JP2008280184A - Composite of ultrafine particle of cerium-containing mesoporous silica and noble metal, production method of the composite, oxidative exclusion method of minute amount of carbon monoxide by using the complex as catalyst, and synthetic method of ketone by oxidative dehydrogenation of alcohol - Google Patents
Composite of ultrafine particle of cerium-containing mesoporous silica and noble metal, production method of the composite, oxidative exclusion method of minute amount of carbon monoxide by using the complex as catalyst, and synthetic method of ketone by oxidative dehydrogenation of alcohol Download PDFInfo
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- JP2008280184A JP2008280184A JP2007122917A JP2007122917A JP2008280184A JP 2008280184 A JP2008280184 A JP 2008280184A JP 2007122917 A JP2007122917 A JP 2007122917A JP 2007122917 A JP2007122917 A JP 2007122917A JP 2008280184 A JP2008280184 A JP 2008280184A
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- mesoporous silica
- catalyst
- carbon monoxide
- composite
- particles
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 35
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 30
- 150000002576 ketones Chemical class 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 8
- 239000011882 ultra-fine particle Substances 0.000 title claims description 19
- 230000001590 oxidative effect Effects 0.000 title claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 title description 5
- 230000007717 exclusion Effects 0.000 title 1
- 238000010189 synthetic method Methods 0.000 title 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052737 gold Inorganic materials 0.000 claims abstract description 50
- 239000010931 gold Substances 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- -1 hydroxide ions Chemical class 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000036541 health Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 5
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 150000003333 secondary alcohols Chemical class 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910003471 inorganic composite material Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000000391 smoking effect Effects 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 206010019233 Headaches Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 231100000869 headache Toxicity 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010003210 Arteriosclerosis Diseases 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000006793 arrhythmia Effects 0.000 description 1
- 206010003119 arrhythmia Diseases 0.000 description 1
- 208000011775 arteriosclerosis disease Diseases 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000002612 cardiopulmonary effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
Description
本発明は、金属、特に好ましくは貴金属の超微粒子と無機酸化物担体からなる複合構造体の製造技術と、その複合構造体の触媒反応への応用技術に関するものである。特に、貴金属として、金を用いた場合の、生活空間の快適化、無害化技術、或いは水素を用いる燃料電池の高性能技術である、微量一酸化炭素の酸化除去に関し、特に、そのための、金の超微粒子を用いた高性能触媒に関するものである。さらに、有機反応で重要な反応のひとつと位置づけられる２級アルコール類のケトン類への酸化反応に関するものである。 The present invention relates to a technique for producing a composite structure composed of ultrafine particles of a metal, particularly preferably a noble metal, and an inorganic oxide support, and a technique for applying the composite structure to a catalytic reaction. In particular, when gold is used as a precious metal, it is related to the oxidative removal of trace amounts of carbon monoxide, which is a technology for making living space comfortable and detoxifying, or a high-performance technology for a fuel cell using hydrogen. The present invention relates to a high-performance catalyst using ultrafine particles. Further, the present invention relates to an oxidation reaction of secondary alcohols to ketones, which is one of the important reactions in organic reactions.
金属、特に貴金属の超微粒子は近年注目を集めており、種々の調製法が提案、開発されている。金属は微粒子化すればするほど総金属量に対して表面に露出する原子数が増加し、同じ金属量でありながら、活性サイトが増大する効果や、電子状態がバルクの状態から変化し新たな機能を示す効果が得られたりする(非特許文献１)。したがって、貴金属の超微粒子を効率的に製造する技術は重要性が高い。
また、貴金属の超微粒子は単独では不安定なため、凝集による粒子サイズの増大などにより超微粒子としての機能を失う場合がある。それを防ぐために高比表面積の担体の表面に固定化する手法により安定した性能を得ることが出来るが、均一な超微粒子の調製法は比較的困難であり、重要技術課題となっている。以下、これまでに一般的に知られている数例を述べる。
In recent years, ultrafine particles of metals, particularly noble metals, have attracted attention, and various preparation methods have been proposed and developed. As the metal becomes finer, the number of atoms exposed on the surface increases with respect to the total amount of metal, and while the same amount of metal, the effect of increasing active sites and the electronic state changes from the bulk state to a new one. The effect which shows a function is acquired (nonpatent literature 1). Therefore, a technique for efficiently producing ultrafine particles of noble metal is highly important.
In addition, since noble metal ultrafine particles are unstable alone, the function as ultrafine particles may be lost due to an increase in particle size due to aggregation. In order to prevent this, a stable performance can be obtained by a method of immobilizing on the surface of a carrier having a high specific surface area. However, it is relatively difficult to prepare uniform ultrafine particles, which is an important technical problem. Hereinafter, several examples generally known so far will be described.
白金やパラジウムの超微粒子を酸化チタン粉末やチタン含有メソポーラスシリカと複合化させる際に紫外線を照射することでチタンを活性化させ、活性化されたチタンサイト上に選択的に白金やパラジウムの超微粒子が生成する手法が報告されている。この複合体は、透過電子顕微鏡測定において、ほぼ均一な粒子の生成を確認して、また、一酸化炭素の酸化反応や過酸化水素の製造においても顕著な活性向上を果たしている(非特許文献２など)。
また、金を酸化チタン粉末又はチタン含有メソポーラスシリカ上に担持する際に金の前駆体である塩化金酸の溶液をアルカリ溶液で中和しｐＨを調節し、酸化チタンの表面電位と整合性を取り、電気的親和力で表面に析出させる手法が発表されており、一酸化炭素の酸化除去やプロピレンオキサイドの合成に効果的な触媒となっている(非特許文献３など)。
さらに、ハイドロキシアパタイト上に均一に担持されたルテニウムやパラジウムの超微粒子は、前駆体を表面イオンと交換するイオン交換法に近い形で担持されていて、還元される事により得られる。この複合体は、アルコールの酸化反応に顕著な活性を示すことが報告されている(非特許文献４など)。
When the ultrafine platinum or palladium particles are combined with titanium oxide powder or titanium-containing mesoporous silica, the titanium is activated by irradiating with ultraviolet rays, and the ultrafine platinum or palladium particles are selectively deposited on the activated titanium sites. The method of generating is reported. This composite confirmed the generation of substantially uniform particles in the transmission electron microscope measurement, and also achieved a remarkable improvement in activity in the oxidation reaction of carbon monoxide and the production of hydrogen peroxide (Non-patent Document 2). Such).
In addition, when supporting gold on titanium oxide powder or titanium-containing mesoporous silica, the solution of gold chloroauric acid, which is a precursor of gold, is neutralized with an alkaline solution to adjust the pH, thereby matching the surface potential of titanium oxide. And a method of depositing on the surface with an electrical affinity has been announced, and has become an effective catalyst for the oxidation removal of carbon monoxide and the synthesis of propylene oxide (Non-patent Document 3, etc.).
Furthermore, the ultrafine particles of ruthenium and palladium uniformly supported on hydroxyapatite are supported in a form close to an ion exchange method in which the precursor is exchanged with surface ions, and are obtained by reduction. It has been reported that this complex exhibits remarkable activity in the oxidation reaction of alcohol (Non-patent Document 4 and the like).
