JP4456229B2 - Reaction promotion method in noble metal supported metal oxide catalytic reaction by light irradiation - Google Patents
Reaction promotion method in noble metal supported metal oxide catalytic reaction by light irradiation Download PDFInfo
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- JP4456229B2 JP4456229B2 JP2000158411A JP2000158411A JP4456229B2 JP 4456229 B2 JP4456229 B2 JP 4456229B2 JP 2000158411 A JP2000158411 A JP 2000158411A JP 2000158411 A JP2000158411 A JP 2000158411A JP 4456229 B2 JP4456229 B2 JP 4456229B2
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- 238000006243 chemical reaction Methods 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 33
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 26
- 150000004706 metal oxides Chemical class 0.000 title claims description 26
- 238000006555 catalytic reaction Methods 0.000 title claims description 12
- 229910000510 noble metal Inorganic materials 0.000 title description 13
- 239000003054 catalyst Substances 0.000 claims description 52
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 239000010931 gold Substances 0.000 claims description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052737 gold Inorganic materials 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 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 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000011882 ultra-fine particle Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 241000255925 Diptera Species 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 229910052703 rhodium Inorganic materials 0.000 description 2
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 150000004685 tetrahydrates Chemical class 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- -1 alkane alkenes Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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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
- 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
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- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、光照射による貴金属担持金属酸化物触媒反応における反応促進方法に関する。
【０００２】
【従来の技術】
貴金属担持酸化物触媒は、様々な反応において、熱反応触媒として高活性を示すことが知られている。より高活性な貴金属担持酸化物触媒を得るために、これまでは、担体と担持貴金属の組合せの変更、触媒の調製方法の変更などの手段が採られている。しかしながら、これらの方法では、満足できる結果が得られてない。
【０００３】
【発明が解決しようとする課題】
本発明は、貴金属担持金属酸化物触媒反応において、反応を促進させる方法を提供することを主な目的とする。
【０００４】
