微細孔酸化物膜の細孔内に金属種核を担持させる工程、（３）前記（２）の工程で得られた金属種核を担持する微細孔複合体（Ｂ）を無電解メッキ処理して、微細孔酸化物膜の細孔を金属により閉塞させる工程、を含むことにより製造できる。また、本発明の複合体は、前記工程（２）において、還元剤を含む溶液と金属源を含む溶液を逆にして、微細孔複合体（Ａ）の微細孔酸化物膜側から金属源を含む溶液を浸透させ、多孔質基材側から還元剤を含む溶液を浸透させることによっても製造できる。 In the composite of the present invention, as described above, the pores of the microporous oxide film are filled with metal, and the pores are blocked by the metal, and the metal is at both ends of the microporous oxide film. Such a composite can be produced as follows, although it is distributed in a distribution pattern existing more in the center than in the case of the above. That is, the composite of the present invention includes (1) a step of preparing a microporous composite (A) in which a microporous oxide film is laminated on a porous substrate, and (2) the microporous composite (A ) Of the microporous oxide film of the microporous composite (A) by infiltrating the solution containing the reducing agent from the side of the microporous oxide film of FIG. A step of supporting metal seed nuclei in the pores; (3) a microporous oxide obtained by electroless plating the microporous composite (B) supporting the metal seed nuclei obtained in the step (2); It can be manufactured by including a step of closing the pores of the membrane with a metal. In the composite of the present invention, in the step (2), the solution containing the reducing agent and the solution containing the metal source are reversed, and the metal source is removed from the microporous oxide film side of the microporous composite (A). It can also be produced by impregnating the solution containing it and infiltrating the solution containing the reducing agent from the porous substrate side.
［工程（１）］
本工程は、微細孔酸化物膜が多孔質基材上に積層されてなる微細孔複合体（Ａ）を準備する工程である。該工程は、例えば、前記多孔質基材の表面に界面活性剤および酸化物源からなるゲル薄膜を形成させて多層構造体とし、該多層構造体を焼成することにより実施できる。
[Step (1)]
This step is a step of preparing a microporous composite (A) in which a microporous oxide film is laminated on a porous substrate. This step can be performed, for example, by forming a gel thin film comprising a surfactant and an oxide source on the surface of the porous substrate to form a multilayer structure, and firing the multilayer structure.
前記ゲル薄膜は、例えば、多孔質基材の表面に、界面活性剤および酸化物源を含む混合溶液（以下、前駆体溶液ともいう）を塗布したのち、乾燥することによって製造できる。 The gel thin film can be produced, for example, by applying a mixed solution containing a surfactant and an oxide source (hereinafter also referred to as a precursor solution) to the surface of a porous substrate and then drying.
前記界面活性剤は、本発明の目的を阻害しない限り特に限定されず、イオン性界面活性剤および非イオン性界面活性剤のいずれであってもよい。
前記イオン性界面活性剤としては、例えば、カチオン性界面活性剤が挙げられ、より具体的には例えば、セチルトリメチルアンモニウムブロミド、セチルトリメチルアンモニウムクロリド、オクタデシルトリメチルアンモニウムブロミドといった臭化物や塩化物が挙げられる。このほかにも、ベンジルトリメチルアンモニウム塩、セチルピリジニウム塩、ミリスチルトリメチルアンモニウム塩、デシルトリメチルアンモニウム塩、ドデシルトリメチルアンモニウム塩、ジメチルジドデシルアンモニウム塩、セチルトリメチルホスホニウム塩、オクタデシルトリメチルホスホニウム塩等が挙げられるが、本発明はこれらに限定されるものではない。
また、前記非イオン性界面活性剤としては、例えば、エチレンオキサイド（ＥＯ）−プロピレンオキサイド（ＰＯ）−エチレンオキサイド（ＥＯ）コポリマーで、Ｐ１２３｛（ＥＯ）２０（ＰＯ）７０（ＥＯ）２０｝やＰ１２７｛（ＥＯ）１０６（ＰＯ）７０（ＥＯ）１０６｝等であるが、エチレンオキサイドおよびプロピレンオキサイドの長さ（重合度）を変えることが出来るのは言うまでもない。また、エチレンオキサイドのポリマーで分子の末端が長鎖のアルキル基であるＢｒｉｊ５６やＢｒｉｊ５８やＢｒｉｊ７００も界面活性剤として用いられる。
The surfactant is not particularly limited as long as it does not hinder the object of the present invention, and may be either an ionic surfactant or a nonionic surfactant.
Examples of the ionic surfactant include cationic surfactants, and more specifically bromides and chlorides such as cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, and octadecyltrimethylammonium bromide. In addition, benzyltrimethylammonium salt, cetylpyridinium salt, myristyltrimethylammonium salt, decyltrimethylammonium salt, dodecyltrimethylammonium salt, dimethyldidodecylammonium salt, cetyltrimethylphosphonium salt, octadecyltrimethylphosphonium salt, etc. The present invention is not limited to these.
The nonionic surfactant is, for example, ethylene oxide (EO) -propylene oxide (PO) -ethylene oxide (EO) copolymer, such as P123 {(EO) 20 (PO) 70 (EO) 20 } or P127 {(EO) 106 (PO) 70 (EO) 106 } and the like, but it goes without saying that the length (degree of polymerization) of ethylene oxide and propylene oxide can be changed. In addition, Brij56, Brij58, and Brij700, which are ethylene oxide polymers whose molecular ends are long-chain alkyl groups, are also used as surfactants.