一方、一酸化炭素は有害なガスで、人体に対する毒性は１０００ｐｐｍで頭痛、頭重、吐き気、めまいなどがあらわれ、継続した曝露により自力脱出が困難になり、死亡に至るものであって（非特許文献５）、米国産業衛生専門官会議が定めている時間加重平均曝露限界閾値（TLV-TWA）は２５ｐｐｍであり、また、米国国立安全衛生研究所が定めている、３０分間曝露で生命・健康危険レベル(IDLH)は１２００ｐｐｍである(非特許文献５)。
生活空間では、石油やガス、木炭、練炭などの燃焼を利用した暖房器具、調理器具が広く普及し、燃料の不完全燃焼により前記の安全基準に達しない程度の微量な一酸化炭素が発生している。一酸化炭素は、微量であっても、血液中のヘモグロビンと結合し、心肺機能の低下、高血圧、動脈硬化、不整脈など健康を害する可能性が高まる。また、健康増進法の施行により公共機関や企業等で喫煙室を設置し、分煙を図ることが義務化されているが、狭い空間内で喫煙をすることにより、局所的に一酸化炭素濃度が高まり、健康に悪影響を及ぼす可能性が生じる。
上記の事情により、一酸化炭素除去触媒が塗布された空気浄化フィルターなどを用いて一酸化炭素を空気中の酸素と反応させて二酸化炭素に変換し除去することが切望されているが、要求を満たす高性能な触媒は開発途上である。
On the other hand, carbon monoxide is a harmful gas, and its toxicity to the human body is 1000 ppm. It causes headache, headache, nausea, dizziness, etc., and continuous exposure makes it difficult to escape and causes death (Non-patent Document) 5) The time-weighted average exposure limit threshold (TLV-TWA) set by the National Council of Occupational Health and Safety is 25 ppm, and the life and health risk of 30-minute exposure set by the National Institute of Health and Safety The level (IDLH) is 1200 ppm (Non-patent Document 5).
In living spaces, heating appliances and cooking utensils that use combustion of oil, gas, charcoal, briquettes, etc. have become widespread, and incomplete combustion of the fuel generates a trace amount of carbon monoxide that does not meet the above safety standards. ing. Even in a trace amount, carbon monoxide binds to hemoglobin in the blood and increases the possibility of harming health such as decreased cardiopulmonary function, hypertension, arteriosclerosis, and arrhythmia. In addition, the enforcement of the Health Promotion Act has made it mandatory to set up smoking rooms in public institutions and companies and to separate smoke, but by smoking in a narrow space, the concentration of carbon monoxide is locally increased. Increased, with potential for adverse health effects.
Due to the above circumstances, there is a strong desire to convert carbon monoxide to carbon dioxide by reacting it with oxygen in the air using an air purification filter coated with a carbon monoxide removal catalyst. A high-performance catalyst to satisfy is under development.
また、近年において燃料電池が次世代のエネルギー発生システムとして注目されており、水素が燃料として用いられることが多いが、水素は炭化水素ガスの改質などで製造され、反応途中に副生する一酸化炭素が水素中に微量残留する。その残留一酸化炭素は、電極材と反応し電極を不活性化し、電極の寿命を大幅に短くする。そのため、水素ガス中の微量の一酸化炭素だけを酸素と反応させて二酸化炭素に転換させることにより、水素の酸化を少量に防ぎつつ一酸化炭素だけを除去しうる触媒の開発が切望されているが、該要求を満たす高性能な触媒は開発途上であって、まだ得られていない。 In recent years, fuel cells have attracted attention as a next-generation energy generation system, and hydrogen is often used as a fuel. Hydrogen is produced by reforming hydrocarbon gas or the like, and is produced as a by-product during the reaction. A small amount of carbon oxide remains in the hydrogen. The residual carbon monoxide reacts with the electrode material to inactivate the electrode and significantly shorten the life of the electrode. Therefore, the development of a catalyst that can remove only carbon monoxide while reacting only a small amount of carbon monoxide in hydrogen gas with oxygen to convert it to carbon dioxide while preventing the oxidation of hydrogen to a small amount is eagerly desired. However, a high-performance catalyst that satisfies this requirement is still under development and has not yet been obtained.
従来、一酸化炭素の酸化除去には貴金属触媒が使われることが多い。貴金属は、一般的には、金、銀、白金、パラジウム、ロジウム、イリジウム、ルテニウム、オスミウムの８種を称するが、その中でも、粒子サイズを精密にコントロールされ、適切な担体と複合化した金（Ａｕ）触媒が、低温、室温での一酸化炭素の酸化除去触媒に好ましく用いられている(非特許文献６〜８、特許文献１〜３)。また、白金（Ｐｔ）も単独または他の金属類と複合化されて水素ガス中の微量一酸化炭素の酸化除去に好ましく用いられることが多い(非特許文献９、１０、特許文献４、５)。 Conventionally, a precious metal catalyst is often used for oxidative removal of carbon monoxide. Precious metals generally refer to eight types of gold, silver, platinum, palladium, rhodium, iridium, ruthenium, and osmium. Among them, the particle size is precisely controlled, and gold ( Au) catalyst is preferably used as an oxidation removal catalyst for carbon monoxide at low temperature and room temperature (Non-patent Documents 6 to 8, Patent Documents 1 to 3). In addition, platinum (Pt) is often used alone or in combination with other metals and is preferably used for the oxidation removal of a small amount of carbon monoxide in hydrogen gas (Non-patent Documents 9 and 10, Patent Documents 4 and 5). .
しかしながら、これらの金触媒又は白金触媒は、通常、金属酸化物からなる担体に担持されるか（特許文献１、特許文献２、特許文献４）、或いは、活性炭、シリカゲル、アルミナ等の多孔質体に担持されて（特許文献３、特許文献５）用いられるが、いまだに、前記のごとき空気又は水素ガス中の微量な一酸化炭素だけを効率的に除去しうる高性能な触媒を得るには至っていないのが現状である。 However, these gold catalysts or platinum catalysts are usually supported on a carrier made of a metal oxide (Patent Document 1, Patent Document 2, Patent Document 4), or a porous body such as activated carbon, silica gel, and alumina. (Patent Document 3 and Patent Document 5) are used, but still have a high-performance catalyst that can efficiently remove only a small amount of carbon monoxide in air or hydrogen gas as described above. There is no current situation.
さらに、アルコール類の酸化は重要な反応であり、２級アルコールは酸化することによりケトンに変換される。
この反応は空気や酸素、過酸化水素を酸化剤として行うことが理想的とされており、種々の触媒の報告例がある。
たとえば、ルテニウムをアルミナに担持した触媒(非特許文献１１)、ルテニウムをハイドロキシアパタイトに担持した触媒(非特許文献１２)、Ｎａ２ＷＯ４系錯体触媒(非特許文献１３)などが報告されており、それぞれ、適切な反応条件を選択することにより、目的の酸化反応を実施することが出来る。
しかしながら、いまだに、目的とする酸化反応を効率的に行うことができる高性能な触媒を得るには至っていないのが現状である。
Furthermore, the oxidation of alcohols is an important reaction, and secondary alcohols are converted to ketones by oxidation.
This reaction is ideally performed using air, oxygen, or hydrogen peroxide as an oxidizing agent, and there are reports of various catalysts.