【課題を解決するための手段】
本発明者は、鋭意研究を重ねた結果、特定の光を照射することなどにより、貴金属担持金属酸化物触媒反応において、反応を促進できることを見出し、本発明を完成するに至った。
【０００５】
即ち、本発明は、下記の方法に係る。
１．貴金属担持金属酸化物触媒を使用する化学反応方法において、触媒に対して光照射をすることにより、反応を促進させることを特徴とする方法。
２．貴金属担持金属酸化物における貴金属が、金、白金、銀、パラジウム、ロジウム、ルテニウム、オスミウムおよびイリジウムからなる群から選択される少なくとも一種である上記１に記載の方法。
３．貴金属担持金属酸化物における貴金属が、超微粒子である上記１または２に記載の方法。
４．貴金属担持金属酸化物において、担体である金属酸化物が、チタン、アルミニウム、珪素、マグネシウム、バナジウム、クロム、マンガン、鉄、コバルト、銅、亜鉛、ガリウム、ゲルマニウム、ストロンチウム、イットリウム、ジルコニウム、カドミウム、インジウム、錫、アンチモン、バリウム、ランタン、ハフニウム、タリウム、タングステン、レニウム、リンおよびセリウムからなる群から選択される少なくとも一種を含む酸化物である上記１〜３のいずれかに記載の方法。
５．貴金属担持金属酸化物が、金-チタニア、金-アルミナ、金-シリカ、白金-チタニア、白金-シリカ、白金-アルミナ、銀-チタニア、銀-アルミナおよび銀-シリカからなる群から選択される少なくとも一種である上記１〜４のいずれかに記載の方法。
【０００６】
【発明の実施の形態】
本発明に係る触媒反応の反応促進方法は、貴金属担持金属酸化物触媒反応に光照射をすることにより、触媒反応を促進させる方法に係る。
【０００７】
照射する光の波長は、用いる触媒の種類、適用する反応などに応じて適宜設定することができる。照射する光の波長は、通常1〜1000nm程度、好ましくは200〜700nm程度である。例えば、COの酸化の場合には、通常約200nm以上、好ましくは200〜700nm程度である。例えば、金担持酸化チタン触媒を用いる場合には、通常約200nm以上、好ましくは200〜600nm程度である。例えば、金担持アルミナ触媒を用いる場合には、通常約200nm以上、好ましくは200〜600nm程度である。
【０００８】
本発明方法を適用できる貴金属担持金属酸化物は、特に制限されず、公知の貴金属担持金属酸化物触媒を適用できる。活性金属である貴金属は、特に制限されないが、例えば、金、白金、銀、パラジウム、ロジウム、ルテニウム、オスミウム、イリジウムなどを例示することができる。これらのなかでは、金が好ましい。活性金属である貴金属は、１種を単独で用いても良いが、２種以上を併用してもよい。
【０００９】
貴金属担持金属酸化物触媒に担持されている貴金属粒子の大きさは、特に制限されないが、超微粒子であることが好ましい。貴金属粒子の平均粒子径は、通常約250nm以下、好ましくは1〜10nm程度である。なお、金属微粒子の平均粒子径は、透過電子顕微鏡法による測定値とする。
【００１０】
貴金属担持金属酸化物触媒における貴金属の担持量は、特に制限されず、貴金属の種類などに応じて適宜設定することができるが、金属酸化物に対して、貴金属単体換算で通常10-3〜50重量％程度、好ましくは0.1〜10重量％程度である。
【００１１】
担体である金属酸化物は、特に制限されず、例えば、チタン、アルミニウム、珪素、マグネシウム、バナジウム、クロム、マンガン、鉄、コバルト、銅、亜鉛、ガリウム、ゲルマニウム、ストロンチウム、イットリウム、ジルコニウム、カドミウム、インジウム、錫、アンチモン、バリウム、ランタン、ハフニウム、タリウム、タングステン、レニウム、リン、セリウムなどの少なくとも一種を含む酸化物を例示することができる。担体である金属酸化物は、一種のみを用いてもよく、或いは上記の元素を含む酸化物の混合物であってもよく、或いは複合酸化物であってもよい。複合酸化物としては、例えば、チタニア-シリカ、シリカ-アルミナ、チタニア-アルミナ、シリカ-ジルコニア、シリカ-バナジアなどを例示することができる。
【００１２】
これらのなかでは、チタニア、アルミナ、シリカ、ジルコニア、酸化亜鉛、セリア、酸化マンガン、マグネシアなどが好ましく、チタニア、アルミナ、シリカなどが特にこのましい。
【００１３】
本発明は、金-チタニア、金-アルミナ、金-シリカ、白金-チタニア、白金-シリカ、白金-アルミナ、銀-チタニア、銀-アルミナ、銀-シリカなどの触媒に好適に適用できる。
【００１４】
貴金属担持金属酸化物触媒の比表面積は、特に制限されず、触媒の種類などに応じて適宜設定することができるが、BET法による測定値として、通常5〜1000m2/g程度、好まし10〜500m2/g程度である。
【００１５】
貴金属担持金属酸化物触媒の平均粒径は、特に制限されず、触媒の種類などに応じて、適宜設定することができるが、通常10〜1000μm程度、好ましくは100〜500μm程度である。この様な触媒は、メッシュを用いて選別する方法などにより得ることができる。
【００１６】
貴金属担持金属酸化物触媒は、公知の方法によって調製したものを用いてもよく、市販品を用いても良い。貴金属担持金属酸化物の調製法としては、例えば、共沈法(特開昭60-238148号など参照)、均一析出沈殿法(特開昭62-155937号など参照)、滴下中和沈殿法(特開昭63-252908号など参照)、還元剤添加法(特開昭63-252908号など参照)、pH制御中和沈殿法(特開昭63-252908号など参照)などを例示することができる。上記以外にも、特開平2-252610号、特開平3-97623号、特開平6-16422号、特開平9-122478号などに記載されている調整法を例示できる。