前記酸化物源としては、例えば金属酸化物源や非金属酸化物源が挙げられ、より具体的には、例えば、シリカ源、アルミナ源、チタニア源、ジルコニア源等の酸化物源が挙げられるが、これらの中でも好ましくはシリカ源である。
前記シリカ源としては、例えば、コロイダルシリカ、ケイ酸ソーダ、テトラアルキルアンモニウムシリケート（例えばテトラメチルアンモニウムシリケート等）、シリコンアルコキシド等が挙げられ、ここで、シリコンアルコキシドとしては、例えばトリメトキシシランやトリエトキシシラン等のトリアルコキシシラン、テトラメトキシシランやテトラエトキシシラン等のテトラアルコキシシラン等が挙げられる。本発明では、これらの１種または２種以上を組み合わせて用いてもよい。
前記混合溶液の塗布方法は、本発明の目的を阻害しない限り特に限定されないが、通常、スピンコーティング法やディップコーティング法が好ましい。
Examples of the oxide source include a metal oxide source and a non-metal oxide source. More specifically, examples include an oxide source such as a silica source, an alumina source, a titania source, and a zirconia source. Of these, a silica source is preferred.
Examples of the silica source include colloidal silica, sodium silicate, tetraalkylammonium silicate (for example, tetramethylammonium silicate), silicon alkoxide, and the like. Here, examples of the silicon alkoxide include trimethoxysilane and triethoxy. Examples include trialkoxysilane such as silane, tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane. In the present invention, one or more of these may be used in combination.
The method for applying the mixed solution is not particularly limited as long as it does not hinder the object of the present invention, but usually a spin coating method or a dip coating method is preferable.
前記前駆体溶液は、例えば、界面活性剤を含む溶液と酸化物源を含む溶液とを混合撹拌することにより、または酸化物源を含む溶液に界面活性剤を含む溶液を加えることにより調製することができる。また、この調製の際に、例えばｐＨ調整剤等の各種添加剤を適宜に用いることができる。 The precursor solution is prepared, for example, by mixing and stirring a solution containing a surfactant and a solution containing an oxide source, or by adding a solution containing a surfactant to a solution containing an oxide source. Can do. In this preparation, various additives such as a pH adjuster can be appropriately used.
前記前駆体溶液の溶媒としては、本発明の目的を阻害しない限り特に限定されず、例えば、水、アルコール等が挙げられる。前記アルコールとしては、例えば、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール等が挙げられる。また、前記溶媒は、水、メタノール、エタノールまたはプロパノールであるのが好ましい。 The solvent for the precursor solution is not particularly limited as long as the object of the present invention is not impaired, and examples thereof include water and alcohol. Examples of the alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol and the like. The solvent is preferably water, methanol, ethanol or propanol.
前記ｐＨ調整剤としては、例えば、酸やアルカリ等が挙げられ、より具体的には、例えば、硫酸、塩酸、硝酸等の無機酸、水酸化ナトリウム、アンモニア等が挙げられる。なお、ｐＨ調整剤として酸を用いる場合には、前記混合液は通常ｐＨ１〜３程度に調整され、また、ｐＨ調整剤としてアルカリを用いる場合には、通常ｐＨ１０〜１３程度に調整される。 Examples of the pH adjuster include acids and alkalis, and more specific examples include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, sodium hydroxide, ammonia, and the like. In addition, when using an acid as a pH adjuster, the said liquid mixture is normally adjusted to about pH 1-3, and when using an alkali as a pH adjuster, it is normally adjusted to about pH 10-13.
前記スピンコーティング法は、多孔質基材を一定速度で回転させ、該多孔質基材上に、界面活性剤および酸化物源を含む混合液を滴下し、均一塗布する方法である。スピンコーティングに続いて乾燥することにより、多孔質基材上に前記前駆体溶液が均一に塗布された塗布物が得られる。なお、スピンコーティング時における回転速度は２０００〜５０００ｒｐｍが好ましい。
前記ディップコーティング法は、多孔質基材を界面活性剤および酸化物源を含む混合液中に浸漬し、一定速度で引き上げることにより、均一塗布する方法である。ディップコーティングに続いて乾燥することにより、多孔質基材上に前記前駆体溶液が均一に塗布された塗布物が得られる。なお、ディップコーティング時における引き上げ速度は０．０１〜５０ｍｍ／ｓｅｃが望ましい。
The spin coating method is a method in which a porous substrate is rotated at a constant speed, and a mixed solution containing a surfactant and an oxide source is dropped onto the porous substrate and uniformly applied. By drying after spin coating, a coated product in which the precursor solution is uniformly coated on a porous substrate is obtained. The rotation speed during spin coating is preferably 2000 to 5000 rpm.
The dip coating method is a method in which a porous substrate is immersed in a mixed solution containing a surfactant and an oxide source, and is uniformly applied by pulling up at a constant speed. By drying following dip coating, a coated product in which the precursor solution is uniformly coated on the porous substrate is obtained. The pulling speed during dip coating is desirably 0.01 to 50 mm / sec.
前記塗布により得られた塗布物を乾燥させることより、多孔質基材の上にゲル薄膜を形成することができる。乾燥温度は、本発明の目的を阻害しなければ特に限定されないが、多孔質基材上に積層したゲル薄膜がより均一に生成するという観点から、室温〜６０℃程度が好ましい。 The gel thin film can be formed on the porous substrate by drying the coated product obtained by the coating. The drying temperature is not particularly limited as long as the object of the present invention is not impaired, but is preferably about room temperature to about 60 ° C. from the viewpoint that the gel thin film laminated on the porous substrate is more uniformly formed.