For example, a catalyst in which ruthenium is supported on alumina (Non-patent document 11), a catalyst in which ruthenium is supported on hydroxyapatite (Non-patent document 12), a Na 2 WO 4 complex catalyst (Non-patent document 13), and the like have been reported. The target oxidation reaction can be carried out by selecting appropriate reaction conditions.
However, the present situation is that a high-performance catalyst capable of efficiently performing the target oxidation reaction has not yet been obtained.
本発明は、以上のような事情に鑑みてなされたものであって、その目的は、空気中又は水素ガス中の微量な一酸化炭素を効率的に除去しうる高性能な触媒を提供することにある。
また、本発明のもう1つの目的は、アルコール類の酸化的脱水素反応によるケトン類の合成を効率的に行うことができる高性能な触媒を提供することにある。
The present invention has been made in view of the above circumstances, and an object thereof is to provide a high-performance catalyst capable of efficiently removing a small amount of carbon monoxide in air or hydrogen gas. It is in.
Another object of the present invention is to provide a high-performance catalyst that can efficiently synthesize ketones by oxidative dehydrogenation of alcohols.
本発明者らは、上記課題を解決すべく鋭意検討を行った結果、金の超微粒子を、特定の担体に担持させた新規な無機複合物は、ナノサイズの金の超微粒子を均一に担持しうるという知見を得た。また、金の超微粒子を担持する方法として、特定の方法を採用することにより、金担持後の比表面積が５００〜１０００ｍ２／ｇに達するような高比表面積を有する無機複合体が得られることが判明した。さらに、該無機複合体が一酸化炭素を効率的に除去する触媒機能及びアルコールの酸化反応を効率的に行うことができる触媒機能を有することを見出し、本発明の完成に至ったものである。 As a result of intensive studies to solve the above problems, the present inventors have found that a novel inorganic composite in which gold ultrafine particles are supported on a specific carrier uniformly supports nano-sized gold ultrafine particles. The knowledge that it is possible was obtained. In addition, by adopting a specific method as a method for supporting gold ultrafine particles, an inorganic composite having a high specific surface area such that the specific surface area after supporting gold reaches 500 to 1000 m 2 / g can be obtained. There was found. Furthermore, the present inventors have found that the inorganic composite has a catalytic function for efficiently removing carbon monoxide and a catalytic function capable of efficiently performing an oxidation reaction of alcohol, and has completed the present invention.
すなわち、本発明によれば、以下の発明が提供される。
（１）金の超微粒子を、セリウムを含有するメソポーラスシリカに担持させたことを特徴とする無機複合体。
（２）前記超微粒子の直径が、０．５〜５ナノメートルの範囲に全粒子数の殆どが含まれることを特徴とする前記（１）の無機複合体。
（３）前記セリウムを含有するメソポーラスシリカに前記金の超微粒子を担持する方法として、塩化金酸の水溶液にアルカリ溶液を添加してｐＨ値を７．０以上１０．０未満の範囲に調整して塩化金酸を水酸化物イオンが配位した状態に変化させ、その溶液中にセリウムを含有するメソポーラスシリカを分散させるか又はその溶液とセリウムを含有メするソポーラスシリカとを接触させることにより、メソポーラスシリカ表面に電気的親和力で前記金の超微粒子の前駆体である水酸化物イオンが配位した金錯体を吸着させる方法を用いることを特徴とする前記（１）又は（２）の無機複合体の製造方法。
（４）前記（１）又は（２）の無機複合体からなることを特徴とする、ガス中に含まれる一酸化炭素の酸化除去用触媒。
（５）前記（１）又は（２）の無機複合体を触媒に用い、ガス中に含まれる微量の一酸化炭素を、同ガス中に含まれている酸素又は必要量添加した酸素と反応させて、該一酸化炭素を酸化除去して二酸化炭素に変換することを特徴とする微量一酸化炭素の酸化除去方法。
（６）前記ガスの主成分が水素又は空気である前記（５）の微量一酸化炭素の酸化除去方法。
（７）前記（１）又は（２）の無機複合体からなることを特徴とする、アルコール類の酸化的脱水素反応によるケトン類の合成用触媒。
（８）前記（１）又は（２）の無機複合体を触媒に用い、アルコール類を酸素で酸化し、酸化的脱水素反応によりケトン類を製造することを特徴とするケトン類の製造方法。
That is, according to the present invention, the following inventions are provided.
(1) An inorganic composite comprising ultrafine gold particles supported on mesoporous silica containing cerium.
(2) The inorganic composite according to (1) above, wherein the ultrafine particles have a diameter of 0.5 to 5 nanometers and most of the total number of particles is included.
(3) As a method of supporting the ultrafine gold particles on the mesoporous silica containing cerium, an alkaline solution is added to an aqueous solution of chloroauric acid to adjust the pH value to a range of 7.0 or more and less than 10.0. By changing the chloroauric acid to a state in which hydroxide ions are coordinated, and dispersing the mesoporous silica containing cerium in the solution or bringing the solution into contact with the mesoporous silica containing cerium. And (1) or (2), wherein the gold complex coordinated with hydroxide ions, which are precursors of the ultrafine gold particles, is adsorbed onto the mesoporous silica surface with an electrical affinity. A method for producing a composite.
(4) A catalyst for oxidizing and removing carbon monoxide contained in a gas, comprising the inorganic composite according to (1) or (2).
(5) Using the inorganic composite according to (1) or (2) as a catalyst, a trace amount of carbon monoxide contained in the gas is reacted with oxygen contained in the gas or oxygen added in a necessary amount. And oxidizing and removing the carbon monoxide to convert it into carbon dioxide.
(6) The method for oxidizing and removing trace carbon monoxide according to (5), wherein the main component of the gas is hydrogen or air.
(7) A catalyst for synthesizing ketones by oxidative dehydrogenation of alcohols, which comprises the inorganic composite according to (1) or (2).
(8) A method for producing a ketone, characterized in that the inorganic complex of (1) or (2) is used as a catalyst, an alcohol is oxidized with oxygen, and a ketone is produced by an oxidative dehydrogenation reaction.
