JP2012055855A - Catalyst carrier, catalyst body, and method for manufacturing the same - Google Patents
Catalyst carrier, catalyst body, and method for manufacturing the same Download PDFInfo
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- JP2012055855A JP2012055855A JP2010203244A JP2010203244A JP2012055855A JP 2012055855 A JP2012055855 A JP 2012055855A JP 2010203244 A JP2010203244 A JP 2010203244A JP 2010203244 A JP2010203244 A JP 2010203244A JP 2012055855 A JP2012055855 A JP 2012055855A
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- aluminum substrate
- pits
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 125
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000000758 substrate Substances 0.000 claims abstract description 82
- 230000036571 hydration Effects 0.000 claims abstract description 22
- 238000006703 hydration reaction Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000002048 anodisation reaction Methods 0.000 claims abstract description 4
- 238000005530 etching Methods 0.000 claims description 36
- 230000000149 penetrating effect Effects 0.000 claims description 12
- 238000007743 anodising Methods 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 9
- 230000000887 hydrating effect Effects 0.000 claims description 5
- 230000035515 penetration Effects 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 239000011888 foil Substances 0.000 description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000002848 electrochemical method Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- -1 halogen ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-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
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 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 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
- Fuel Cell (AREA)
Abstract
Description
本発明は、各種フィルター、吸着剤または充填材などの用途に有用な酸化物系多孔体である触媒担体、触媒体及びその製造方法に関するものである。 The present invention relates to a catalyst carrier that is an oxide-based porous body useful for various filters, adsorbents, fillers, and the like, a catalyst body, and a method for producing the same.
アルミニウムまたはアルミニウム合金の表面を陽極酸化によりアルミナ皮膜を化成せしめ、これを焼成してアルミナ触媒担体を製造せしめるものとして、引用文献１がある。
There is cited
また、アルミニウム表面に陽極酸化によりアルミナ層を形成せしめ、次に５０℃〜３５０℃で熱水処理した後、又は、熱水処理を行ないながら触媒活性を有する金属を前記アルミナ層に担持させて触媒体を製造して、前記触媒体のＢＥＴ表面積を増大させるものとして、引用文献２がある。
In addition, an alumina layer is formed on the aluminum surface by anodic oxidation and then hydrothermally treated at 50 ° C. to 350 ° C., or a metal having catalytic activity is supported on the alumina layer while performing hydrothermal treatment. There is cited
また、陽極酸化された金属表面を、５℃〜４５℃の水又は温水で水和処理した後、焼成することにより、細孔半径分布のピークを調整するものとして、引用文献３がある。
Moreover, there exists cited
また、陽極酸化によって形成されたアルミナ層表面を、水和処理、ゾルゲル処理及び触媒担持処理及び焼成処理することにより触媒体を製造するものとして、引用文献４がある。
Further, there is cited
また、陽極酸化によって形成されたアルマイト表面を酸処理して、アルマイト表面の細孔の孔径を拡大し、次いで水和処理、焼成処理してアルマイト触媒担体を製造して、触媒担体のＢＥＴ比表面積を増大させるものとして、引用文献５がある。
Also, the anodized surface formed by anodic oxidation is acid-treated to enlarge the pore size of the pores on the anodized surface, then hydrated and calcined to produce an anodized catalyst support, and the BET specific surface area of the catalyst support There is cited
また、アルミニウム表面に窪み状のピットを形成した後に、陽極酸化処理によって皮膜を形成し、その皮膜に形成された微細孔に触媒を担持せしめて触媒体を製造して、従来よりも陽極酸化皮膜厚を薄くして、ローコストで、高比表面積を得られるものとして、引用文献６及び引用文献７がある。
In addition, after forming hollow pits on the aluminum surface, a film is formed by anodizing treatment, and a catalyst is produced by supporting the catalyst in the micropores formed in the film. There are cited
しかしながら、前記引用文献６及び引用文献７に記載の触媒体は、ピットが非貫通である為、物質の拡散律速により、ピットの深い部分まで有効に使われない為、性能が十分ではなかった。
However, the catalyst bodies described in the above cited
本発明は触媒性能を向上せしめた触媒担体、触媒体を提供することを目的としたものである。 An object of the present invention is to provide a catalyst carrier and a catalyst body with improved catalyst performance.
本発明においては、アルミニウム基板（アルミニウム箔、アルミニウム合金基板を含む。以下同じ。）に、例えば、エッチング処理により前記アルミニウム基板の一方の面から他方の面まで貫通する複数の貫通ピットを形成せしめ、このアルミニウム基板を陽極酸化処理して、前記アルミニウム基板の表面及び貫通ピットの表面に陽極酸化皮膜（アルマイト皮膜）を形成せしめて触媒担体を作成させめる。また、このアルミニウム基板を水和処理して水酸化アルミニウムの皮膜（水和皮膜）を形成せしめ、これを焼成して触媒担体を作成せしめてもよい。その後、前記触媒担体に触媒を担持して触媒体を形成せしめる。 In the present invention, an aluminum substrate (including an aluminum foil and an aluminum alloy substrate; the same shall apply hereinafter) is formed with, for example, a plurality of penetrating pits penetrating from one surface of the aluminum substrate to the other by etching. This aluminum substrate is anodized to form an anodized film (alumite film) on the surface of the aluminum substrate and the surface of the through pits, thereby preparing a catalyst carrier. Alternatively, the aluminum substrate may be hydrated to form an aluminum hydroxide film (hydrated film), which may be fired to form a catalyst carrier. Thereafter, the catalyst is supported on the catalyst carrier to form a catalyst body.