上記のようにして多孔質基材上にゲル薄膜を積層し、得られた多層構造体を焼成することにより界面活性剤を除去する。本工程により、微細孔酸化物膜が多孔質基材上に積層されてなる微細孔複合体であって、前記多孔質基材の内部に前記微細孔酸化物膜を構成する酸化物が実質的に存在しない微細孔複合体（Ａ）が得られる。前記焼成温度は、通常、界面活性剤の熱分解温度よりも高い温度であり、界面活性剤の種類等によって適宜に設定されるが、あえて好ましい焼成温度をあげると、約３００℃〜７００℃であり、より好ましくは約４００℃〜６００℃である。焼成時の昇温速度は、０．１〜１℃／分程度が好ましい。また、焼成時の保持時間については、焼成温度が例えば約４００℃〜６００℃の範囲内である場合、焼成時の保持時間は１〜４８時間程度が好ましい。
本工程により、多孔質基材上に微細孔酸化物膜が均一に積層された微細孔複合体（Ａ）が得られる。
A gel thin film is laminated on the porous substrate as described above, and the resulting multilayer structure is fired to remove the surfactant. By this step, a microporous composite comprising a microporous oxide film laminated on a porous substrate, wherein the oxide constituting the microporous oxide film is substantially inside the porous substrate. A microporous composite (A) that does not exist is obtained. The firing temperature is usually higher than the thermal decomposition temperature of the surfactant, and is appropriately set depending on the type of the surfactant, etc., but if a preferred firing temperature is raised, it is about 300 ° C. to 700 ° C. More preferably, it is about 400 ° C to 600 ° C. The temperature rising rate during firing is preferably about 0.1 to 1 ° C./min. Moreover, about the holding time at the time of baking, when the baking temperature is in the range of about 400 ° C. to 600 ° C., for example, the holding time at the time of baking is preferably about 1 to 48 hours.
By this step, a microporous composite (A) in which microporous oxide films are uniformly laminated on the porous substrate is obtained.
［工程（２）］
本工程は、前記微細孔複合体（Ａ）の微細孔酸化物膜側から還元剤を含む溶液を浸透させ、多孔質基材側から金属源を含む溶液を浸透させることにより、微細孔酸化物膜の細孔内に金属種核を担持させる工程である。このようにして、金属源を含む溶液および還元剤を含む溶液を微細孔酸化物膜の両側より相互に拡散させることにより、微細孔酸化物膜の細孔内に金属種核を担持させることができる。前記微細孔複合体（Ａ）の微細孔酸化物膜側から還元剤を含む溶液を浸透させると同時に、多孔質基材側から金属源を含む溶液を浸透させるのが好ましい。
前記金属源を含む溶液としては、周期表の４族、５族、８族、９族、１０族または１１族の遷移金属の単体または合金、具体的には、銀、パラジウム、ロジウム、ルテニウム、金、白金、イリジウム、オスミウム、銅、ニッケル、コバルト、鉄、バナジウム、チタン等の単体またはこれらの合金等の金属源を適当な溶媒に溶解した溶液が挙げられる。金属をパラジウムとした場合、例えば酢酸パラジウム、硝酸パラジウム、塩化パラジウム、塩化パラジウム酸、パラジウムアセチルアセトナート、パラジウムヘキサフルオロアセチルアセトナート等が挙げられる。溶媒としては、水、エタノール、クロロホルム等が挙げられる。金属源を含む溶液の濃度は、通常０．０１〜１Ｍ程度、好ましくは０．０５〜０．５Ｍ程度である。
前記還元剤を含む溶液としては、アスコルビン酸、アスコルビン酸ナトリウム、水素化ホウ素ナトリウム、水素化ホウ素カリウム、ジメチルアミンボラン、トリメチルアミンボラン、クエン酸、クエン酸ナトリウム、タンニン酸、ジボラン、ヒドラジン、アルデヒド類（例えばホルムアルデヒド）、グルコース、塩化スズ等の還元剤を適当な溶媒に溶解した溶液が挙げられる。溶媒としては、水、メタノール、エタノール等が挙げられる。前記還元剤は溶液で用いられるのが好ましい。還元剤溶液の濃度は、通常０．００１〜１Ｍ程度、好ましくは０．００２〜０．０５Ｍ程度である。
[Step (2)]
In this step, the fine pore oxide is obtained by infiltrating a solution containing a reducing agent from the fine pore oxide film side of the fine pore composite (A) and infiltrating a solution containing a metal source from the porous substrate side. In this step, metal seed nuclei are supported in the pores of the membrane. In this way, the metal seed nucleus can be supported in the pores of the microporous oxide film by diffusing the solution containing the metal source and the solution containing the reducing agent from both sides of the microporous oxide film. it can. It is preferable that the solution containing the reducing agent is infiltrated from the microporous oxide film side of the microporous composite (A) and at the same time the solution containing the metal source is infiltrated from the porous substrate side.
As the solution containing the metal source, a simple substance or an alloy of a transition metal of Group 4, Group 8, Group 8, Group 9, Group 10 or Group 11 of the periodic table, specifically, silver, palladium, rhodium, ruthenium, Examples thereof include a solution in which a metal source such as gold, platinum, iridium, osmium, copper, nickel, cobalt, iron, vanadium, titanium or the like or a metal source thereof is dissolved in a suitable solvent. When the metal is palladium, for example, palladium acetate, palladium nitrate, palladium chloride, chloropalladic acid, palladium acetylacetonate, palladium hexafluoroacetylacetonate and the like can be mentioned. Examples of the solvent include water, ethanol, chloroform and the like. The density | concentration of the solution containing a metal source is about 0.01-1M normally, Preferably it is about 0.05-0.5M.
Examples of the solution containing the reducing agent include ascorbic acid, sodium ascorbate, sodium borohydride, potassium borohydride, dimethylamine borane, trimethylamine borane, citric acid, sodium citrate, tannic acid, diborane, hydrazine, and aldehydes ( For example, a solution in which a reducing agent such as formaldehyde), glucose, tin chloride or the like is dissolved in an appropriate solvent may be mentioned. Examples of the solvent include water, methanol, ethanol and the like. The reducing agent is preferably used in a solution. The concentration of the reducing agent solution is usually about 0.001 to 1M, preferably about 0.002 to 0.05M.