本発明によれば、直径が０．５〜５ナノメートルの範囲に全粒子数の殆どが含まれる金の超微粒子を、均一に担持した無機複合体を得ることができる。また、本発明の製造方法は、セリウム含有メソポーラスシリカ担体に、金の超微粒子を担持させる方法として優れた方法を提供するものであって、本発明の製造方法によれば、金担持後の前記複合材料の比表面積が５００〜１０００ｍ２／ｇに達する高比表面積を有する無機複合材料、すなわち金の超微粒子が効率よく担持され、反応ガスとの接触効率が高い無機複合材料を得ることができる。さらに、本発明の無機複合体は、ガス中の微量の一酸化炭素を効率的に除去しうる高性能な触媒作用を提供するものであり、特に、（１）空気中の微量の一酸化炭素を酸化して二酸化炭素に転換して無害化しうる触媒作用、（２）水素ガス中の微量の一酸化炭素だけを酸素と反応させて二酸化炭素に転換させることにより、水素の酸化を少量に防ぎつつ一酸化炭素だけを除去しうる触媒作用を提供するものである。また、本発明の無機複合体は、アルコール類を酸素で酸化し、酸化的脱水素反応によりケトン類を製造するアルコールの酸化反応方法において、高性能な触媒作用を提供するものである。 According to the present invention, it is possible to obtain an inorganic composite that uniformly supports ultrafine gold particles having a total particle number in the range of 0.5 to 5 nanometers in diameter. The manufacturing method of the present invention provides an excellent method as a method for supporting ultrafine gold particles on a cerium-containing mesoporous silica support, and according to the manufacturing method of the present invention, An inorganic composite material having a high specific surface area in which the specific surface area of the composite material reaches 500 to 1000 m 2 / g, that is, an inorganic composite material in which ultrafine gold particles are efficiently supported and contact efficiency with the reaction gas can be obtained. . Furthermore, the inorganic composite of the present invention provides a high-performance catalytic action that can efficiently remove a trace amount of carbon monoxide in a gas. In particular, (1) a trace amount of carbon monoxide in air. Catalytic action that can oxidize and convert to carbon dioxide to make it harmless, (2) Only a small amount of carbon monoxide in hydrogen gas reacts with oxygen to convert to carbon dioxide, thereby preventing hydrogen oxidation to a small amount However, it provides a catalytic action capable of removing only carbon monoxide. The inorganic composite of the present invention provides a high-performance catalytic action in an alcohol oxidation reaction method in which alcohols are oxidized with oxygen and ketones are produced by oxidative dehydrogenation.
以下、本発明のセリウム含有メソポーラスシリカである担体と、金の超微粒子とを複合化した無機複合材料について、詳細に説明する。
メソポーラスシリカは、大きな比表面積と特有の細孔構造をもつ材料として既に公知であって、界面活性剤等が溶液中で自己集合する性質を利用して、シリカ源との反応により、直径１〜１０ｎｍ（ナノメートル）の均一な円筒状メソ孔を有するメソポーラスシリカを合成することができるものであり、具体的には、一般的な呼称としてＭＣＭ−４１、ＦＳＭ−１６等と称されている物質がある。
Hereinafter, an inorganic composite material in which a carrier which is the cerium-containing mesoporous silica of the present invention and gold ultrafine particles are combined will be described in detail.
Mesoporous silica is already known as a material having a large specific surface area and a unique pore structure. By utilizing the property that a surfactant or the like is self-assembled in a solution, a diameter of 1 to Mesoporous silica having uniform cylindrical mesopores of 10 nm (nanometers) can be synthesized. Specifically, substances generally called MCM-41, FSM-16, etc. There is.
本発明において担体として用いるセリウム含有メソポーラスシリカは、前述のメソポーラスシリカのテンプレート剤(界面活性剤)を含有したままの状態である前駆物質を適切な粒子径に粉砕し、イオン交換水に分散しスラリー状にしたところに、セリウム原料であるセリウム塩を溶解し、充分に撹拌後、加熱処理及び濾過洗浄を行い、乾燥させることで得ることができる。セリウムの含有率は０．１重量％以上２０重量％以下の範囲が好ましく、１重量％以上１０重量％以下の範囲がさらに好ましい。また、前記の洗浄、乾燥などの処理をした後に、テンプレート剤として含有されている有機物を空気または酸素中の焼成処理により除去することが好ましい。この際の加熱温度は２００℃以上１０００℃以下が好ましく、より好ましくは３００℃以上７００℃以下である。加熱時間は１分以上２４時間未満が好ましく、さらに好ましくは１時間以上６時間以下である。 The cerium-containing mesoporous silica used as a carrier in the present invention is a slurry obtained by pulverizing a precursor having the above-mentioned mesoporous silica template agent (surfactant) into an appropriate particle size and dispersing it in ion-exchanged water. The cerium salt which is a cerium raw material is melt | dissolved in the place, and it can obtain by drying after performing heat processing and filtration washing | cleaning after fully stirring. The content of cerium is preferably in the range of 0.1% by weight to 20% by weight, and more preferably in the range of 1% by weight to 10% by weight. Moreover, it is preferable to remove the organic substance contained as the template agent by a baking treatment in air or oxygen after the treatment such as washing and drying. The heating temperature at this time is preferably 200 ° C. or higher and 1000 ° C. or lower, more preferably 300 ° C. or higher and 700 ° C. or lower. The heating time is preferably 1 minute or more and less than 24 hours, more preferably 1 hour or more and 6 hours or less.
次に、一酸化炭素除去に効果的な金の複合化方法について詳述する。
金の超微粒子の担持方法としては、前述の担体の表面に均一に超微粒子を担持することができる析出沈殿法が最も好ましい。
以下、析出沈殿法の概要を述べる。なお、この析沈殿法は、酸化チタン担体やチタン含有メソポーラスシリカ担体に金を担持する手法としてすでに公知であるが、セリウム含有メソポーラスシリカ担体に適用して成功した例はまだ知られていない。
Next, a gold compounding method effective for removing carbon monoxide will be described in detail.
As a method for supporting the ultrafine gold particles, the precipitation method that can uniformly support the ultrafine particles on the surface of the carrier is most preferable.
The outline of the precipitation method is described below. This precipitation method is already known as a technique for supporting gold on a titanium oxide carrier or a titanium-containing mesoporous silica carrier, but an example of successful application to a cerium-containing mesoporous silica carrier is not yet known.
水溶性の塩化金酸(テトラクロロ金酸)をイオン交換水などに溶解し酸性の水溶液を調製する。その溶液にアルカリを添加して中和しｐＨの値が中性〜アルカリ性である７．０以上１０．０未満に調整する。この場合、ｐＨの値が７．０未満である酸性側では、後述する金の塩素配位子が水酸化物配位子に置換される反応が十分に起きずに、あまり好ましくはない。また、１０．０以上では得られた無機複合体を触媒に用いた際に、高温でないとＣＯの除去率を１００％にすることができなくなり、一酸化炭素除去触媒としては好ましくない。
ここで用いることができるアルカリは特に限定されるものではないが、水酸化ナトリウムがもっとも好ましく、それ以外にはアンモニア水、水酸化カリウム、水酸化リチウム、水酸化ルビジウム、水酸化セシウム、炭酸ナトリウム、炭酸水素ナトリウムなども好ましく用いられる。この際、金原子に配位している塩素配位子(Ｃｌ)が水酸化物配位子(ＯＨ)に交換される。金に水酸化物イオンが配位している状態になると、セリウム含有メソポーラスシリカの表面との電気的親和力が働き、金錯体はセリウム含有メソポーラスシリカ表面に高分散状態で吸着する。ｐＨの調整後のスラリー液を３０〜８０℃に保ち、好ましくは１分〜２４時間、さらに好ましくは１時間〜５時間撹拌し、吸着状態を安定化させるのが好ましい。金錯体が十分吸着した後に、蒸留水、イオン交換水などで十分に洗浄し、残留している塩素や、吸着しきれなかった金錯体を洗浄除去して、真空乾燥などの方法で乾燥処理を行う。その後、金属の担持後は金属を活性状態にするために適切な温度での加熱が好ましい。活性化のための加熱温度は２００℃〜７００℃が好ましく、中でも２５０℃〜４５０℃が特に好ましい。加熱時間は、１分〜２４時間の範囲が好ましく、さらに好ましくは１時間〜５時間である。加熱処理後の金の含有率は０．１重量％以上２０重量％以下が好ましく、さらに好ましくは１重量％以上１０重量％以下である。
A water-soluble chloroauric acid (tetrachloroauric acid) is dissolved in ion-exchanged water to prepare an acidic aqueous solution. The solution is neutralized by adding an alkali, and the pH value is adjusted to 7.0 to less than 10.0, which is neutral to alkaline. In this case, on the acidic side where the pH value is less than 7.0, the reaction of replacing the gold chlorine ligand described later with the hydroxide ligand does not occur sufficiently, which is not preferable. In addition, when the obtained inorganic composite is used as a catalyst at 10.0 or more, the CO removal rate cannot be made 100% unless the temperature is high, which is not preferable as a carbon monoxide removal catalyst.