【００１７】
本発明の方法を適用できる反応は、熱触媒反応(反応自体が熱反応であって、触媒が熱触媒である反応)であれば、特に制限されない。このような、反応としては、COなどの可燃ガスのCO2への酸化反応、ホルムアルデヒドのCO2への酸化反応、水素の水への酸化反応、アルカンアルケンおよびアルキンの酸化反応などの可燃物の酸化反応などを例示することができる。アルカン・アルケンおよびアルキンの酸化反応における生成物としては、これらに対応するアルコール、アルデヒド、カルボン酸、エポキサイド；CO、CO2などを例示することができる。より具体的には、エチレンのエチレンオキサイドへの酸化、プロピレンのプロピレンオキサイドへの酸化などを例示することができる。
【００１８】
本発明方法を適用する場合の反応条件(例えば、反応圧力、反応温度、反応時間、触媒量)などは、特に制限されず、用いる触媒、反応系などに応じて適宜設定することができる。反応条件は、光照射を行わない場合と同様に設定してもよい。
【００１９】
本発明に適用する場合において用いる触媒量は、触媒の種類、反応の種類などに応じて適宜設定することができる。例えば、COなどの可燃ガスの酸化反応などの酸化反応においては、触媒中の貴金属の担持量に対して、通常約1000倍mol以下、好ましくは約100倍mol以下の反応原料を酸化することが可能である。或いは、流通式反応装置などを用いる場合には、触媒１gあたり、通常5000〜100000ml・h-1程度のガス(このうち反応原料となるガスの割合は0.1〜10vol％程度)を流通させることが可能である。流通させるガスに含まれる反応原料以外のガスとしては、Arなどの希ガス、N2などの不活性ガスを例示することができる。
【００２０】
【発明の効果】
本発明によれば、光を照射することにより、公知の触媒反応における触媒活性を高めることができる。
【００２１】
本発明によれば、光を照射することにより、より穏和な温度・圧力条件下で、高い触媒活性を得ることができる。
【００２２】
【実施例】
以下、実施例および比較例を示し、本発明の特徴とするところをより詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００２３】
実施例1および比較例１
金担持酸化チタン触媒(Au/TiO2)を用いたCOのCO2への酸化反応における光照射の有無による触媒活性の変化を調べた。光照射を行った場合を実施例１とし、光照射を行わなかった場合を比較例１とする。
【００２４】
反応条件は、以下の通りである。
・CO量：18μmol
・O2量：18μmol
・触媒量：50mg
・反応圧力：1kPa
・反応温度：5℃
・光源：高圧水銀ランプ(波長：200〜500nm)
用いた触媒は、S. Tsubota, D.A.H. Cunningham, Y. Bando and M. haruta, Preparation of Catalysts VI, eds. G. Poncelet et al., 227(Elsevier, Amsterdam, 1995)に記載されている析出沈殿法により調製した。即ち、塩化金酸四水和物(特級、キシダ化学製)0.2gと二酸化チタン(触媒学会参照触媒、JRC-TIO-4、アナターゼ：ルチル=3：1、比表面積約50m2/g)10gとを用い、析出沈殿法により形成された沈殿物を空気中400℃で4時間焼成した。得られた触媒の粒径は、125〜212μm程度であり、金微粒子の平均粒径は、約3nmであり、触媒における金の担持量は、酸化チタンに対して、1重量％であった。
【００２５】
比較例２
触媒として二酸化チタン(触媒学会参照触媒、JRC-TIO-4、アナターゼ：ルチル=3：1、比表面積約50m2/g)を用いた以外は、比較例１と同様の条件で光照射をせずにCOの酸化反応を行った。
【００２６】
比較例３
触媒として二酸化チタン(触媒学会参照触媒、JRC-TIO-4、アナターゼ：ルチル=3：1、比表面積約50m2/g)を用いた以外は、実施例１と同様の条件で光照射を行いながらCOの酸化反応を行った。
【００２７】
実施例１および比較例１〜３に記載したCO酸化反応におけるCO転換率の時間依存性を図１に示す。図１から明らかなように、Au/TiO2は、暗所においてもCOの酸化反応において、触媒活性を示すが(比較例１)、光を照射することにより、更に触媒反応が促進された。
【００２８】
一方、光触媒であるTiO2は、光照射を行わないと全く反応が進行せず(比較例２)、光照射下において、若干の光酸化触媒活性能を示した(比較例３)。
【００２９】
Au/TiO2系における光照射によって触媒活性が促進された程度は、TiO2系における光照射による触媒活性の促進程度に比して、著しく高いものであった。Au/TiO2系において、熱反応下、光照射によって、触媒反応の促進効果が得られたことが明らかである。
【００３０】
実施例２および比較例４
金担持アルミナ触媒(Au/Al2O3)のCOのCO2への酸化反応における光照射の有無による触媒活性の変化を調べた。光照射を行った場合を実施例２とし、光照射を行わなかった場合を比較例４とする。
【００３１】
反応条件は、以下の通りである。
・CO量：18μmol
・O2量：18μmol