前記金属源を含む溶液および前記還元剤を含む溶液を微細孔酸化物膜への浸透は、通常２〜６０℃程度、好ましくは２０〜４０℃程度にて、通常１〜１２０分程度、好ましくは１０〜４０分程度行う。次いで、溶液を除去し、通常１〜４８時間程度、好ましくは８〜１６時間程度、２０〜１１０℃程度にて乾燥させることにより、微細孔酸化物膜の細孔内に金属が担持される。
上記の操作によって、前記金属源を含む溶液と前記還元剤を含む溶液が接触した部分で金属源が還元されて金属種核が形成される。
なお、本発明の複合体は、金属が微細孔酸化物膜の表面に付着することはないため、微細孔酸化物膜の表面に保護材を積層することを要しない。
The penetration of the solution containing the metal source and the solution containing the reducing agent into the microporous oxide film is usually about 2 to 60 ° C., preferably about 20 to 40 ° C., usually about 1 to 120 minutes, preferably Perform for about 10 to 40 minutes. Next, the solution is removed, and the metal is supported in the pores of the microporous oxide film by drying at about 20 to 110 ° C., usually for about 1 to 48 hours, preferably about 8 to 16 hours.
By the above operation, the metal source is reduced at the portion where the solution containing the metal source and the solution containing the reducing agent are in contact to form a metal seed nucleus.
Note that the composite of the present invention does not require metal to adhere to the surface of the microporous oxide film, so that it is not necessary to stack a protective material on the surface of the microporous oxide film.
［工程（３）］
本工程は、前記（２）の工程で得られた金属種核を担持する微細孔複合体（Ｂ）を無電解メッキ処理して、金属種核を成長させ、微細孔酸化物膜の細孔を成長した金属により閉塞させて金属充填層を形成する工程である。無電解メッキ処理の方法としては、通常用いられる方法であれば、特に限定されず、前記特許文献６（特開２００６−９５５２１号公報）、特開２００５−２４８１９２号公報等に示される方法と同様にして行うことができる。
無電解メッキ処理には、メッキ液として、金属イオン、錯形成剤、還元剤、溶剤を含むものを用いるのが好ましい。この金属イオンは、適当な金属塩、例えば酢酸塩、塩化物、硝酸塩、硫酸塩等のメッキ液成分として供され、該金属イオンに相応する金属としては、前記したように、無電解メッキの可能な金属、例えば遷移金属等が挙げられ、遷移金属として好ましくは周期表の４族、５族、８族、９族、１０族または１１族の金属等が挙げられ、中でも銀、パラジウム、ロジウム、ルテニウム、金、白金、イリジウム、オスミウム、銅、ニッケル、コバルト、鉄、バナジウムまたはチタン等が挙げられる。これらの金属は単独で用いてもよく、２以上を混合して用いてもよい。
前記錯形成剤としては、金属イオンを安定に溶存させるものであればよく、その例として好ましくはアンモニアとキレート剤との組合せ、中でもアンモニアとＥＤＴＡとの組合せが挙げられ、キレート剤としては、ＥＤＴＡの他、ＮＴＡ（ニトリロトリ酢酸）や、クエン酸、酒石酸等の脂肪族オキシ酸等が挙げられる。
前記還元剤としては、アスコルビン酸、アスコルビン酸ナトリウム、水素化ホウ素ナトリウム、水素化ホウ素カリウム、ジメチルアミンボラン、トリメチルアミンボラン、クエン酸、クエン酸ナトリウム、タンニン酸、ジボラン、ヒドラジン、アルデヒド類、グルコースまたは塩化スズ等が挙げられる。
前記溶剤としては、錯形成剤の種類等にもよるが、水、あるいはアセトニトリル、ベンゼン、クロロホルム等の有機溶媒等が挙げられる。
メッキ液組成について、例えば金属イオン、キレート剤、アンモニアおよび還元剤を含有する場合、各濃度は、０．００１〜０．０５Ｍ程度、０．０１〜０．５Ｍ程度、５〜１５Ｍ程度、０．００５〜０．０５Ｍ程度がよい。メッキ液を調製する場合、前記無電解メッキ処理の直前に還元剤を加えることが好ましい。
[Step (3)]
In this step, the microporous composite (B) carrying the metal seed nuclei obtained in the step (2) is electrolessly plated to grow the metal seed nuclei, and the pores of the microporous oxide film Is a step of forming a metal-filled layer by closing the substrate with the grown metal. The method of electroless plating treatment is not particularly limited as long as it is a commonly used method, and is the same as the method disclosed in Patent Document 6 (JP 2006-95521 A), JP 2005-248192 A, and the like. Can be done.
In the electroless plating treatment, it is preferable to use a plating solution containing a metal ion, a complexing agent, a reducing agent, and a solvent. This metal ion is provided as a plating solution component of an appropriate metal salt, for example, acetate, chloride, nitrate, sulfate, etc., and the metal corresponding to the metal ion can be electrolessly plated as described above. Examples of the transition metal include, but are not limited to, metals of Group 4, Group 5, Group 8, Group 10, Group 11 or Group 11 of the periodic table. Among them, silver, palladium, rhodium, Examples include ruthenium, gold, platinum, iridium, osmium, copper, nickel, cobalt, iron, vanadium or titanium. These metals may be used alone or in combination of two or more.
The complexing agent is not particularly limited as long as it can stably dissolve metal ions, and examples thereof include a combination of ammonia and a chelating agent, and particularly a combination of ammonia and EDTA. In addition, NTA (nitrilotriacetic acid) and aliphatic oxyacids such as citric acid and tartaric acid can be used.
Examples of the reducing agent include ascorbic acid, sodium ascorbate, sodium borohydride, potassium borohydride, dimethylamine borane, trimethylamine borane, citric acid, sodium citrate, tannic acid, diborane, hydrazine, aldehydes, glucose or chloride. Tin etc. are mentioned.
Examples of the solvent include water, and organic solvents such as acetonitrile, benzene, and chloroform, depending on the type of complexing agent.