The alkali that can be used here is not particularly limited, but sodium hydroxide is most preferable, and other than that, ammonia water, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, sodium carbonate, Sodium bicarbonate and the like are also preferably used. At this time, the chlorine ligand (Cl) coordinated to the gold atom is exchanged for the hydroxide ligand (OH). When the hydroxide ions are coordinated to gold, the electric affinity with the surface of the cerium-containing mesoporous silica works, and the gold complex is adsorbed on the cerium-containing mesoporous silica surface in a highly dispersed state. The slurry after the pH adjustment is maintained at 30 to 80 ° C., and preferably stirred for 1 minute to 24 hours, more preferably 1 hour to 5 hours to stabilize the adsorption state. After the gold complex has been sufficiently adsorbed, it is thoroughly washed with distilled water, ion exchange water, etc., and residual chlorine and gold complex that cannot be adsorbed are washed away and dried by vacuum drying or other methods. Do. Thereafter, after loading the metal, heating at an appropriate temperature is preferable to bring the metal into an active state. The heating temperature for activation is preferably 200 ° C to 700 ° C, and particularly preferably 250 ° C to 450 ° C. The heating time is preferably in the range of 1 minute to 24 hours, more preferably 1 hour to 5 hours. The gold content after the heat treatment is preferably 0.1 wt% or more and 20 wt% or less, more preferably 1 wt% or more and 10 wt% or less.
この方法を用いると、含浸法など他の公知の手法を用いたときと異なり、アセリウム含有メソポーラスシリカ表面に担持された金の粒子は、大きな粒子に凝集することがなく、その直径が０．５〜５ナノメートルの範囲に全粒子数の殆ど、好ましくは０．５〜３ｎｍの範囲に全粒子数の９８％が含まれる、ほぼ均一な超微粒子状で担持することができる。 When this method is used, unlike other known methods such as the impregnation method, the gold particles supported on the surface of the acelium-containing mesoporous silica are not aggregated into large particles, and the diameter is 0.5. It can be supported in the form of almost uniform ultrafine particles in which most of the total number of particles is in the range of ˜5 nanometers, preferably 98% of the total number of particles is in the range of 0.5 to 3 nm.
一酸化炭素が微量含まれているガス中から一酸化炭素を酸素と反応させて除去する反応は、大きく２種類の用途がある。一つは、空気中からの除去、もう一つは水素中からの除去である。ここでは、空気中の除去を中心に述べるが、水素からの除去にも本触媒は適用可能である。 The reaction for removing carbon monoxide by reacting it with oxygen from a gas containing a small amount of carbon monoxide has two major uses. One is removal from the air, and the other is removal from hydrogen. Here, the description will focus on the removal in the air, but the present catalyst can also be applied to the removal from hydrogen.
空気は十分に乾燥剤などを用いて十分に乾燥した状態から、日常生活空間での相対湿度の最も高い状態に相当する相対湿度１００％までの範囲で好ましく用いることが出来る。触媒の使用法は、燃料の不完全燃焼や喫煙の副流煙など、何らかの理由で微量の一酸化炭素を含有する空気をポンプやファンなどを用いて触媒を充填した層を通過させるか、触媒や触媒を塗布した支持体に吹き付けるなどの方法で、効率的に接触させ、一酸化炭素を二酸化炭素に変換しほぼ無害化する。二酸化炭素も、２％以上で呼吸困難のような毒性を有するが、１％以下の低濃度では、一酸化炭素と比較すれば人体に対する影響は極めて少ない。 Air can be preferably used in a range from a sufficiently dried state using a desiccant or the like to a relative humidity of 100% corresponding to the highest relative humidity in the daily living space. The catalyst can be used by passing air containing a minute amount of carbon monoxide for some reason, such as incomplete combustion of fuel or smoking sidestream smoke, through a layer filled with catalyst using a pump or fan, etc. The carbon monoxide is converted into carbon dioxide and made almost harmless by contacting it efficiently, for example, by spraying on a support coated with a catalyst. Carbon dioxide also has toxicity such as dyspnea at 2% or more, but at a low concentration of 1% or less, there is very little influence on the human body compared to carbon monoxide.
また、本発明の無機複合体を触媒として用いるアルコール類の酸化は、例えば、２級アルコールの場合、下記の反応式に示すとおり、ケトンに変換される。
反応の基質として用いることの出来るアルコールは２級アルコールが好ましい。ベンジルアルコールを除く末端アルコールは反応性が低く、また、３級アルコールは酸化反応生成物が生成できない場合が多い。原料として適したアルコールの例を挙げれば、上記（化１）において、Ｒ１及びＲ２として、メチル基、エチル基、n-プロピル基、iso-プロピル基、フェニル基、その他の直鎖状、分岐を持つ炭化水素基が用いられる。また、炭素-炭素間に二重結合などを有していても良い。 The alcohol that can be used as a substrate for the reaction is preferably a secondary alcohol. Terminal alcohols other than benzyl alcohol have low reactivity, and tertiary alcohols often cannot produce oxidation reaction products. Examples of alcohols suitable as a raw material include, in the above (Chemical Formula 1), as R 1 and R 2 , methyl group, ethyl group, n-propyl group, iso-propyl group, phenyl group, other straight chain, A branched hydrocarbon group is used. Further, a double bond or the like may be present between carbon and carbon.
また、反応の基質として、下記の式で代表例が例示される環を形成する炭素数が３以上の環状アルコールも用いることができる。
次に、本発明を実施例によりさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
（実施例１）
（１）メソポーラスシリカの合成
メソポーラスシリカは一次元の筒状構造が特徴的である、通常ＭＣＭ−４１と称される構造のものを合成した。合成法は公知の文献を基にした（非特許文献：第１７回キャタリシススクールテキスト２２３頁参照）。テンプレート（界面活性剤）であるセチルトリメチルアンモニウムブロマイド（以後ＣＴＡＢｒと省略する）４０．４ｇをテフロン製容器中で５０℃の１７４．５ｇの温水に溶解し、３０分ほど撹拌し均一な溶液を得た。これを溶液Ａとする。イオン交換水４０．０ｇで希釈したケイ酸ナトリウム（水ガラス３号）３５．５ｇを溶液Ａにゆっくりと滴下し、ＣＴＡＢｒとケイ酸ナトリウムが均一に分散した混合溶液を得た。この溶液に５０％硫酸を５２ｇの水で希釈した溶液をゆっくり滴下して混合し、ケイ酸ナトリウムのアルカリ分を中和した。その後、容器を密封し１１０℃の条件で７２時間静置しメソポーラスシリカ前駆体を得た。前駆体をろ過洗浄し、１１０℃で乾燥を行い、テンプレート（界面活性剤）含有ＭＣＭ−４１を得た。
EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.