・触媒量：50mg
・反応圧力：1kPa
・反応温度：5℃
・光源：高圧水銀ランプ(波長：200〜500nm)
用いた触媒は、S. Tsubota, D.A.H. Cunningham, Y. Bando and M. haruta, Preparation of Catalysts VI, eds. G. Poncelet et al., 227(Elsevier, Amsterdam, 1995)に記載されている析出沈殿法により調製した。即ち、塩化金酸四水和物(特級、キシダ化学製)0.1gと酸化アルミニウム(触媒学会参照触媒、JRC-ALO-7、比表面積約180m2/g)5gとを用い、析出沈殿法により形成された沈殿物を空気中400℃で4時間焼成した。得られた触媒の粒径は、125〜212μm程度であり、金微粒子の平均粒径は、約3nmであり、触媒における金の担持量は、アルミナに対して、1重量％であった。
【００３２】
実施例２および比較例４に記載したCO酸化反応におけるCO転換率の時間依存性を図２に示す。図２から明らかなように、反応開始後20分間は、実施例２と比較例４とは、ほぼ同等の触媒活性を示した。その後も実施例１では、触媒活性の低下がみられないのに対して、比較例４では、触媒活性の失活がみられた。
【００３３】
このことから、光照射により触媒活性の失活が妨げられた。
【図面の簡単な説明】
【図１】図１は、実施例１および比較例１〜３に記載したCO酸化反応におけるCO変換率/％の時間依存性を示す図である。
【図２】図２は、実施例２および比較例４に記載したCO酸化反応におけるCO変換率/％の時間依存性を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a reaction promotion method in a noble metal-supported metal oxide catalytic reaction by light irradiation.
[0002]
[Prior art]
The noble metal-supported oxide catalyst is known to exhibit high activity as a thermal reaction catalyst in various reactions. In order to obtain a more highly active noble metal-supported oxide catalyst, measures such as changing the combination of the support and the supported noble metal and changing the method for preparing the catalyst have been taken. However, these methods do not give satisfactory results.
[0003]
[Problems to be solved by the invention]
The main object of the present invention is to provide a method for promoting the reaction in the noble metal-supported metal oxide catalytic reaction.
[0004]
[Means for Solving the Problems]
As a result of intensive studies, the present inventor has found that the reaction can be promoted in the noble metal-supported metal oxide catalytic reaction by irradiating specific light, and the present invention has been completed.
[0005]
That is, the present invention relates to the following method.
1. In the chemical reaction method using a noble metal carrying | support metal oxide catalyst, reaction is accelerated | stimulated by irradiating light to a catalyst.
2. 2. The method according to 1 above, wherein the noble metal in the noble metal-supported metal oxide is at least one selected from the group consisting of gold, platinum, silver, palladium, rhodium, ruthenium, osmium and iridium.
3. 3. The method according to 1 or 2 above, wherein the noble metal in the noble metal-supported metal oxide is ultrafine particles.