または、アルミニウム基板に、例えば、エッチング処理により前記アルミニウム基板の一方の面から他方の面まで貫通する複数の貫通ピットを形成せしめ、このアルミニウム基板を水和処理して、前記アルミニウム基板の表面と貫通ピットの表面を水和処理して水酸化アルミニウムの皮膜（水和皮膜）を形成せしめ、これを焼成して触媒担体を作成せしめた後に、触媒を担持して触媒体を形成せしめる。 Alternatively, a plurality of penetrating pits that penetrate from one surface of the aluminum substrate to the other surface are formed on the aluminum substrate, for example, by etching, and the aluminum substrate is hydrated to penetrate the surface of the aluminum substrate. The surface of the pits is hydrated to form an aluminum hydroxide film (hydrated film), which is fired to form a catalyst carrier, and then the catalyst is supported to form a catalyst body.
前記エッチング処理とは、特に限定されず、電気化学的手法またはサンドブラストや機械加工などの物理的手法等があるが、電気化学的手法が好ましい。 The etching treatment is not particularly limited, and includes an electrochemical method or a physical method such as sandblasting or machining, but an electrochemical method is preferable.
前記電気化学的手法は、例えば、図１に示すように、アルミニウム基板１をハロゲンイオンを含んだ溶液（例えば、塩酸）浴２で直流により電解処理して、貫通ピットを発生させた後、中性または酸性溶液中で直流により電解処理せしめて、前記貫通ピットの径を拡大せしめる。
For example, as shown in FIG. 1, the electrochemical method includes electrolytic treatment of an
前記アルミニウム基板は、電気化学的手法の場合においては、表面における（１，０，０）面の結晶方位占有率が５０％以上で、アルミ純度が９８％以上の厚さが５〜１０００μｍであり、好ましくは、表面における（１，０，０）面の結晶方位占有率が９５％以上で、アルミ純度が９９．９％以上で、厚さが１００μｍ前後である。 In the case of the electrochemical method, the aluminum substrate has a (1,0,0) plane crystal orientation occupancy ratio of 50% or more and an aluminum purity of 98% or more and a thickness of 5 to 1000 μm. Preferably, the crystal orientation occupancy of the (1, 0, 0) plane on the surface is 95% or more, the aluminum purity is 99.9% or more, and the thickness is about 100 μm.
前記エッチング処理により形成される、アルミニウム基板を貫通する貫通ピットは、アルミニウム基板に対して垂直である以外に斜めであってもよい。 The through pits penetrating the aluminum substrate formed by the etching process may be oblique in addition to being perpendicular to the aluminum substrate.
また、アルミニウム基板を貫通する貫通ピットのピット径は孔径が細かすぎると、反応物質の流通が律速となり、孔径が大きすぎると、拡面効率が悪くなるため、貫通ピット中、最小のピット径は０．１μｍ以上で、平均ピット径が０．３〜５μｍが好ましいが、特に、最小ピット径が０．３μｍ以上で、平均ピット径が０．５μｍ以上が好ましい。 In addition, if the pit diameter of the penetrating pits penetrating the aluminum substrate is too small, the flow rate of the reactant becomes rate limiting, and if the hole diameter is too large, the surface expansion efficiency deteriorates. The average pit diameter is preferably 0.1 to 5 μm and is preferably 0.3 to 5 μm. In particular, the minimum pit diameter is 0.3 μm and the average pit diameter is preferably 0.5 μm and more.
なお、図２は貫通ピットを有する酸化物レプリカ（貫通ピットの観察のためにアルミニウム部分を溶解除去した酸化物レプリカ）の断面のＳＥＭ写真を示し、図３は貫通ピットを有するアルミニウム基板の一部の模式図を表し、３はアルミニウム基板に形成された貫通ピットである。 2 shows an SEM photograph of a cross section of an oxide replica having through pits (an oxide replica in which an aluminum portion is dissolved and removed for observation of the through pits), and FIG. 3 is a part of an aluminum substrate having through pits. 3 is a through pit formed in the aluminum substrate.
前記陽極酸化処理は、酸性電解浴で行い、燐酸、硫酸、蓚酸、クロム酸、スルファサリチル酸、ピロリン酸、スルファミン酸、リンモリブデン酸、マロン酸、マレイン酸、コハク酸、酒石酸、フタル酸、クエン酸、イタコン酸、リンゴ酸、グリコール酸、硼酸、等一種類以上を溶解した水溶液で行う。 The anodizing treatment is carried out in an acidic electrolytic bath, and phosphoric acid, sulfuric acid, oxalic acid, chromic acid, sulfasalicylic acid, pyrophosphoric acid, sulfamic acid, phosphomolybdic acid, malonic acid, maleic acid, succinic acid, tartaric acid, phthalic acid, citric acid An aqueous solution in which one or more of acid, itaconic acid, malic acid, glycolic acid, boric acid and the like are dissolved is used.
前記アルマイト皮膜形成後に、形成された微細孔の孔径を酸浸漬によるポアワイドニング処理により拡大せしめてもよい。 After forming the alumite film, the pore diameter of the formed micropores may be enlarged by pore widening treatment by acid immersion.