Example 1
(1) Synthesis of mesoporous silica Mesoporous silica was synthesized with a structure generally called MCM-41, which is characterized by a one-dimensional cylindrical structure. The synthesis method was based on known literature (see non-patent literature: page 223 of the 17th Catalysis School Text). 40.4 g of cetyltrimethylammonium bromide (hereinafter abbreviated as CTABr) as a template (surfactant) is dissolved in 174.5 g of hot water at 50 ° C. in a Teflon container, and stirred for about 30 minutes to obtain a uniform solution. It was. This is designated as Solution A. 35.5 g of sodium silicate (water glass No. 3) diluted with 40.0 g of ion-exchanged water was slowly added dropwise to the solution A to obtain a mixed solution in which CTABr and sodium silicate were uniformly dispersed. To this solution, a solution obtained by diluting 50% sulfuric acid with 52 g of water was slowly added dropwise and mixed to neutralize the alkali content of sodium silicate. Thereafter, the container was sealed and allowed to stand for 72 hours at 110 ° C. to obtain a mesoporous silica precursor. The precursor was filtered and washed, and dried at 110 ° C. to obtain a template (surfactant) -containing MCM-41.
（２）セリウムとメソポーラスシリカの複合化
テンプレートイオン交換法を用いた。（１）で合成したテンプレート含有ＭＣＭ−４１を粉砕して微粉末状にしてイオン交換水に分散した。ここに、セリウム原料である硝酸セリウムを溶解し十分に撹拌を行った。撹拌終了後、混合液をテフロン容器内に密封し１１０℃１８時間の加熱処理を行った。加熱処理後、ろ過洗浄を行い１１０℃で乾燥させた。その後５４０℃において４時間加熱焼成しセリウム含有ＭＣＭ−４１を得た。
(2) Compounding of cerium and mesoporous silica A template ion exchange method was used. The template-containing MCM-41 synthesized in (1) was pulverized into a fine powder and dispersed in ion-exchanged water. Here, cerium nitrate as a cerium raw material was dissolved and sufficiently stirred. After completion of the stirring, the mixed solution was sealed in a Teflon container and subjected to a heat treatment at 110 ° C. for 18 hours. After the heat treatment, it was washed by filtration and dried at 110 ° C. Thereafter, it was heated and fired at 540 ° C. for 4 hours to obtain cerium-containing MCM-41.
（３）金の複合化
析出沈殿法を用いて行った。塩化金酸（ＨＡｕＣｌ４・Ｈ２Ｏ）をイオン交換水に溶解し、水酸化ナトリウムを加え溶液のpHを７．０に調節した。その後、（２）で合成されたセリウム含有メソポーラスシリカを添加し、７０℃で２時間撹拌した。ろ過洗浄を行い、得られた粉末を４００℃、３時間の加熱焼成を行い目的の複合体（Ａ）を得た。
(3) Compounding of gold It was carried out using a precipitation method. Chloroauric acid (HAuCl 4 · H 2 O) was dissolved in ion-exchanged water, and sodium hydroxide was added to adjust the pH of the solution to 7.0. Thereafter, the cerium-containing mesoporous silica synthesized in (2) was added and stirred at 70 ° C. for 2 hours. Filtration washing was performed, and the obtained powder was heated and fired at 400 ° C. for 3 hours to obtain the intended composite (A).
（４）無機複合体の評価
上記（３）で得られた複合体の比表面積をＢＥＴ法による窒素吸着測定により算出した。その結果は５４８ｍ２／ｇであった。
また、（３）で得られた複合体のＸ線回折測定を行った。その結果を図１に示す。縦軸は回折線の強度を示し、横軸は角度を示す。良好な規則性の高いハニカム状構造を示す標準的なＭＣＭ−４１（図中の(ａ)）と比較すると、得られた複合体（図中の（ｂ））も、３．７〜４．３度付近の２つのピークが、ピーク強度は小さいが、はっきりと確認でき、かつその二つが明確に分離されている。これはハニカム状の規則的な細孔構造が整っている証拠の一つである。
さらに（３）で得られた複合体のＩＣＰ発光分析を行い各成分の含有率を求めた。その結果、金の含有率が２．２重量％、セリウムの含有率が６．４重量％であった。
(4) Evaluation of inorganic composite The specific surface area of the composite obtained in (3) above was calculated by nitrogen adsorption measurement by the BET method. The result was 548 m 2 / g.
Moreover, the X-ray-diffraction measurement of the composite_body | complex obtained by (3) was performed. The result is shown in FIG. The vertical axis represents the intensity of the diffraction line, and the horizontal axis represents the angle. Compared with standard MCM-41 ((a) in the figure) showing a honeycomb structure with good regularity, the obtained composite ((b) in the figure) is also 3.7-4. Two peaks near 3 degrees have a small peak intensity but are clearly identifiable, and the two are clearly separated. This is one of the evidence that the honeycomb-like regular pore structure is in order.
Further, the composite obtained in (3) was subjected to ICP emission analysis to determine the content of each component. As a result, the gold content was 2.2% by weight and the cerium content was 6.4% by weight.
また、（３）で得られた複合体の走査透過電子顕微鏡法（ＳＴＥＭ）撮影を行った。図２と図３に示した写真はＳＴＥＭの暗視野像である。図２において薄い灰色の蜂の巣状（ハニカム状）の構造はセリウム含有ＭＣＭ−４１の担体の構造に帰属され、規則的細孔構造が非常に整っていることを示す像である。また、白く見える微粒子は担持されている金の粒子に帰属され、粒子径がほぼ均一にそろった超微粒子が、担体上に均一に分散していることを示す像である。図３は角度を変えて撮影した像であるが、担体のセリウム含有メソポーラスシリカの直線的な細孔の良好な規則的が示される像であり、白い点状の像は超微粒子状になっている金に帰属される。 Further, scanning transmission electron microscopy (STEM) imaging of the composite obtained in (3) was performed. The photographs shown in FIGS. 2 and 3 are dark field images of STEM. In FIG. 2, the light gray honeycomb-like (honeycomb-like) structure is attributed to the structure of the cerium-containing MCM-41 carrier and is an image showing that the regular pore structure is very well-organized. In addition, the fine particles that appear white are attributed to the supported gold particles, and the image shows that ultra-fine particles having a substantially uniform particle size are uniformly dispersed on the carrier. FIG. 3 is an image taken at a different angle. This image shows a good regularity of the linear pores of the cerium-containing mesoporous silica as a support, and the white dot-like image is in the form of ultrafine particles. Is attributed to the gold.