4). In the noble metal-supported metal oxide, the metal oxide as a support is titanium, aluminum, silicon, magnesium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, cadmium, indium. 4. The method according to any one of 1 to 3 above, which is an oxide containing at least one selected from the group consisting of tin, antimony, barium, lanthanum, hafnium, thallium, tungsten, rhenium, phosphorus and cerium.
5). The noble metal-supported metal oxide is at least selected from the group consisting of gold-titania, gold-alumina, gold-silica, platinum-titania, platinum-silica, platinum-alumina, silver-titania, silver-alumina and silver-silica. 5. The method according to any one of the above 1 to 4, which is a kind.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The method for promoting the catalytic reaction according to the present invention relates to a method for promoting the catalytic reaction by irradiating the noble metal-supported metal oxide catalytic reaction with light.
[0007]
The wavelength of the irradiated light can be appropriately set according to the type of catalyst used, the reaction to be applied, and the like. The wavelength of the irradiated light is usually about 1 to 1000 nm, preferably about 200 to 700 nm. For example, in the case of oxidation of CO, it is usually about 200 nm or more, preferably about 200 to 700 nm. For example, when a gold-supported titanium oxide catalyst is used, it is usually about 200 nm or more, preferably about 200 to 600 nm. For example, when a gold supported alumina catalyst is used, it is usually about 200 nm or more, preferably about 200 to 600 nm.
[0008]
The noble metal-supported metal oxide to which the method of the present invention can be applied is not particularly limited, and a known noble metal-supported metal oxide catalyst can be applied. The noble metal that is an active metal is not particularly limited, and examples thereof include gold, platinum, silver, palladium, rhodium, ruthenium, osmium, and iridium. Of these, gold is preferred. The noble metal which is an active metal may be used alone or in combination of two or more.
[0009]
The size of the noble metal particles supported on the noble metal-supported metal oxide catalyst is not particularly limited, but is preferably ultrafine particles. The average particle diameter of the noble metal particles is usually about 250 nm or less, preferably about 1 to 10 nm. The average particle diameter of the metal fine particles is a value measured by transmission electron microscopy.
[0010]
The amount of the noble metal supported in the noble metal-supported metal oxide catalyst is not particularly limited and can be appropriately set according to the kind of the noble metal, but is usually 10 −3 to 50 in terms of the noble metal simple substance. It is about 0.1% by weight, preferably about 0.1 to 10% by weight.
[0011]
The metal oxide as the support is not particularly limited, and for example, titanium, aluminum, silicon, magnesium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, cadmium, indium Examples thereof include oxides containing at least one of tin, antimony, barium, lanthanum, hafnium, thallium, tungsten, rhenium, phosphorus, cerium, and the like. As the metal oxide as the support, only one kind may be used, or a mixture of oxides containing the above elements may be used, or a complex oxide may be used. Examples of the composite oxide include titania-silica, silica-alumina, titania-alumina, silica-zirconia, and silica-vanadia.
[0012]
Of these, titania, alumina, silica, zirconia, zinc oxide, ceria, manganese oxide, magnesia, and the like are preferable, and titania, alumina, silica, and the like are particularly preferable.
[0013]
The present invention can be suitably applied to catalysts such as gold-titania, gold-alumina, gold-silica, platinum-titania, platinum-silica, platinum-alumina, silver-titania, silver-alumina, and silver-silica.
[0014]
The specific surface area of the noble metal-supported metal oxide catalyst is not particularly limited and can be appropriately set according to the type of the catalyst, etc., but the measured value by the BET method is usually about 5 to 1000 m 2 / g, preferably 10 ~500m is about 2 / g.
[0015]
The average particle diameter of the noble metal-supported metal oxide catalyst is not particularly limited and can be appropriately set according to the type of the catalyst, but is usually about 10 to 1000 μm, preferably about 100 to 500 μm. Such a catalyst can be obtained by a method of selecting using a mesh.