なお、図４は陽極酸化後の貫通ピット表面にアルマイト皮膜を有するアルミニウム基板の断面のＳＥＭ写真であり、図５はアルマイト皮膜を有するアルミニウム基板の貫通ピット付近の断面のＳＥＭ写真であり、図６はその模式図を表し、４はアルミニウム基板の貫通ピット３の表面に形成されたアルマイト皮膜、５はそのアルマイト皮膜４上に多数形成された微細孔である。
4 is a SEM photograph of a cross section of an aluminum substrate having an alumite film on the surface of the through pit after anodization, and FIG. 5 is a SEM photograph of a cross section in the vicinity of the through pit of the aluminum substrate having an alumite film. Represents a schematic diagram thereof, wherein 4 is an alumite film formed on the surface of the through-
前記水和処理は、前記アルミニウム基板の表面積を増大するためのもので、水和処理液は特に限定されず、例えば、１０〜１００℃の水または温水、熱水によって行なわれる。また、反応促進剤として、トリエタノールアミン、アンモニア、ケイ酸ナトリウムなどを添加してもよい。 The hydration treatment is for increasing the surface area of the aluminum substrate, and the hydration treatment liquid is not particularly limited. For example, the hydration treatment is performed with water of 10 to 100 ° C., hot water or hot water. Moreover, you may add triethanolamine, ammonia, sodium silicate, etc. as a reaction accelerator.
なお、図７は水和皮膜を有するアルミニウム基板の貫通ピット付近の断面のＳＥＭ写真を表し、６はアルミニウム基板の貫通ピット３の表面に形成された水和皮膜であり、前記水和皮膜６には微細孔が多数形成されている。
7 shows an SEM photograph of a cross section in the vicinity of the through pit of the aluminum substrate having a hydrated film.
前記焼成処理は、前記水和皮膜中の水分を脱水すると共にアルミナ層とすることによりアルミニウム基板の表面積を拡大するもので、焼成温度が３００℃未満であるとアルミナの出来方が不十分であり、５５０℃より高い温度では基体が損傷したり、表面積が低下するので好ましくないため、３００〜５５０℃で５分〜３時間行う。 The firing treatment expands the surface area of the aluminum substrate by dehydrating moisture in the hydrated film and forming an alumina layer. If the firing temperature is less than 300 ° C., the production of alumina is insufficient. Since the substrate is damaged at a temperature higher than 550 ° C. or the surface area is reduced, it is not preferable.
前記触媒担体に担持される触媒活性を有する金属は、特に限定されず、例えば、触媒活性を有する公知の金属、合金または金属化合物が挙げられる。例えば、白金系金属、白金系金属の化合物、パラジウム、ロジウム、インジウム、銀、レニウム、錫、セリウム、ジルコニウム、金、金合金、マンガン、鉄、亜鉛、銅、ニッケル、ニッケル合金、コバルト、コバルト合金、ルテニウム等の中から選択することが望ましい。また、これらの触媒物質を組み合わせてもよい。 The metal having catalytic activity supported on the catalyst carrier is not particularly limited, and examples thereof include known metals, alloys or metal compounds having catalytic activity. For example, platinum metal, platinum metal compound, palladium, rhodium, indium, silver, rhenium, tin, cerium, zirconium, gold, gold alloy, manganese, iron, zinc, copper, nickel, nickel alloy, cobalt, cobalt alloy It is desirable to select from among ruthenium and the like. Moreover, you may combine these catalyst substances.
前記触媒担体に触媒を担持する方法は、例えば、触媒活性を有する金属を前記皮膜に吸着させ、更に触媒反応に用いられる物質と接触しても脱着しない程度固定させる。 In the method of supporting the catalyst on the catalyst carrier, for example, a metal having catalytic activity is adsorbed on the film, and is fixed to such an extent that it does not desorb even when contacted with a substance used in the catalytic reaction.
具体的には、例えば、含浸法、電着法、イオン交換法、共沈法、沈着法、水熱合成法、気相合成法等の公知の方法を用いる。特に、触媒活性を有する金属イオンを含有する水溶液に浸漬させる含浸法が好ましい。含浸法に用いられる水溶液は、触媒活性を有する金属を含む、塩化物、臭化物、アンモニウム化合物、シアン化物、アルカリ金属塩、これらの複合化合物を用いて調整することができる。 Specifically, for example, known methods such as an impregnation method, an electrodeposition method, an ion exchange method, a coprecipitation method, a deposition method, a hydrothermal synthesis method, and a gas phase synthesis method are used. In particular, an impregnation method of immersing in an aqueous solution containing metal ions having catalytic activity is preferable. The aqueous solution used for the impregnation method can be prepared by using a chloride, bromide, ammonium compound, cyanide, alkali metal salt, or a complex compound thereof containing a metal having catalytic activity.
また、触媒活性を有する金属を固着させるために焼成処理を行うこともできる。 In addition, a calcination treatment can be performed to fix a metal having catalytic activity.
また、必要に応じて、前記触媒体のアルミニウム基板面に対して、垂直方向から前記触媒体により分解される物質を供給せしめ、前記物質を前記貫通ピット内に流通せしめて触媒反応せしめる。 Further, if necessary, a substance decomposed by the catalyst body is supplied from the vertical direction to the aluminum substrate surface of the catalyst body, and the substance is allowed to flow through the through pits to cause a catalytic reaction.
なお、前記垂直方向から物質を供給する場合の物質流量範囲は、例えば、貫通ピット１本当たり、４．７×１０-14ｍｏｌ／ｓ〜１．８×１０-19ｍｏｌ／ｓとする。また、この場合の圧力損失は、特に問題のある範囲ではない。 The material flow rate range when the material is supplied from the vertical direction is, for example, 4.7 × 10 −14 mol / s to 1.8 × 10 −19 mol / s per penetrating pit. Further, the pressure loss in this case is not in a particularly problematic range.
