JP2013116440A - Oxidation catalyst - Google Patents
Oxidation catalyst Download PDFInfo
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- JP2013116440A JP2013116440A JP2011264534A JP2011264534A JP2013116440A JP 2013116440 A JP2013116440 A JP 2013116440A JP 2011264534 A JP2011264534 A JP 2011264534A JP 2011264534 A JP2011264534 A JP 2011264534A JP 2013116440 A JP2013116440 A JP 2013116440A
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- oxidation catalyst
- organic sulfur
- oxidation
- metal oxide
- catalyst according
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 230000003647 oxidation Effects 0.000 title claims abstract description 72
- 239000010931 gold Substances 0.000 claims abstract description 44
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 43
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 43
- 229910052737 gold Inorganic materials 0.000 claims abstract description 36
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000002898 organic sulfur compounds Chemical class 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 239000010419 fine particle Substances 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 13
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 claims description 12
- 150000003462 sulfoxides Chemical class 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 150000003457 sulfones Chemical class 0.000 claims description 7
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 34
- 239000011572 manganese Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 10
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- 229910016978 MnOx Inorganic materials 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
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- 238000010304 firing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
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- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002344 gold compounds Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 4
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- AUFHQOUHGKXFEM-UHFFFAOYSA-N C[Au]C Chemical compound C[Au]C AUFHQOUHGKXFEM-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- MIQUYXUHGQNVDN-UHFFFAOYSA-N ethane-1,2-diamine;gold Chemical compound [Au].NCCN MIQUYXUHGQNVDN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YEUYZNNBXLMFCW-UHFFFAOYSA-N 1-bromo-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(Br)C=C1 YEUYZNNBXLMFCW-UHFFFAOYSA-N 0.000 description 1
- KIQQUVJOLVCZKG-UHFFFAOYSA-N 1-chloro-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(Cl)C=C1 KIQQUVJOLVCZKG-UHFFFAOYSA-N 0.000 description 1
- XFUMHENRNCUHOH-UHFFFAOYSA-N 1-fluoro-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(F)C=C1 XFUMHENRNCUHOH-UHFFFAOYSA-N 0.000 description 1
- DQNSKXYRRRCKGH-UHFFFAOYSA-N 1-methoxy-4-methylsulfanylbenzene Chemical compound COC1=CC=C(SC)C=C1 DQNSKXYRRRCKGH-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- -1 NaAuCl 4) Chemical class 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AEHWKBXBXYNPCX-UHFFFAOYSA-N ethylsulfanylbenzene Chemical compound CCSC1=CC=CC=C1 AEHWKBXBXYNPCX-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VHILIAIEEYLJNA-UHFFFAOYSA-N methyl p-tolyl sulfide Chemical compound CSC1=CC=C(C)C=C1 VHILIAIEEYLJNA-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- GKYQBMNOFTZZSX-UHFFFAOYSA-K n-ethylethanamine;trichlorogold Chemical compound Cl[Au](Cl)Cl.CCNCC GKYQBMNOFTZZSX-UHFFFAOYSA-K 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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、有機硫黄化合物の酸化触媒に関し、さらに詳細には、有機硫黄化合物の特定基を選択的に酸化することができる酸化触媒に関するものである。 The present invention relates to an oxidation catalyst for an organic sulfur compound, and more particularly to an oxidation catalyst capable of selectively oxidizing a specific group of an organic sulfur compound.
環境負荷低減化や安全性確保の観点から、従来の毒性・爆発性の高い含重金属酸化剤に代わる酸化剤として酸素が注目され、酸素を用いた酸化反応のための触媒開発が進んでいる。大気中に豊富に存在する酸素だけを酸化剤とする反応は省資源・省エネルギーの理想的反応であるが、酸素の化学反応性の制御が難しく、酸化反応を特定の官能基において特定の価数に制御する点で選択性が低いという問題がある。
酸素を酸化剤として用いた酸化反応系として、特許文献１には二酸化マンガンの存在下で酸素含有気体を用いてポリスルフィドを含む白液を酸化し、パルプの収量を高めることが開示されている。しかし、かかる反応系では有機硫黄化合物を選択的に酸化し、スルホキシドやスルホンを合成するものではない。
From the viewpoint of reducing environmental burden and ensuring safety, oxygen is attracting attention as an oxidant that replaces the conventional highly toxic and explosive heavy metal oxidants, and catalysts for oxidation reactions using oxygen are being developed. The reaction using only oxygen abundant in the atmosphere as an oxidant is an ideal reaction for saving resources and energy, but it is difficult to control the chemical reactivity of oxygen, and the oxidation reaction has a specific valence at a specific functional group. However, there is a problem that the selectivity is low in terms of control.