（実施例２：粒径の測定）
走査透過電子顕微鏡の暗視野像をもとに、実施例１で用いた触媒中の金粒子の粒径の測定を行った。その結果、０〜０．５ｎｍの範囲には全粒子数の１％、０．５〜１ｎｍの範囲には全粒子数の１６％、１〜１．５ｎｍの範囲には全粒子数の５１％、１．５〜２．０ｎｍの範囲には全粒子数の２１％、２．０〜２．５ｎｍの範囲には全粒子数の９％、２．５〜３．０ｎｍの範囲には全粒子数の２％であった。特に０．５〜２．０の範囲内に全粒子数の８８％が含まれ、さらに１．０〜１．５ｎｍの範囲内に全粒子数の５１％が含まれており、単に微粒子であるだけではなく、粒子の直径も均一に制御されていることが確認された。
(Example 2: Measurement of particle size)
Based on the dark field image of the scanning transmission electron microscope, the particle size of the gold particles in the catalyst used in Example 1 was measured. As a result, the range of 0 to 0.5 nm is 1% of the total number of particles, the range of 0.5 to 1 nm is 16% of the total number of particles, and the range of 1 to 1.5 nm is 51% of the total number of particles. In the range of 1.5 to 2.0 nm, 21% of the total number of particles, in the range of 2.0 to 2.5 nm, 9% of the total number of particles, and in the range of 2.5 to 3.0 nm, all the particles 2% of the number. In particular, 88% of the total number of particles is included in the range of 0.5 to 2.0, and 51% of the total number of particles is included in the range of 1.0 to 1.5 nm, which is simply a fine particle. In addition, it was confirmed that the diameter of the particles was uniformly controlled.
（実施例３：ＣＯの酸化的除去反応（１））
上記で得られた複合体（Ａ）を１００ｍｇ量り取り、内径８ｍｍ外径１０ｍｍの石英製触媒反応管に充填した。乾燥空気で２５０℃３０分の乾燥処理を行った後に、１．０%の一酸化炭素ガスを含有する空気を流通させ、ＣＯ除去反応を行った。ＣＯの除去率は事前に測定しておいたバイパスラインの測定値を元に次の計算式により行った。測定値はガスクロマトグラフ（島津製作所ＧＣ−８Ａ）によって行い、ガスクロマトグラフからの出力をインテグレーター（島津製作所ＣＲ−８Ａ）を用いて面積値に変換した。
ＣＯ除去率（５）＝｛１−（残存ＣＯの面積値）／（バイパスラインの面積値）｝×１００
複合体（Ａ）を用いたところ−８．０℃という低温状態にあってもＣＯの除去率が１００％であった。また、−２７．０℃においてＣＯの除去率が５０％であった。触媒調製の再現性を確認するために、複合体（Ａ）と同じ手法で複合体（Ａ−２）を調製し同様の測定を行ったところ、−８．０℃においてＣＯの除去率が１００％、−３５．７℃においてＣＯの除去率が５０％となり、安定した再現性を示した。
(Example 3: CO oxidative removal reaction (1))
100 mg of the composite (A) obtained above was weighed and filled into a quartz catalyst reaction tube having an inner diameter of 8 mm and an outer diameter of 10 mm. After a drying treatment at 250 ° C. for 30 minutes with dry air, air containing 1.0% carbon monoxide gas was circulated to perform a CO removal reaction. The CO removal rate was determined by the following calculation formula based on the measured value of the bypass line measured in advance. The measured value was measured by a gas chromatograph (Shimadzu Corporation GC-8A), and the output from the gas chromatograph was converted into an area value using an integrator (Shimadzu Corporation CR-8A).
CO removal rate (5) = {1- (area value of residual CO) / (area value of bypass line)} × 100
When the composite (A) was used, the CO removal rate was 100% even at a low temperature of -8.0 ° C. Further, the CO removal rate at −27.0 ° C. was 50%. In order to confirm the reproducibility of the catalyst preparation, the composite (A-2) was prepared in the same manner as the composite (A), and the same measurement was performed. As a result, the CO removal rate at −8.0 ° C. was 100. %, The CO removal rate was 50% at −35.7 ° C., indicating stable reproducibility.
（実施例４：ＣＯの酸化的除去反応（２））
金を担持する際にｐＨを８．５に調節するところ以外はすべて同じ手法で複合体を調製した。得られた複合体の比表面積は５１９ｍ２／ｇ、ＩＣＰ分析の結果は金含有率が１．６重量％、セリウム含有率が７．５重量％であった。
得られた複合体を、ＣＯの除去反応に供した。その結果、−１１．５℃においてもＣＯ除去率１００％を示し、−２９．２℃においてCO除去率５０％であった。
(Example 4: CO oxidative removal reaction (2))
A composite was prepared in the same manner except that the pH was adjusted to 8.5 when supporting gold. The obtained composite had a specific surface area of 519 m 2 / g, and the results of ICP analysis showed that the gold content was 1.6% by weight and the cerium content was 7.5% by weight.
The resulting composite was subjected to CO removal reaction. As a result, the CO removal rate was 100% even at -11.5 ° C, and the CO removal rate was 50% at -29.2 ° C.
（実施例５：ＣＯの酸化的除去反応（３））
金の担持量を増やすために、金の前駆体である塩化金酸を金原子換算で担体に対して５重量％になるように溶解して前記実施例とまったく同様に、調製、反応試験を行った。その結果、−１６．６℃までＣＯ除去率１００％を維持し、−３６．１℃において、除去率が５０％であった。
(Example 5: CO oxidative removal reaction (3))
In order to increase the amount of gold supported, chloroauric acid, which is a gold precursor, was dissolved so as to be 5% by weight with respect to the support in terms of gold atoms, and the preparation and reaction test were performed in exactly the same manner as in the previous examples. went. As a result, the CO removal rate of 100% was maintained up to -16.6 ° C, and at -36.1 ° C, the removal rate was 50%.
（実施例６：アルコールの酸化（１））
２−オクタノール０．７ｇ、実施例(１)で調製した複合体（Ａ）２０ｍｇを容量１０ｍＬのステンレス製オートクレーブへ入れ、酸素ガスで内部を置換し、酸素圧８気圧を加えて封入した。その後、１２０℃に保ったオイルバスを用いてオートクレーブを加熱し、４時間反応させた。その後、オートクレーブを冷却し反応後の液体を取り出し、エタノールで希釈してＦＩＤ検出器を有するガスクロマトグラフにて分析を行った。その結果、希釈液のエタノール、生成物の２−オクタノン、原料の２−オクタノールに帰属されるピークが確認された。ピークの面積値から原料の転化率は３３％、他に明確な副生成物が観測されないことから、ほぼ１００％の非常に高選択性であることが明らかになった。
(Example 6: Oxidation of alcohol (1))
0.7 g of 2-octanol and 20 mg of the composite (A) prepared in Example (1) were put into a stainless steel autoclave having a capacity of 10 mL, the inside was replaced with oxygen gas, and the mixture was sealed by applying an oxygen pressure of 8 atm. Thereafter, the autoclave was heated using an oil bath maintained at 120 ° C. and reacted for 4 hours. Thereafter, the autoclave was cooled, the liquid after the reaction was taken out, diluted with ethanol, and analyzed by a gas chromatograph having an FID detector. As a result, peaks attributed to ethanol as a diluent, 2-octanone as a product, and 2-octanol as a raw material were confirmed. From the peak area value, the conversion rate of the raw material was 33%, and no other clear by-product was observed, which revealed that the selectivity was very high of almost 100%.