本発明においては、アルミニウム基板の表面積を増大することができ、触媒担持量を増やす事ができるので、触媒活性に優れる。また、貫通ピット内に物質を流通できるので、高効率な触媒活性を得ることができる。 In the present invention, since the surface area of the aluminum substrate can be increased and the amount of catalyst supported can be increased, the catalyst activity is excellent. Moreover, since a substance can be distributed in the through pits, highly efficient catalytic activity can be obtained.
本発明の触媒担体は、アルミニウム基板と前記アルミニウム基板を貫通する複数の貫通ピットとからなる。 The catalyst carrier of the present invention comprises an aluminum substrate and a plurality of through pits that penetrate the aluminum substrate.
また、本発明の触媒担体は、前記アルミニウム基板表面及び貫通ピット表面に、陽極酸化処理による皮膜が形成されていることを特徴とする。 The catalyst carrier of the present invention is characterized in that a film formed by anodization is formed on the surface of the aluminum substrate and the surface of the through pits.
また、本発明の触媒担体は、前記アルミニウム基板表面及び貫通ピット表面に、陽極酸化処理をした後に水和処理をした皮膜が形成されていることを特徴とする。 The catalyst carrier of the present invention is characterized in that a film that has been hydrated after anodizing is formed on the surface of the aluminum substrate and the surface of the through pits.
また、本発明の触媒担体は、前記アルミニウム基板表面及び貫通ピット表面に、陽極酸化処理をした後に水和処理をし、その後に焼成した皮膜が形成されていることを特徴とする。 Further, the catalyst carrier of the present invention is characterized in that a film is formed on the surface of the aluminum substrate and the surface of the through pits by anodizing and then hydrating and then firing.
また、本発明の触媒担体は、前記アルミニウム基板表面及び貫通ピット表面に、水和処理による皮膜が形成されていることを特徴する。 Moreover, the catalyst carrier of the present invention is characterized in that a film by hydration treatment is formed on the surface of the aluminum substrate and the surface of the through pits.
また、本発明の触媒担体は、前記アルミニウム基板表面及び貫通ピット表面に、水和処理をした後に焼成した皮膜が形成されていることを特徴する。 Further, the catalyst carrier of the present invention is characterized in that a film baked after hydration is formed on the surface of the aluminum substrate and the surface of the through pits.
本発明の触媒担体の製造方法は、アルミニウム基板に複数の貫通ピットを形成せしめる第一の工程と、前記アルミニウム基板を陽極酸化処理する第二の工程ととよりなることを特徴とする。 The method for producing a catalyst carrier according to the present invention includes a first step of forming a plurality of through pits on an aluminum substrate and a second step of anodizing the aluminum substrate.
本発明の触媒担体の製造方法は、アルミニウム基板に複数の貫通ピットを形成せしめる第一の工程と、前記アルミニウム基板を陽極酸化処理する第二の工程と、前記アルミニウム基板を水和処理する第三の工程と、前記アルミニウム基板を焼成する第四の工程とよりなることを特徴とする。 The method for producing a catalyst carrier according to the present invention includes a first step of forming a plurality of through pits on an aluminum substrate, a second step of anodizing the aluminum substrate, and a third step of hydrating the aluminum substrate. And a fourth step of firing the aluminum substrate.
本発明の触媒担体の製造方法は、アルミニウム基板に複数の貫通ピットを形成せしめる第一の工程と、前記アルミニウム基板を水和処理する第二の工程と、前記アルミニウム基板を焼成する第三の工程とよりなることを特徴とする。 The method for producing a catalyst carrier according to the present invention includes a first step of forming a plurality of through pits on an aluminum substrate, a second step of hydrating the aluminum substrate, and a third step of firing the aluminum substrate. It is characterized by comprising.
本発明の触媒体は、前記触媒担体に、触媒を担持せしめる。 In the catalyst body of the present invention, the catalyst is supported on the catalyst carrier.
また、本発明の触媒体は、触媒体により分解される物質の供給方向に対して、前記アルミニウム基板面が垂直になるよう前記アルミニウム基板を設置せしめる手段を更に有することを特徴とする。 In addition, the catalyst body of the present invention further includes means for installing the aluminum substrate so that the aluminum substrate surface is perpendicular to the supply direction of the substance to be decomposed by the catalyst body.
本発明の物質の分解方法は、前記触媒体のアルミニウム基板面に対して、垂直方向から前記触媒体により分解される物質を供給せしめる工程を更に有することを特徴とする。 The method for decomposing a substance of the present invention further includes a step of supplying a substance to be decomposed by the catalyst body from a vertical direction to the aluminum substrate surface of the catalyst body.
前記アルミニウム基板の厚さが５〜１０００μｍであることを特徴とする。 The aluminum substrate has a thickness of 5 to 1000 μm.
前記貫通ピットの最小のピット径が０．１μｍ以上であることを特徴とする。 The minimum pit diameter of the through pits is 0.1 μm or more.
前記貫通ピットの平均ピット径が０．３〜５μｍであることを特徴とする。 An average pit diameter of the through pits is 0.3 to 5 μm.
前記貫通ピットはエッチング処理によって形成されたことを特徴とする。 The through pits are formed by an etching process.
以下、本発明を実施例によって更に詳述するが、本発明はこれによって限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in full detail, this invention is not limited by this.