About a plating solution composition, when it contains a metal ion, a chelating agent, ammonia, and a reducing agent, each density | concentration is about 0.001-0.05M, about 0.01-0.5M, about 5-15M, 0.00. About 005-0.05M is good. When preparing a plating solution, it is preferable to add a reducing agent immediately before the electroless plating treatment.
前記無電解メッキ処理により微細孔酸化物膜内の細孔内に担持された金属が成長し、前記細孔内が前記金属で充填された金属充填層が形成される。
前記無電解メッキ処理の温度は、適宜に設定できるが、通常１〜６０℃程度であり、より好ましくは２〜２５℃程度である。無電解メッキ処理時間はメッキ液温度や膜厚にもよるが、通常１分〜１００時間程度、好ましくは１〜７２時間程度である。前記無電解メッキ処理後、常法により、得られた複合体を洗浄し、乾燥させて本発明の複合体が得られる。
本発明の複合体は、水素分離膜として好適に用いることができる。
By the electroless plating process, the metal supported in the pores in the microporous oxide film grows, and a metal-filled layer in which the pores are filled with the metal is formed.
The temperature of the electroless plating treatment can be appropriately set, but is usually about 1 to 60 ° C, more preferably about 2 to 25 ° C. Although the electroless plating treatment time depends on the plating solution temperature and film thickness, it is usually about 1 minute to 100 hours, preferably about 1 to 72 hours. After the electroless plating treatment, the obtained composite is washed and dried by a conventional method to obtain the composite of the present invention.
The composite of the present invention can be suitably used as a hydrogen separation membrane.
次いで、本発明の水素分離方法について説明する。本発明の水素分離方法は、水素を含有する混合ガス（以下、水素混合ガスという）を前記複合体に接触させて、水素を選択的に透過させることを特徴とする。 Next, the hydrogen separation method of the present invention will be described. The hydrogen separation method of the present invention is characterized in that hydrogen is selectively permeated by bringing a mixed gas containing hydrogen (hereinafter referred to as hydrogen mixed gas) into contact with the composite.
本方法の具体的な態様としては、前記複合体の片側（微細孔酸化物膜側）に水素混合ガスを置き、その反対側（多孔質基材表面側）の水素分圧を微細孔酸化物膜側の水素分圧以下にすれば、複合体中を水素が選択的に透過し、水素混合ガス中にある水素を多孔質基材表面側に分離することができる。この水素分離方法は通常室温〜７００℃程度、好ましくは３００〜６００℃程度の温度で好適に実施することができる。 As a specific embodiment of this method, a hydrogen mixed gas is placed on one side (microporous oxide film side) of the composite, and the hydrogen partial pressure on the opposite side (porous substrate surface side) is adjusted to microporous oxide. If the hydrogen partial pressure is lower than the membrane side, hydrogen selectively permeates through the composite, and hydrogen in the hydrogen mixed gas can be separated to the porous substrate surface side. This hydrogen separation method can be suitably carried out at a temperature of usually room temperature to about 700 ° C., preferably about 300 to 600 ° C.
前記水素混合ガスとしては、水素を含有しているガスであれば特に限定されず、例えば、水素と、酸素、窒素、ヘリウム、ネオン、アルゴン、クリプトン、キセノン、ラドン、フッ素、塩素、臭素、一酸化炭素、二酸化炭素、一酸化窒素、二酸化窒素、アンモニア、二酸化イオウ、硫化水素、塩化水素、水（水蒸気）、メタノール、エタノール、パラフィン系炭化水素またはオレフィン系炭化水素等との混合ガスが挙げられる。なお、前記パラフィン系炭化水素は、飽和鎖式炭化水素、アルカンまたはメタン系炭化水素とも呼ばれ、このようなパラフィン系炭化水素としては、例えば、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン等が挙げられる。 The hydrogen mixed gas is not particularly limited as long as it contains hydrogen. For example, hydrogen and oxygen, nitrogen, helium, neon, argon, krypton, xenon, radon, fluorine, chlorine, bromine, one Carbon dioxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, ammonia, sulfur dioxide, hydrogen sulfide, hydrogen chloride, water (steam), methanol, ethanol, paraffinic hydrocarbons, olefinic hydrocarbons, etc. . The paraffinic hydrocarbons are also called saturated chain hydrocarbons, alkanes, or methane hydrocarbons. Examples of such paraffinic hydrocarbons include methane, ethane, propane, butane, pentane, hexane, and heptane. , Octane and the like.
以下に、実施例、比較例および試験例を用いて本発明を説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described using examples, comparative examples, and test examples, but the present invention is not limited to these examples.
［実施例］
（メソ細孔シリカ膜の作製）
メソ細孔シリカ膜はS. Besson, T. Gacoin, C. Jacquiod, C. Ricolleau, D. Babonneau, J. -P. Boilot, Journal of Materials Chemistry 2000, 10, 1331-1336を参考にして作製した。
ガラス瓶にテトラエチルオルソシリケート（Tetraethylorthosilicate，ＴＥＯＳ，シグマ アルドリッチ ジャパン株式会社）４．１６ｇ、塩酸にてｐＨ＝１．２５に調製した脱イオン水１．８ｇ、およびエタノール３．５ｇを加え、６０℃にて１時間撹拌を行った。その後、セチルトリメチルアンモニウムブロミド（Cethyltrimethylammonium bromide，ＣＴＡＢ）０．７２ｇを加え、超音波洗浄器（ＵＳ−１０１，株式会社エスエヌディ）を用いて超音波を５分間照射することにより溶解させ、前駆体溶液を調製した。該前駆体溶液を多孔質基材のαアルミナ（株式会社ノリタケカンパニーリミテド製）上に１００μｌ滴下し、４０００ｒｐｍにて６０秒スピンコーティングを行った後、室温にて１時間乾燥させた。スピンコーティングおよび乾燥工程を数回繰り返した後、５００℃にて２０時間焼成し、界面活性剤であるＣＴＡＢを除去することにより、多孔質基材上にメソ細孔シリカ膜が積層されたメソ細孔複合体（Ａ）を得た（以下、ＭＳ／Ａｌ２Ｏ３ともいう）。
[Example]
(Preparation of mesoporous silica film)
Mesoporous silica membranes were prepared with reference to S. Besson, T. Gacoin, C. Jacquiod, C. Ricolleau, D. Babonneau, J.-P. Boilot, Journal of Materials Chemistry 2000, 10, 1331-1336. .