As an oxidation reaction system using oxygen as an oxidizing agent, Patent Document 1 discloses that white liquor containing polysulfide is oxidized using an oxygen-containing gas in the presence of manganese dioxide to increase the yield of pulp. However, such a reaction system does not synthesize sulfoxide or sulfone by selectively oxidizing an organic sulfur compound.
そこで選択性高く酸化反応を制御できる酸素を用いた酸化反応用の触媒として金ナノ粒子触媒の開発が行われており、以前にアルコールやアミンの酸素酸化反応用の金ナノ粒子触媒を本発明者らは報告している(非特許文献１及び２)。
また、特許文献２には、酸化マンガンとアルミナを含む担体に白金成分等を担持させた炭化水素の水蒸気改質、自己熱改質又は部分酸化改質触媒が、特許文献３には、酸化マンガンと酸化鉄とからなる担体に金顆粒（５ナノ以下）を担持させた、選択的に一酸化炭素を酸化する触媒が、特許文献４には、酸化マンガンの存在下、マンガンイオン、クロムイオンおよびコバルトイオンからなる群より選ばれる少なくとも一種の金属イオンを含む水溶液からなる、二酸化炭素および酸素を接触させて二酸化炭素を酢酸に変換する触媒が、それぞれ提案されている。
Therefore, gold nanoparticle catalysts have been developed as catalysts for oxidation reactions using oxygen that can control the oxidation reaction with high selectivity, and gold nanoparticle catalysts for oxygen oxidation reactions of alcohols and amines have been developed by the present inventors. Have reported (Non-Patent Documents 1 and 2).
Patent Document 2 discloses a hydrocarbon steam reforming, autothermal reforming or partial oxidation reforming catalyst in which a platinum component or the like is supported on a carrier containing manganese oxide and alumina, and Patent Document 3 discloses manganese oxide. A catalyst that selectively oxidizes carbon monoxide, in which gold granules (5 nano or less) are supported on a support made of iron oxide and iron oxide, is disclosed in Patent Document 4 in the presence of manganese oxide. There have been proposed catalysts that convert carbon dioxide into acetic acid by contacting carbon dioxide and oxygen, which are made of an aqueous solution containing at least one metal ion selected from the group consisting of cobalt ions.
上述の金ナノ粒子触媒は、確かに酸化反応の触媒として有用であるが有機硫黄化合物の酸化に有用なものは提案されていないのが現状である。
有機硫黄化合物の酸化反応用の触媒として従来提案されているものでは、スルホキシドからさらにスルホンまで過剰酸化が進行し、スルホキシドを選択的に得ることが難しい。特に、酸素を酸化剤とした系ではスルフィドのスルホキシドへの選択的な酸化は未だ十分なものではない。
そのため、有機硫黄化合物の酸化反応を選択的に収率よく進行させることができる触媒の開発が要望されているのが現状である。
The gold nanoparticle catalyst described above is certainly useful as a catalyst for oxidation reaction, but at present, no catalyst useful for oxidation of organic sulfur compounds has been proposed.
Conventionally proposed catalysts for the oxidation reaction of organic sulfur compounds undergo excessive oxidation from sulfoxide to sulfone, making it difficult to selectively obtain sulfoxide. In particular, in a system using oxygen as an oxidizing agent, selective oxidation of sulfide to sulfoxide is not yet sufficient.
Therefore, at present, there is a demand for the development of a catalyst that can selectively advance the oxidation reaction of the organic sulfur compound with a high yield.
したがって本発明の目的は、有機硫黄化合物の酸化反応を選択的に収率よく進行させることができる触媒を提供するものである。 Accordingly, an object of the present invention is to provide a catalyst capable of allowing the oxidation reaction of an organic sulfur compound to proceed selectively with high yield.