（比較例１）
アルミニウム箔に陽極酸化皮膜を浴温２０℃蓚酸濃度７ｗｔ％の水溶液中で直流４０Ｖにより１２時間陽極酸化を行った。その結果、陽極酸化皮膜厚さが片面約５０μｍ、微細孔径が３０ｎｍ程度である皮膜が生成していることを確認した。その後、この陽極酸化処理したアルミニウム箔を８０℃のイオン交換水中にて１時間水和処理を行った。そのアルミニウム箔を銅、亜鉛イオンの溶解する液に浸漬し、銅、亜鉛を担持して触媒体を得た。
この場合の触媒担持量は、５ｇ／ｍ2であった。
(Comparative Example 1)
The anodized film was anodized on an aluminum foil in an aqueous solution having a bath temperature of 20 ° C. and an oxalic acid concentration of 7 wt% by DC 40 V for 12 hours. As a result, it was confirmed that a film having an anodized film thickness of about 50 μm on one side and a fine pore diameter of about 30 nm was formed. Thereafter, the anodized aluminum foil was hydrated in ion exchange water at 80 ° C. for 1 hour. The aluminum foil was immersed in a solution in which copper and zinc ions were dissolved, and copper and zinc were supported to obtain a catalyst body.
In this case, the amount of catalyst supported was 5 g / m 2 .
（比較例２）
（１，０，０）面占有率が９９％以上で、アルミニウム純度が９９．９９％以上の１００μｍ厚のアルミニウム箔をエッチング浴温８０℃、５ｗｔ％塩酸＋２０ｗｔ％硫酸の浴で電流密度０．２０Ａ／ｃｍ2で５０秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．１０Ａ／ｃｍ2で５００秒間、いずれも直流で電解した。その場合のエッチング深さは、片面約３０μｍ、ピット径の平均は１．０μｍのアルミニウム箔を得た。その後、このエッチング処理したアルミニウム箔を浴温２０℃蓚酸濃度７ｗｔ％の水溶液中で直流４０Ｖにより２時間陽極酸化を行った。その後同浴に８時間浸漬し、孔径拡大処理を行なった。その結果、陽極酸化皮膜厚さが約０．８μｍ、微細孔径が３０ｎｍ程度である皮膜が生成していることを確認した。その後、このエッチング処理したアルミニウム箔を８０℃のイオン交換水中にて１時間水和処理を行った。このアルミニウム箔を銅、亜鉛イオンの溶解する液に浸漬し、銅、亜鉛を担持して触媒体を得た。
この場合の触媒担持量は、５ｇ／ｍ2であった。
(Comparative Example 2)
A 100 μm-thick aluminum foil having a (1,0,0) plane occupancy of 99% or more and an aluminum purity of 99.99% or more was etched at a current density of 0.00 in an etching bath temperature of 80 ° C., 5 wt% hydrochloric acid + 20 wt% sulfuric acid. Electrolysis was performed at 20 A / cm 2 for 50 seconds, and then electrolysis was performed with direct current in an etching bath temperature of 80 ° C. and a 5 wt% nitric acid bath at a current density of 0.10 A / cm 2 for 500 seconds. In this case, an aluminum foil having an etching depth of about 30 μm on one side and an average pit diameter of 1.0 μm was obtained. Thereafter, the etched aluminum foil was anodized for 2 hours at a direct current of 40 V in an aqueous solution having a bath temperature of 20 ° C. and an oxalic acid concentration of 7 wt%. Thereafter, it was immersed in the same bath for 8 hours to carry out a pore size expansion treatment. As a result, it was confirmed that a film having an anodized film thickness of about 0.8 μm and a fine pore diameter of about 30 nm was formed. Then, this etched aluminum foil was hydrated in ion exchange water at 80 ° C. for 1 hour. This aluminum foil was immersed in a solution in which copper and zinc ions were dissolved, and copper and zinc were supported to obtain a catalyst body.
In this case, the amount of catalyst supported was 5 g / m 2 .
（１，０，０）面占有率が９９％以上で、アルミニウム純度が９９．９９％以上の１００μｍ厚のアルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．２０Ａ／ｃｍ2で１００秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．１０Ａ／ｃｍ2で５００秒間、いずれも直流で電解した。その場合のエッチングピットは、反対面に伸びて貫通しており、貫通ピットの占有率は９５％であり、ピット径の平均は１．５μｍであるアルミニウム箔を得た。その後、このエッチング処理したアルミニウム箔を浴温２０℃蓚酸濃度７ｗｔ％の水溶液中で直流４０Ｖにより２時間陽極酸化を行った。その後同浴に８時間浸漬し、孔径拡大処理を行なった。その結果、陽極酸化皮膜厚さが片面約０．８μｍ、微細孔径が３０ｎｍ程度である皮膜が生成していることを確認した。その後、エッチング処理したアルミニウム箔を８０℃のイオン交換水中にて１時間水和処理を行った。このアルミニウム箔を銅、亜鉛イオンの溶解する液に浸漬し、銅、亜鉛を担持して触媒体を得た。
この場合の触媒担持量は、５ｇ／ｍ2であった。
A 100 μm-thick aluminum foil having a (1,0,0) plane occupancy of 99% or higher and an aluminum purity of 99.99% or higher in an etching bath temperature of 80 ° C. and a 10 wt% hydrochloric acid bath has a current density of 0.20 A / cm. 2 in electrolysis for 100 seconds, then, the etching bath temperature 80 ° C., 500 seconds at a current density of 0.10 a / cm 2 at 5 wt% nitric acid bath were both electrolysis with direct current. The etching pits in that case extended to the opposite surface and penetrated, and the occupying ratio of the through pits was 95%, and an aluminum foil having an average pit diameter of 1.5 μm was obtained. Thereafter, the etched aluminum foil was anodized for 2 hours at a direct current of 40 V in an aqueous solution having a bath temperature of 20 ° C. and an oxalic acid concentration of 7 wt%. Thereafter, it was immersed in the same bath for 8 hours to carry out a pore size expansion treatment. As a result, it was confirmed that a film having an anodic oxide film thickness of about 0.8 μm on one side and a fine pore diameter of about 30 nm was formed. Thereafter, the etched aluminum foil was hydrated in ion exchange water at 80 ° C. for 1 hour. This aluminum foil was immersed in a solution in which copper and zinc ions were dissolved, and copper and zinc were supported to obtain a catalyst body.