Add 4.16 g of tetraethylorthosilicate (TEOS, Sigma Aldrich Japan Co., Ltd.) to a glass bottle, 1.8 g of deionized water adjusted to pH = 1.25 with hydrochloric acid, and 3.5 g of ethanol at 60 ° C. Stir for 1 hour. Thereafter, 0.72 g of cetyltrimethylammonium bromide (CTAB) is added, and the precursor solution is dissolved by irradiating with ultrasonic waves for 5 minutes using an ultrasonic cleaner (US-101, SND Co., Ltd.). Prepared. 100 μl of the precursor solution was dropped on α-alumina (manufactured by Noritake Company Limited) as a porous substrate, spin-coated at 4000 rpm for 60 seconds, and then dried at room temperature for 1 hour. After repeating the spin coating and drying steps several times, baking is carried out at 500 ° C. for 20 hours to remove CTAB, which is a surfactant, so that a mesofine silica film having a mesoporous silica film laminated on a porous substrate is obtained. A pore complex (A) was obtained (hereinafter also referred to as MS / Al 2 O 3 ).
（メソ細孔シリカ膜での金属種核の担持）
前記メソ細孔複合体（Ａ）のメソ細孔シリカ膜内へのパラジウム複合化は以下の手順にて実施した。
還元剤を含む溶液としてヒドラジン水溶液を、金属源を含む溶液として塩化パラジウム酸水溶液を用いた。前記ヒドラジン水溶液は、ヒドラジン１水和物０．５ｍｌを脱イオン水に加え、さらに脱イオン水で希釈し、全量１０００ｍｌとすることにより調製し、前記塩化パラジウム酸水溶液は、塩化パラジウム（ＩＩ）１７．７３３ｇを０．２ｍｏｌ／ｌ塩酸に溶解させ、全量を１０００ｍｌとすることにより調製した。
ガラスシャーレに、前記メソ細孔複合体（Ａ）を置き、図１に示されるように、塩化パラジウム酸水溶液を多孔質基材（アルミナ）表面側から、ヒドラジン水溶液をメソ細孔シリカ膜側から同時に室温で３０分、浸透させることにより、メソ細孔シリカ膜内へパラジウムを担持させた。
パラジウム種核形成後、脱イオン水にて、十分に洗浄を行い、６０℃で１日、乾燥を行い、パラジウム種核を含むメソ細孔シリカ膜（膜厚は０．５〜１μｍ程度）が積層されたメソ細孔複合体（Ｂ）を得た（以下、Ｐｄ−ＭＳ／Ａｌ２Ｏ３ともいう）。
(Support of metal seed nuclei on mesoporous silica membrane)
Palladium complexation of the mesopore composite (A) into the mesopore silica membrane was performed by the following procedure.
A hydrazine aqueous solution was used as a solution containing a reducing agent, and a chloropalladium acid aqueous solution was used as a solution containing a metal source. The hydrazine aqueous solution was prepared by adding 0.5 ml of hydrazine monohydrate to deionized water and further diluting with deionized water to a total volume of 1000 ml. The aqueous palladium chloride solution was prepared by adding palladium (II) chloride 17 .733 g was dissolved in 0.2 mol / l hydrochloric acid to make a total volume of 1000 ml.
The mesopore composite (A) is placed in a glass petri dish, and as shown in FIG. 1, the aqueous solution of chloropalladium acid is from the porous substrate (alumina) surface side, and the aqueous hydrazine solution is from the mesoporous silica membrane side. Simultaneously, it was allowed to permeate at room temperature for 30 minutes, thereby supporting palladium in the mesoporous silica membrane.
After the formation of the palladium seed nucleus, it is thoroughly washed with deionized water, dried at 60 ° C. for 1 day, and a mesoporous silica film containing palladium seed nucleus (film thickness is about 0.5 to 1 μm) A laminated mesopore composite (B) was obtained (hereinafter also referred to as Pd-MS / Al 2 O 3 ).
（組織観察）
作製したメソ細孔複合体（Ｂ）を走査型電子顕微鏡（ＳＥＭ、製品名：Ｓ−５０００、株式会社日立製作所）およびエネルギー分散型Ｘ線分析装置（ＥＤＸ、製品名：Genesis-XM2、エダックス・ジャパン株式会社）により評価した。図２にパラジウム種核形成後のメソ細孔シリカ膜断面のＳＥＭおよびＥＤＸ像を示す。
ＥＤＸの結果から、パラジウム種核はメソ細孔シリカ膜内に担持されており、その存在範囲は５００ｎｍ程度と非常に狭いことがわかった。
(Tissue observation)
Scanning electron microscope (SEM, product name: S-5000, Hitachi, Ltd.) and energy dispersive X-ray analyzer (EDX, product name: Genesis-XM2, Edax Japan Corporation). FIG. 2 shows an SEM and EDX image of the cross section of the mesoporous silica film after formation of palladium seed nuclei.
From the results of EDX, it was found that the palladium seed nucleus was supported in the mesoporous silica film, and its existence range was as narrow as about 500 nm.