[0016]
As the noble metal-supported metal oxide catalyst, one prepared by a known method may be used, or a commercially available product may be used. Examples of the method for preparing the noble metal-supported metal oxide include coprecipitation methods (see JP-A-60-238148, etc.), uniform precipitation precipitation methods (see JP-A-62-155937, etc.), drop neutralization precipitation methods ( Examples include JP-A-63-252908), reducing agent addition methods (see JP-A-63-252908 etc.), pH-controlled neutralization precipitation methods (see JP-A-63-252908 etc.), etc. it can. In addition to the above, the adjustment methods described in JP-A-2-52610, JP-A-3-97623, JP-A-6-16422, JP-A-9-122478 and the like can be exemplified.
[0017]
The reaction to which the method of the present invention can be applied is not particularly limited as long as it is a thermal catalytic reaction (the reaction itself is a thermal reaction and the catalyst is a thermal catalyst). Such reactions include oxidation reactions of combustible gases such as CO to CO 2 , oxidation reactions of formaldehyde to CO 2 , oxidation reactions of hydrogen to water, oxidation reactions of alkane alkenes and alkynes, etc. An oxidation reaction etc. can be illustrated. Examples of products in the oxidation reaction of alkanes, alkenes and alkynes include alcohols, aldehydes, carboxylic acids, epoxides corresponding to these, CO, CO 2 and the like. More specifically, oxidation of ethylene to ethylene oxide, oxidation of propylene to propylene oxide, and the like can be exemplified.
[0018]
Reaction conditions (for example, reaction pressure, reaction temperature, reaction time, amount of catalyst) and the like when applying the method of the present invention are not particularly limited, and can be appropriately set according to the catalyst used, the reaction system, and the like. You may set reaction conditions similarly to the case where light irradiation is not performed.
[0019]
The amount of catalyst used in the present invention can be appropriately set according to the type of catalyst, the type of reaction, and the like. For example, in an oxidation reaction such as an oxidation reaction of a combustible gas such as CO, the reaction raw material is usually oxidized about 1000 times mol or less, preferably about 100 times mol or less with respect to the amount of noble metal supported in the catalyst. Is possible. Alternatively, when using a flow reactor or the like, a gas of about 5000 to 1000 ml · h −1 is normally circulated per gram of catalyst (of which the ratio of the gas used as a reaction raw material is about 0.1 to 10 vol%). Is possible. Examples of the gas other than the reaction raw material contained in the gas to be circulated include a rare gas such as Ar and an inert gas such as N 2 .
[0020]
【The invention's effect】
According to the present invention, the catalytic activity in a known catalytic reaction can be enhanced by irradiating light.
[0021]
According to the present invention, high catalytic activity can be obtained by irradiating light under milder temperature and pressure conditions.
[0022]
【Example】
Examples and comparative examples will be described below to describe the features of the present invention in more detail. However, the present invention is not limited to these examples.
[0023]
Example 1 and Comparative Example 1
The change of catalytic activity with and without light irradiation in the oxidation reaction of CO to CO 2 using gold-supported titanium oxide catalyst (Au / TiO 2 ) was investigated. The case where light irradiation is performed is referred to as Example 1, and the case where light irradiation is not performed is referred to as Comparative Example 1.
[0024]
The reaction conditions are as follows.
・ CO amount: 18μmol
・ O 2 content: 18μmol
・ Catalyst amount: 50mg
・ Reaction pressure: 1kPa
・ Reaction temperature: 5 ℃
・ Light source: High-pressure mercury lamp (wavelength: 200-500 nm)
The catalyst used was a precipitation precipitation method described in S. Tsubota, DAH Cunningham, Y. Bando and M. haruta, Preparation of Catalysts VI, eds. G. Poncelet et al., 227 (Elsevier, Amsterdam, 1995). It was prepared by. That is, 0.2 g of chloroauric acid tetrahydrate (special grade, manufactured by Kishida Chemical Co., Ltd.) and titanium dioxide (see Catalytic Society Reference Catalyst, JRC-TIO-4, anatase: rutile = 3: 1, specific surface area of about 50 m 2 / g) The precipitate formed by the precipitation method was calcined in air at 400 ° C. for 4 hours. The obtained catalyst had a particle size of about 125 to 212 μm, the average particle size of the gold fine particles was about 3 nm, and the amount of gold supported on the catalyst was 1% by weight with respect to titanium oxide.