In this case, the amount of catalyst supported was 5 g / m 2 .
なお、貫通ピットの占有率とは、アルミニウム基板に形成された貫通ピット及び非貫通ピットの全体数に対する、貫通ピット数の割合を示し、「貫通ピットの占有率（％）＝（貫通しているピットの本数）／（全てのピットの本数）×１００」で表される。 The through-pit occupancy ratio is the ratio of the number of through-pits to the total number of through-pits and non-through-pits formed on the aluminum substrate. The number of pits) / (the number of all pits) × 100 ”.
実施例１と同じである。 Same as Example 1.
実施例１において、（１，０，０）面占有率を８０％にして、その後の処理を同様に行った。その結果、形成された貫通ピットの占有率が５０％程度で、ピット径の平均が２．０μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、２．５ｇ／ｍ2であった。
In Example 1, the (1,0,0) plane occupancy was set to 80%, and the subsequent processing was performed in the same manner. As a result, an aluminum foil having an occupation ratio of the formed through pits of about 50% and an average pit diameter of 2.0 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the amount of catalyst supported was 2.5 g / m 2 .
実施例１において、（１，０，０）面占有率を９５％にして、その後の処理を同様に行った。その結果、形成された貫通ピットの占有率が７０％程度で、ピット径の平均が１．５μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、３．０ｇ／ｍ2であった。
In Example 1, the (1,0,0) plane occupancy was set to 95%, and the subsequent processing was performed in the same manner. As a result, an aluminum foil having an occupation ratio of the formed through pits of about 70% and an average pit diameter of 1.5 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the amount of catalyst supported was 3.0 g / m 2 .
実施例１において、アルミニウム純度を９９．０％にし、（１，０，０）面占有率を４５％にして、その後の処理を同様に行った。その結果、形成された貫通ピットの占有率が３０％程度で、ピット径の平均が２．５μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、２．０ｇ／ｍ2であった。
In Example 1, the aluminum purity was set to 99.0%, the (1,0,0) plane occupancy was set to 45%, and the subsequent processing was similarly performed. As a result, an aluminum foil having an occupation ratio of the formed through pits of about 30% and an average pit diameter of 2.5 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the amount of catalyst supported was 2.0 g / m 2 .
実施例１において、箔厚を５μｍ厚にして、アルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．１０Ａ／ｃｍ2で２０秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．１０Ａ／ｃｍ2で５０秒間、いずれも直流で電解した。その後の処理を同様に行った。その結果、形成された貫通ピットの占有率が９５％程度で、ピット径の平均が１．５μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、０．３ｇ／ｍ2であった。
In Example 1, the foil thickness was 5 μm, and the aluminum foil was electrolyzed for 20 seconds at a current density of 0.10 A / cm 2 in an etching bath temperature of 80 ° C. and a 10 wt% hydrochloric acid bath, and then the etching bath temperature of 80 ° C. Both were electrolyzed by direct current in a 5 wt% nitric acid bath at a current density of 0.10 A / cm 2 for 50 seconds. Subsequent processing was similarly performed. As a result, an aluminum foil having an occupation ratio of the formed through pits of about 95% and an average pit diameter of 1.5 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the catalyst loading was 0.3 g / m 2 .
実施例１において、箔厚を７０μｍ厚にして、アルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．２０Ａ／ｃｍ2で７５秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．１０Ａ／ｃｍ2で５００秒間、いずれも直流で電解した。その後の処理を同様に行った。その結果、形成された貫通ピットの占有率が９５％程度で、ピット径の平均が１．５μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、４ｇ／ｍ2であった。
In Example 1, the foil thickness was set to 70 μm, and the aluminum foil was electrolyzed with an etching bath temperature of 80 ° C. and a 10 wt% hydrochloric acid bath at a current density of 0.20 A / cm 2 for 75 seconds, and then the etching bath temperature of 80 ° C. Both were electrolyzed with a direct current in a 5 wt% nitric acid bath at a current density of 0.10 A / cm 2 for 500 seconds. Subsequent processing was similarly performed. As a result, an aluminum foil having an occupation ratio of the formed through pits of about 95% and an average pit diameter of 1.5 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the amount of catalyst supported was 4 g / m 2 .
実施例１において、箔厚を１８０μｍ厚にして、アルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．２０Ａ／ｃｍ2で１５０秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．１０Ａ／ｃｍ2で７５０秒間、いずれも直流で電解した。その後の処理を同様に行った。その結果、形成された貫通ピットの占有率が９５％程度で、ピット径の平均が１．５μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、８ｇ／ｍ2であった。
In Example 1, the foil thickness was 180 μm, and the aluminum foil was electrolyzed for 150 seconds at a current density of 0.20 A / cm 2 with an etching bath temperature of 80 ° C. and a 10 wt% hydrochloric acid bath, and then the etching bath temperature of 80 ° C. Both were electrolyzed with direct current in a 5 wt% nitric acid bath at a current density of 0.10 A / cm 2 for 750 seconds. Subsequent processing was similarly performed. As a result, an aluminum foil having an occupation ratio of the formed through pits of about 95% and an average pit diameter of 1.5 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the amount of catalyst supported was 8 g / m 2 .