（無電解メッキ処理）
パラジウム種核形成後、パラジウム充填率の向上を目的としてメソ細孔複合体（Ｂ）へ無電解メッキ処理を実施した。
まず、２８％アンモニア水溶液６５１．３ｍｌに、塩化パラジウム３．９ｇおよびエチレンジアミン４酢酸・２ナトリウム塩６７．２ｇを溶解させた後、脱イオン水を加えて１０００ｍｌとした。その後、無電解メッキ処理直前にヒドラジン１水和物０．３５ｍｌを加え、無電解メッキ液とした。図３に示すように前記メッキ液をメソ細孔シリカ膜側から浸透させることにより、３℃で４８時間無電解メッキを行った。無電解メッキ後、膜を十分な量の脱イオン水で洗浄し、６０℃で１日乾燥を行い、目的の複合体を得た。
(Electroless plating treatment)
After the formation of palladium seed nuclei, electroless plating treatment was performed on the mesoporous composite (B) for the purpose of improving the palladium filling rate.
First, 3.9 g of palladium chloride and 67.2 g of ethylenediaminetetraacetic acid / disodium salt were dissolved in 651.3 ml of 28% aqueous ammonia solution, and then deionized water was added to make 1000 ml. Thereafter, 0.35 ml of hydrazine monohydrate was added immediately before the electroless plating treatment to obtain an electroless plating solution. As shown in FIG. 3, electroless plating was performed at 3 ° C. for 48 hours by infiltrating the plating solution from the mesoporous silica film side. After electroless plating, the membrane was washed with a sufficient amount of deionized water and dried at 60 ° C. for 1 day to obtain the desired composite.
（組織観察）
作製した複合体の構造観察をＳＥＭ、ＥＤＸおよび透過型電子顕微鏡（ＴＥＭ，製品名：ＨＦ−２０００、株式会社日立製作所）にて実施した。図４に無電解メッキ処理後のパラジウム複合化メソ細孔シリカ膜断面のＳＥＭ、ＥＤＸ像を、図５にＴＥＭ像を示す。
ＳＥＭ、ＥＤＸで観察した結果、無電解メッキ処理により形成されたパラジウムが担持されている部分の厚さは１μｍであり、メソ細孔シリカ膜内に選択的に金属充填層が形成されていることがわかった。これは、無電解メッキの反応場となるパラジウム核が、予めメソ細孔シリカ層内に選択的に配されていることによる。ＴＥＭ観察の結果、数ｎｍのパラジウム粒子がシリカに内包された構造を取っていることがわかった。また、充填されたパラジウムの分布パターンは、メソ細孔シリカ膜のαアルミナと接触している面側と接触していない面側との間の中央付近にピークを有する山型もしくは釣り鐘型パターンであった。
以上のことから、本発明の複合体を構成する金属充填層を、５μｍ以下でも容易に薄膜化できることが確認された。
(Tissue observation)
The structure of the produced composite was observed with SEM, EDX, and transmission electron microscope (TEM, product name: HF-2000, Hitachi, Ltd.). FIG. 4 shows an SEM / EDX image of the cross section of the palladium composite mesoporous silica film after the electroless plating treatment, and FIG. 5 shows a TEM image.
As a result of observation by SEM and EDX, the thickness of the portion on which palladium formed by electroless plating is carried is 1 μm, and a metal-filled layer is selectively formed in the mesoporous silica film. I understood. This is because palladium nuclei serving as a reaction field for electroless plating are selectively arranged in advance in the mesoporous silica layer. As a result of TEM observation, it was found that palladium particles of several nm had a structure encapsulated in silica. The distribution pattern of the filled palladium is a mountain-shaped or bell-shaped pattern having a peak near the center between the surface side of the mesoporous silica film that is in contact with the α-alumina and the surface side that is not in contact. there were.
From the above, it was confirmed that the metal filling layer constituting the composite of the present invention can be easily thinned even with a thickness of 5 μm or less.
［試験例］
実施例で得られたパラジウム複合化メソ細孔シリカ膜について、１００℃および３００℃における水素／二酸化炭素（Ｈ２／ＣＯ２＝５０：５０）混合ガスの透過試験を下記条件にて行った。その結果を図６および図７に示す。なお、Ｈ２／ＣＯ２混合ガスの分離実験の実験装置を模式的に図８に示す。図８に示すように、Ｈ２／ＣＯ２混合ガスを、実施例で得られた複合体に接触させて、前記複合体を透過したガス（透過ガス）をサンプリングして、下記実験条件にてガスクロマトグラフィー（ＧＣ）測定を行った。
[Test example]
With respect to the palladium-complexed mesoporous silica membrane obtained in the Examples, a hydrogen / carbon dioxide (H 2 / CO 2 = 50: 50) mixed gas permeation test at 100 ° C. and 300 ° C. was performed under the following conditions. The results are shown in FIGS. Incidentally, showing the experimental apparatus separation experiments H 2 / CO 2 gas mixture schematically in FIG. As shown in FIG. 8, the H 2 / CO 2 mixed gas was brought into contact with the composite obtained in the example, and the gas permeated through the composite (permeated gas) was sampled and subjected to the following experimental conditions. Gas chromatography (GC) measurement was performed.
（実験条件）
ガス分析：ガスクロマトグラフィー；ＧＣ（ＴＣＤ）
カラム：Ｐｏｒａｐａｋ−Ｑ ２ｍ、活性炭＋Chromosorb W AW-DMCS ２ｍ（株式会社ラウンドサイエンス）
キャリアガス：Ｈｅ
テストガス：Ｈ２／ＣＯ２＝５０／５０
ガス流量：１００ｍｌ／分
入口ガス圧力：１５０ｋＰａ
(Experimental conditions)
Gas analysis: gas chromatography; GC (TCD)
Column: Porapak-Q 2m, activated carbon + Chromosorb W AW-DMCS 2m (Round Science Co., Ltd.)