[0025]
Comparative Example 2
Irradiate light under the same conditions as in Comparative Example 1, except that titanium dioxide (catalyst society reference catalyst, JRC-TIO-4, anatase: rutile = 3: 1, specific surface area of about 50 m 2 / g) was used as the catalyst. The oxidation reaction of CO was performed.
[0026]
Comparative Example 3
Irradiation was carried out under the same conditions as in Example 1 except that titanium dioxide (catalyst society reference catalyst, JRC-TIO-4, anatase: rutile = 3: 1, specific surface area of about 50 m 2 / g) was used as the catalyst. The oxidation reaction of CO was performed.
[0027]
The time dependency of the CO conversion rate in the CO oxidation reaction described in Example 1 and Comparative Examples 1 to 3 is shown in FIG. As is clear from FIG. 1, Au / TiO 2 exhibited catalytic activity in the CO oxidation reaction even in the dark (Comparative Example 1), but the catalytic reaction was further promoted by irradiation with light.
[0028]
On the other hand, TiO 2 which is a photocatalyst does not proceed at all unless it is irradiated with light (Comparative Example 2), and exhibits a slight photooxidation catalytic activity ability under the light irradiation (Comparative Example 3).
[0029]
The degree to which the catalytic activity was promoted by light irradiation in the Au / TiO 2 system was significantly higher than the degree to which the catalytic activity was promoted by light irradiation in the TiO 2 system. In the Au / TiO 2 system, it is clear that the catalytic reaction promotion effect was obtained by light irradiation under thermal reaction.
[0030]
Example 2 and Comparative Example 4
The change in catalytic activity of gold-supported alumina catalyst (Au / Al 2 O 3 ) with and without light irradiation in the oxidation of CO to CO 2 was investigated. The case where light irradiation is performed is referred to as Example 2, and the case where light irradiation is not performed is referred to as Comparative Example 4.
[0031]
The reaction conditions are as follows.
・ CO amount: 18μmol
・ O 2 content: 18μmol
・ Catalyst amount: 50mg
・ Reaction pressure: 1kPa
・ Reaction temperature: 5 ℃
・ Light source: High-pressure mercury lamp (wavelength: 200-500 nm)
The catalyst used was a precipitation precipitation method described in S. Tsubota, DAH Cunningham, Y. Bando and M. haruta, Preparation of Catalysts VI, eds. G. Poncelet et al., 227 (Elsevier, Amsterdam, 1995). It was prepared by. That is, 0.1 g of chloroauric acid tetrahydrate (special grade, manufactured by Kishida Chemical Co., Ltd.) and 5 g of aluminum oxide (Catalyst Society Reference Catalyst, JRC-ALO-7, specific surface area of about 180 m 2 / g) are used, The formed precipitate was calcined in air at 400 ° C. for 4 hours. The obtained catalyst had a particle size of about 125 to 212 μm, the average particle size of the gold fine particles was about 3 nm, and the amount of gold supported on the catalyst was 1% by weight with respect to alumina.
[0032]
The time dependence of the CO conversion rate in the CO oxidation reaction described in Example 2 and Comparative Example 4 is shown in FIG. As is clear from FIG. 2, Example 2 and Comparative Example 4 exhibited almost the same catalytic activity for 20 minutes after the start of the reaction. Thereafter, in Example 1, no decrease in the catalyst activity was observed, whereas in Comparative Example 4, the catalyst activity was deactivated.
[0033]
For this reason, deactivation of the catalytic activity was prevented by light irradiation.
[Brief description of the drawings]
FIG. 1 is a graph showing the time dependence of CO conversion rate /% in the CO oxidation reaction described in Example 1 and Comparative Examples 1 to 3. FIG.
FIG. 2 is a graph showing the time dependence of CO conversion rate /% in the CO oxidation reaction described in Example 2 and Comparative Example 4;
Claims (5)
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