実施例１において、箔厚を１０００μｍ厚にして、アルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．６０Ａ／ｃｍ2で５００秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．２０Ａ／ｃｍ2で１０００秒間、いずれも直流で電解した。その後の処理を同様に行った。その結果、形成された貫通ピットの占有率が９５％程度で、ピット径の平均が１．５μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、５０ｇ／ｍ2であった。
In Example 1, the foil thickness was 1000 μm, and the aluminum foil was electrolyzed in an etching bath temperature of 80 ° C. with a 10 wt% hydrochloric acid bath at a current density of 0.60 A / cm 2 for 500 seconds, and then the etching bath temperature of 80 ° C. Both were electrolyzed with direct current in a 5 wt% nitric acid bath at a current density of 0.20 A / cm 2 for 1000 seconds. Subsequent processing was similarly performed. As a result, an aluminum foil having an occupation ratio of the formed through pits of about 95% and an average pit diameter of 1.5 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the amount of catalyst supported was 50 g / m 2 .
実施例１において、アルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．２０Ａ／ｃｍ2で１００秒間電解した。その場合のエッチングピットは、反対面に伸び貫通しており、貫通ピットの占有率は９５％であり、最小ピット径は０．１μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、４ｇ／ｍ2であった。
In Example 1, an aluminum foil was electrolyzed for 100 seconds at a current density of 0.20 A / cm 2 in an etching bath temperature of 80 ° C. and a 10 wt% hydrochloric acid bath. In this case, the etching pits extended and penetrated to the opposite surface, and the occupation ratio of the through pits was 95%, and an aluminum foil having a minimum pit diameter of 0.1 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the amount of catalyst supported was 4 g / m 2 .
実施例１において、アルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．２０Ａ／ｃｍ2で１００秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．１０Ａ／ｃｍ2で１００秒間、いずれも直流で電解した。その場合のエッチングピットは、反対面に伸び貫通しており、貫通ピットの占有率は９５％であり、最小ピット径は０．３μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、５ｇ／ｍ2であった。
In Example 1, an aluminum foil was electrolyzed for 100 seconds at a current density of 0.20 A / cm 2 in an etching bath temperature of 80 ° C. and a 10 wt% hydrochloric acid bath, and then in an etching bath temperature of 80 ° C. and a 5 wt% nitric acid bath. Both were electrolyzed with direct current at 0.10 A / cm 2 for 100 seconds. In this case, the etching pits extended and penetrated to the opposite surface, and the occupation ratio of the through pits was 95%, and an aluminum foil having a minimum pit diameter of 0.3 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the amount of catalyst supported was 5 g / m 2 .
実施例１において、アルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．２０Ａ／ｃｍ2で１００秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．１０Ａ／ｃｍ2で１０００秒間、いずれも直流で電解した。その場合のエッチングピットは、反対面に伸び貫通しており、貫通ピットの占有率は９５％であり、ピット径の平均は３μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、７ｇ／ｍ2であった。
In Example 1, an aluminum foil was electrolyzed for 100 seconds at a current density of 0.20 A / cm 2 in an etching bath temperature of 80 ° C. and a 10 wt% hydrochloric acid bath, and then in an etching bath temperature of 80 ° C. and a 5 wt% nitric acid bath. Both were electrolyzed with direct current at 0.10 A / cm 2 for 1000 seconds. In this case, the etching pits extended and penetrated to the opposite surface, and the occupation ratio of the through pits was 95%, and an aluminum foil having an average pit diameter of 3 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the amount of catalyst supported was 7 g / m 2 .
実施例１において、アルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．２０Ａ／ｃｍ2で１００秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．１０Ａ／ｃｍ2で３０００秒間、いずれも直流で電解した。その場合のエッチングピットは、反対面に伸び貫通しており、貫通ピットの占有率は９５％であり、ピット径の平均は５μｍであるアルミニウム箔を得た。その後、陽極酸化処理、水和処理、触媒担持処理については、実施例１と同様に行い、触媒体を得た。
この場合の触媒担持量は、６ｇ／ｍ2であった。
In Example 1, an aluminum foil was electrolyzed for 100 seconds at a current density of 0.20 A / cm 2 in an etching bath temperature of 80 ° C. and a 10 wt% hydrochloric acid bath, and then in an etching bath temperature of 80 ° C. and a 5 wt% nitric acid bath. Both were electrolyzed with direct current at 0.10 A / cm 2 for 3000 seconds. In this case, the etching pits extended and penetrated to the opposite surface, and the occupation ratio of the through pits was 95%, and an average pit diameter of 5 μm was obtained. Thereafter, the anodic oxidation treatment, hydration treatment, and catalyst support treatment were performed in the same manner as in Example 1 to obtain a catalyst body.
In this case, the catalyst loading was 6 g / m 2 .