Carrier gas: He
Test gas: H 2 / CO 2 = 50/50
Gas flow rate: 100 ml / min Inlet gas pressure: 150 kPa
（結果）
１００℃における気体透過試験の結果、水素の透過度ＰＨ２は５×１０−８ｍｏｌ ｍ−２ｓ−１Ｐａ−１程度であり、水素選択性α＝ＰＨ２／ＰＣＯ２は５００程度で試験中ほぼ安定な性能を示した。また、試験温度を３００℃まで上昇させたところ、水素選択性αは３００程度を維持しており、水素透過度ＰＨ２は６×１０−７ｍｏｌ ｍ−２ｓ−１Ｐａ−１以上と優れた値を示した。試験開始７２時間後においても性能の大きな低下は認められなかった。
以上の結果より、本複合体は水素透過性に優れるとともに、メソ細孔シリカ膜の表面に保護材を表面に積層することなく、耐久性に優れることが確認された。また、メソ細孔シリカ膜内にパラジウム粒子が内包された構造を取っており、膜表面の保護等、実用化面においても有用である。また、電子顕微鏡撮影結果から、Ｐｄを含むメソ細孔シリカ膜の膜厚は１μｍ程度と極めて薄く、また、作製したメソ細孔シリカ膜の構造から推定される空隙率は２０〜３０％程度であるため、これまでに報告されている無電解メッキ等で調製された５μｍのＰｄ金属薄膜と比較して、少なくともＰｄの使用量を１／１６程度に低減できた。
(result)
As a result of the gas permeation test at 100 ° C., the hydrogen permeability P H2 is about 5 × 10 −8 mol m −2 s −1 Pa −1 and the hydrogen selectivity α = P H2 / P CO2 is about 500. The performance was almost stable. Moreover, when the test temperature was raised to 300 ° C., the hydrogen selectivity α was maintained at about 300, and the hydrogen permeability PH 2 was as excellent as 6 × 10 −7 mol m −2 s −1 Pa −1 or more. The value was shown. Even after 72 hours from the start of the test, no significant decrease in performance was observed.
From the above results, it was confirmed that this composite was excellent in hydrogen permeability and excellent in durability without laminating a protective material on the surface of the mesoporous silica film. Further, it has a structure in which palladium particles are encapsulated in a mesoporous silica film, which is useful in practical use such as protection of the film surface. The mesoporous silica film containing Pd has an extremely thin film thickness of about 1 μm, and the porosity estimated from the structure of the prepared mesoporous silica film is about 20-30%. Therefore, the amount of Pd used can be reduced to at least about 1/16 compared to a 5 μm Pd metal thin film prepared by electroless plating or the like reported so far.
本発明の複合体は、水素透過性および耐久性に優れ、安価に提供されるため、燃料電池システムに含まれる水素製造装置等に有用である。 Since the composite of the present invention is excellent in hydrogen permeability and durability and is provided at low cost, it is useful for a hydrogen production apparatus included in a fuel cell system.
１ ヒドラジン水溶液
２ 塩化パラジウム酸水溶液
３ メソ細孔シリカ膜
４ 多孔質基材
５ 無電解メッキ液
DESCRIPTION OF SYMBOLS 1 Hydrazine aqueous solution 2 Palladium chloride acid aqueous solution 3 Mesoporous silica membrane 4 Porous base material 5 Electroless plating liquid
Claims (25)
（１）微細孔酸化物膜が多孔質基材上に積層されてなる微細孔複合体（Ａ）を準備する工程、
（２）前記微細孔複合体（Ａ）の微細孔酸化物膜表面側から還元剤を含む溶液を浸透させ、多孔質基材側から金属源を含む溶液を浸透させることにより、前記微細孔複合体（Ａ）の微細孔酸化物膜の細孔内に金属種核を担持させる工程、
（３）前記（２）の工程で得られた金属種核を担持する微細孔複合体（Ｂ）を無電解メッキ処理して、微細孔酸化物膜の細孔を金属により閉塞させる工程、
を含むことを特徴とする複合体の製造方法。 A method for producing a composite, comprising:
(1) a step of preparing a microporous composite (A) in which a microporous oxide film is laminated on a porous substrate;
(2) By infiltrating a solution containing a reducing agent from the surface of the microporous oxide film of the microporous composite (A) and permeating a solution containing a metal source from the porous substrate side, the microporous composite A step of supporting metal seed nuclei in the pores of the microporous oxide film of the body (A),
(3) a step of electroless plating the fine pore composite (B) carrying the metal seed nucleus obtained in the step (2) to close the pores of the fine pore oxide film with a metal;
The manufacturing method of the composite_body | complex characterized by including.
（１）微細孔酸化物膜が多孔質基材上に積層されてなる微細孔複合体（Ａ）を準備する工程、
（２）前記微細孔複合体（Ａ）の微細孔酸化物膜表面側から金属源を含む溶液を浸透させ、多孔質基材側から還元剤を含む溶液を浸透させることにより、前記微細孔複合体（Ａ）の微細孔酸化物膜の細孔内に金属種核を担持させる工程、
（３）前記（２）の工程で得られた金属種核を担持する微細孔複合体（Ｂ）を無電解メッキ処理して、微細孔酸化物膜の細孔を金属により閉塞させる工程、
を含むことを特徴とする複合体の製造方法。 A method for producing a composite, comprising:
(1) a step of preparing a microporous composite (A) in which a microporous oxide film is laminated on a porous substrate;
(2) By infiltrating a solution containing a metal source from the surface of the microporous oxide film of the microporous composite (A) and permeating a solution containing a reducing agent from the porous substrate side, the microporous composite A step of supporting a metal seed nucleus in the pores of the microporous oxide film of the body (A),
(3) a step of electroless plating the fine pore composite (B) carrying the metal seed nucleus obtained in the step (2) to close the pores of the fine pore oxide film with a metal;
The manufacturing method of the composite_body | complex characterized by including.
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| JPWO2013146622A1 (en) * | 2012-03-28 | 2015-12-14 | 日本碍子株式会社 | Method for producing silica membrane filter and silica membrane filter |
| JP6014920B1 (en) * | 2015-08-19 | 2016-10-26 | 株式会社山王 | Metal composite hydrogen permeable membrane and manufacturing method thereof |
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