（実施例７：アルコールの酸化（２））
2−オクタノール０．２５ｇ、トルエン０．７５ｇ、実施例(１)で調製した複合体３０ｍｇを容量１０ｍＬのステンレス製オートクレーブへ入れ、酸素ガスで内部を置換し、酸素圧７．５気圧を加えて封入した。その後、１２０℃に保ったオイルバスを用いてオートクレーブを加熱し、１５時間反応させた。その後、オートクレーブを冷却し反応後の液体を取り出し、エタノールで希釈してＦＩＤ検出器を有するガスクロマトグラフにて分析を行った。その結果、希釈液のエタノール、溶媒のトルエン、生成物の２−オクタノン、原料の２−オクタノールに帰属されるピークが確認された。ピークの面積値から原料の転化率は６５％、他に明確な副生成物が観測されないことから、ほぼ１００％の非常に高選択性であることが明らかになった。
(Example 7: Oxidation of alcohol (2))
2-octanol 0.25 g, toluene 0.75 g, 30 mg of the composite prepared in Example (1) was put into a 10 mL stainless steel autoclave, the inside was replaced with oxygen gas, and an oxygen pressure of 7.5 atm was added. Enclosed. Thereafter, the autoclave was heated using an oil bath maintained at 120 ° C. and reacted for 15 hours. Thereafter, the autoclave was cooled, the liquid after the reaction was taken out, diluted with ethanol, and analyzed by a gas chromatograph having an FID detector. As a result, the peaks attributed to the diluted ethanol, the solvent toluene, the product 2-octanone, and the raw material 2-octanol were confirmed. From the peak area value, the conversion rate of the raw material was 65%, and no other clear by-product was observed, which revealed that the selectivity was very high of almost 100%.
（比較例１）
金を担持する際にpHを１０．０に調節するところ以外はすべて同じ手法で複合体を調製しCOの酸化的除去反応に供した。その結果、ＣＯ除去率１００％を示す温度が１４８℃に上昇し、ＣＯ除去率５０％を示す温度が９２．０℃まで上昇した。これは、金を複合化させる際にはpHの調節が非常に重要な条件で、１０．０未満に調節することが特に重要であることを示すものである。
(Comparative Example 1)
A composite was prepared in the same manner except that the pH was adjusted to 10.0 when supporting gold, and subjected to CO oxidative removal reaction. As a result, the temperature at which the CO removal rate was 100% rose to 148 ° C., and the temperature at which the CO removal rate was 50% rose to 92.0 ° C. This shows that it is particularly important to adjust the pH to less than 10.0 under the condition that the pH is very important when complexing gold.
（比較例２）
金を担持する過程を行わず、セリウム含有メソポーラスシリカのみでCOの酸化除去反応を行った。その結果１００〜１５０℃という高温においてもＣＯの除去率が０％となり、金を複合化させる有効性が示されている。
(Comparative Example 2)
Without the process of supporting gold, the oxidation removal reaction of CO was performed only with cerium-containing mesoporous silica. As a result, even at a high temperature of 100 to 150 ° C., the CO removal rate becomes 0%, which shows the effectiveness of compounding gold.
（比較例３）
金を担持しないセリウム含有メソポーラスシリカを用いて実施例と同条件でアルコールの酸化反応を行ったが、反応はほとんど進行しなかった。
(Comparative Example 3)
Alcohol oxidation reaction was carried out under the same conditions as in Examples using cerium-containing mesoporous silica not supporting gold, but the reaction hardly proceeded.
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| JP2009061372A (en) * | 2007-09-05 | 2009-03-26 | Taiyo Kagaku Co Ltd | Catalyst for selective oxidation of carbon monoxide and method of removing carbon monoxide in hydrogen by using it |
| WO2010110447A1 (en) * | 2009-03-26 | 2010-09-30 | 国立大学法人北海道大学 | Mesoporous silica-supported gold cluster, catalyst comprising same, and process for producing same |
| JP2010221119A (en) * | 2009-03-23 | 2010-10-07 | Nippon Steel Corp | Catalyst for purifying exhaust gas and honeycomb catalytic structure for exhaust gas purification |
| WO2012144532A1 (en) * | 2011-04-19 | 2012-10-26 | 独立行政法人産業技術総合研究所 | Solution of gold/hydroxoanion complex and process for producing substance loaded with gold nanoparticles |
| KR20170000960A (en) * | 2015-06-25 | 2017-01-04 | 주식회사 엘지화학 | Manufacturing method of Heterogeneous Catalyst for Production of Acrylic acid and Heterogeneous Catalyst for Production of Acrylic acid using them |
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| WO2000016898A1 (en) * | 1998-09-22 | 2000-03-30 | Osaka Gas Co., Ltd. | Catalyst for decomposing chlorinated organic compound |
| WO2005120686A1 (en) * | 2004-06-08 | 2005-12-22 | National Institute Of Advanced Industrial Science And Technology | Catalyst for carbon monoxide removal and method of removing carbon monoxide with the catalyst |
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| WO2000016898A1 (en) * | 1998-09-22 | 2000-03-30 | Osaka Gas Co., Ltd. | Catalyst for decomposing chlorinated organic compound |
| WO2005120686A1 (en) * | 2004-06-08 | 2005-12-22 | National Institute Of Advanced Industrial Science And Technology | Catalyst for carbon monoxide removal and method of removing carbon monoxide with the catalyst |
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| JP2009061372A (en) * | 2007-09-05 | 2009-03-26 | Taiyo Kagaku Co Ltd | Catalyst for selective oxidation of carbon monoxide and method of removing carbon monoxide in hydrogen by using it |
| JP2010221119A (en) * | 2009-03-23 | 2010-10-07 | Nippon Steel Corp | Catalyst for purifying exhaust gas and honeycomb catalytic structure for exhaust gas purification |
| WO2010110447A1 (en) * | 2009-03-26 | 2010-09-30 | 国立大学法人北海道大学 | Mesoporous silica-supported gold cluster, catalyst comprising same, and process for producing same |
| WO2012144532A1 (en) * | 2011-04-19 | 2012-10-26 | 独立行政法人産業技術総合研究所 | Solution of gold/hydroxoanion complex and process for producing substance loaded with gold nanoparticles |
| JP5740658B2 (en) * | 2011-04-19 | 2015-06-24 | 国立研究開発法人産業技術総合研究所 | Gold hydroxo anion complex solution and method for producing gold nanoparticle carrier |
| KR20170000960A (en) * | 2015-06-25 | 2017-01-04 | 주식회사 엘지화학 | Manufacturing method of Heterogeneous Catalyst for Production of Acrylic acid and Heterogeneous Catalyst for Production of Acrylic acid using them |
| KR102015625B1 (en) | 2015-06-25 | 2019-08-28 | 주식회사 엘지화학 | Manufacturing method of Heterogeneous Catalyst for Production of Acrylic acid and Heterogeneous Catalyst for Production of Acrylic acid using them |
| CN111286216A (en) * | 2020-03-28 | 2020-06-16 | 哈尔滨工程大学 | Improve Ce3+In hollow mesoporous SiO2Method for loading in microspheres |
| CN111286216B (en) * | 2020-03-28 | 2021-09-10 | 哈尔滨工程大学 | Improve Ce3+In hollow mesoporous SiO2Method for loading in microspheres |
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