実施例１において、アルミニウム箔をエッチング浴温８０℃、１０ｗｔ％塩酸の浴で電流密度０．２０Ａ／ｃｍ2で１００秒間電解し、次に、エッチング浴温８０℃、５ｗｔ％硝酸浴で電流密度０．１０Ａ／ｃｍ2で５００秒間、いずれも直流で電解した。その場合のエッチングピットは、反対面に伸び貫通しており、貫通ピットの占有率は９５％であり、ピット径の平均は１．５μｍであるアルミニウム箔を得た。その後、このエッチング処理したアルミニウム箔を８０℃のイオン交換水中にて１時間水和処理を行った。このアルミニウム箔を銅、亜鉛イオンの溶解する液に浸漬し、銅、亜鉛を担持して触媒体を得た。
この場合の触媒担持量は、４ｇ／ｍ2であった。
In Example 1, an aluminum foil was electrolyzed for 100 seconds at a current density of 0.20 A / cm 2 in an etching bath temperature of 80 ° C. and a 10 wt% hydrochloric acid bath, and then in an etching bath temperature of 80 ° C. and a 5 wt% nitric acid bath. Both were electrolyzed with direct current at 0.10 A / cm 2 for 500 seconds. In this case, the etching pits extended and penetrated to the opposite surface, and the occupation ratio of the through pits was 95%, and an aluminum foil having an average pit diameter of 1.5 μm was obtained. Then, this etched aluminum foil was hydrated in ion exchange water at 80 ° C. for 1 hour. This aluminum foil was immersed in a solution in which copper and zinc ions were dissolved, and copper and zinc were supported to obtain a catalyst body.
In this case, the amount of catalyst supported was 4 g / m 2 .
前記比較例、実施例のデータを表１に示す。 Table 1 shows the data of the comparative examples and examples.
本発明は、非常に高比表面積であり、厚さが薄いため、小型素子への応用が期待される。そこで、今後伸張が期待される携帯電子機器の燃料電池用小型改質器への応用を視野に入れ、メタノールの水蒸気改質を行い、比較例及び実施例のメタノール分解率の評価を行った。また、比較例及び実施例２については、物質の供給を箔に対して並行に行い、その他については、箔の貫通ピットに物質を流通させ反応を行った。 Since the present invention has a very high specific surface area and a small thickness, application to a small element is expected. In view of the application of portable electronic devices, which are expected to grow in the future, to small reformers for fuel cells, methanol steam reforming was performed, and the methanol decomposition rates of comparative examples and examples were evaluated. Moreover, about the comparative example and Example 2, supply of the substance was performed in parallel with respect to foil, and it reacted by distribute | circulating a substance to the penetration pit of foil about others.
その分解測定データを表２に示す。 The decomposition measurement data is shown in Table 2.
その結果、本発明の貫通ピットを有するエッチング箔を用いた触媒体は優れた性能であることが判明した。 As a result, it was found that the catalyst body using the etching foil having through pits of the present invention has excellent performance.
１ アルミニウム基板
２ 浴
３ 貫通ピット
４ アルマイト皮膜
５ 微細孔
６ 水和皮膜
DESCRIPTION OF
Claims (20)
前記アルミニウム基板を陽極酸化処理する第二の工程と
とよりなることを特徴とする触媒担体の製造方法。 A first step of forming a plurality of through pits penetrating the aluminum substrate in the aluminum substrate;
And a second step of anodizing the aluminum substrate. A method for producing a catalyst carrier.
前記アルミニウム基板を陽極酸化処理する第二の工程と、
前記アルミニウム基板を水和処理する第三の工程と、
前記アルミニウム基板を焼成する第四の工程と
よりなることを特徴とする触媒担体の製造方法。 A first step of forming a plurality of through pits penetrating the aluminum substrate in the aluminum substrate;
A second step of anodizing the aluminum substrate;
A third step of hydrating the aluminum substrate;
A method for producing a catalyst carrier, comprising: a fourth step of firing the aluminum substrate.
前記アルミニウム基板を水和処理する第二の工程と、
前記アルミニウム基板を焼成する第三の工程と
よりなることを特徴とする触媒担体の製造方法。 A first step of forming a plurality of through pits penetrating the aluminum substrate in the aluminum substrate;
A second step of hydrating the aluminum substrate;
A method for producing a catalyst carrier, comprising: a third step of firing the aluminum substrate.
Priority Applications (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014018711A (en) * | 2012-07-13 | 2014-02-03 | Hitachi Aic Inc | Catalytic member |
| EP3489974A4 (en) * | 2016-09-16 | 2019-09-25 | Japan Capacitor Industrial Co., Ltd. | Electrode member for electrolytic capacitor and electrolytic capacitor |
| WO2020065956A1 (en) * | 2018-09-28 | 2020-04-02 | 日立化成株式会社 | Steam reforming method, steam reforming member, and steam reformer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014018711A (en) * | 2012-07-13 | 2014-02-03 | Hitachi Aic Inc | Catalytic member |
| EP3489974A4 (en) * | 2016-09-16 | 2019-09-25 | Japan Capacitor Industrial Co., Ltd. | Electrode member for electrolytic capacitor and electrolytic capacitor |
| US10957491B2 (en) | 2016-09-16 | 2021-03-23 | Japan Capacitor Industrial Co., Ltd. | Electrolytic capacitor-specific electrode member and electrolytic capacitor |
| WO2020065956A1 (en) * | 2018-09-28 | 2020-04-02 | 日立化成株式会社 | Steam reforming method, steam reforming member, and steam reformer |
| WO2020066282A1 (en) * | 2018-09-28 | 2020-04-02 | 日立化成株式会社 | Processing method, processing member, production method therefor, and processing apparatus |
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| JP5726466B2 (en) | 2015-06-03 |
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