本発明者らは上記課題を解消するために鋭意検討した結果、特定の金属酸化物に有機硫黄化合物の酸化触媒機能があることを知見し、さらに検討した結果、当該金属酸化物のみならず当該金属化合物に金微粒子を担持させてなるものも上記目的を達成しうることを見出し、本発明を完成するに至った。
すなわち、本発明は、以下の各発明を提供するものである。
１．下記式で表される化合物、ＣｕＭｎ２Ｏ４及びＶ2Ｏ5、からなる群より選択される１種以上の金属酸化物からなることを特徴とする有機硫黄化合物の酸化触媒（以下、「第１発明」という場合には、この発明をいう）。
式：ＭｎxＯy
（式中、ｘは１〜１０の整数を、ｙは１〜２０の整数を示し、ｙ≧ｘ、２≧ｙ／ｘ≧１である）
２．上記金属酸化物は、その形状が球状、板状又は棒状である粒子であり、粒子径が０．５ｎｍ〜１μｍである１記載の酸化触媒。
３．上記金属酸化物は、その形状が板状又は棒状である粒子であり、その厚さが５〜１００ｎｍである２記載の酸化触媒。
４．上記有機硫黄化合物の酸化に用いられる酸化剤が、酸素である１記載の酸化触媒。
５．上記有機硫黄化合物がメチルフェニルスルフィドであり、酸化反応により生成される生成物がスルホキシド又はスルホンである１記載の酸化触媒。
６．担体に金微粒子が担持されてなる、有機硫黄化合物の酸化触媒であって、
上記担体が、下記式で表される化合物、ＣｕＭｎ２Ｏ４、Ｖ2Ｏ5、Ｃｏ3Ｏ4及びＣｅＯ2からなる群より選択される１種以上の金属酸化物であることを特徴とする酸化触媒（以下、「第２発明」という場合には、この発明をいう）。
式：ＭｎxＯy
（式中、ｘは１〜１０の整数を、ｙは１〜２０の整数を示し、ｙ≧ｘ、２≧ｙ／ｘ≧１である）
７．上記金属酸化物は、その形状が球状、板状又は棒状である粒子であり、粒子径が０．５ｎｍ〜１μｍである６記載の酸化触媒。
８．上記金属酸化物は、その形状が板状又は棒状である粒子であり、その厚さが５〜１００ｎｍである７記載の酸化触媒。
９．上記金微粒子は、原子が８〜１００００個凝集してなる原子集合体を形成して担持されており、上記金微粒子各々の粒子径が０．８〜１０ｎｍである６記載の酸化触媒。
１０．上記有機硫黄化合物の酸化に用いられる酸化剤が、酸素である６記載の酸化触媒。
１１．上記有機硫黄化合物がメチルフェニルスルフィドであり、酸化反応により生成される生成物がスルホキシド又はスルホンである６記載の酸化触媒。
As a result of intensive investigations to solve the above problems, the present inventors have found that a specific metal oxide has an oxidation catalyst function of an organic sulfur compound, and as a result of further investigation, as a result of not only the metal oxide, The inventors have found that a metal compound having gold fine particles supported thereon can also achieve the above object, and have completed the present invention.
That is, the present invention provides the following inventions.
1. An organic sulfur compound oxidation catalyst (hereinafter referred to as “No. 1”) comprising at least one metal oxide selected from the group consisting of a compound represented by the following formula: CuMn 2 O 4 and V 2 O 5 "Invention" refers to this invention).
Formula: Mn x O y
(Wherein x represents an integer of 1 to 10, y represents an integer of 1 to 20, and y ≧ x, 2 ≧ y / x ≧ 1)
2. 2. The oxidation catalyst according to 1, wherein the metal oxide is a particle having a spherical shape, a plate shape, or a rod shape, and a particle diameter of 0.5 nm to 1 μm.
3. 3. The oxidation catalyst according to 2, wherein the metal oxide is a particle having a plate shape or a rod shape and a thickness of 5 to 100 nm.
4). 2. The oxidation catalyst according to 1, wherein the oxidizing agent used for oxidizing the organic sulfur compound is oxygen.
5. 2. The oxidation catalyst according to 1, wherein the organic sulfur compound is methylphenyl sulfide, and the product produced by the oxidation reaction is sulfoxide or sulfone.
6). An oxidation catalyst of an organic sulfur compound, in which gold fine particles are supported on a carrier,
The carrier is one or more metal oxides selected from the group consisting of a compound represented by the following formula, CuMn 2 O 4 , V 2 O 5 , Co 3 O 4 and CeO 2. Oxidation catalyst (hereinafter referred to as "the second invention" refers to this invention).
Formula: Mn x O y
(Wherein x represents an integer of 1 to 10, y represents an integer of 1 to 20, and y ≧ x, 2 ≧ y / x ≧ 1)
7). 7. The oxidation catalyst according to 6, wherein the metal oxide is a particle having a spherical shape, a plate shape, or a rod shape, and a particle diameter of 0.5 nm to 1 μm.
8). 8. The oxidation catalyst according to 7, wherein the metal oxide is a particle having a plate shape or a rod shape and a thickness of 5 to 100 nm.
9. 7. The oxidation catalyst according to 6, wherein the gold fine particles are supported by forming an atomic aggregate formed by agglomerating 8 to 10,000 atoms, and each of the gold fine particles has a particle diameter of 0.8 to 10 nm.
10. 7. The oxidation catalyst according to 6, wherein the oxidizing agent used for oxidizing the organic sulfur compound is oxygen.
11. 7. The oxidation catalyst according to 6, wherein the organic sulfur compound is methylphenyl sulfide, and the product produced by the oxidation reaction is sulfoxide or sulfone.
本発明の酸化触媒は、有機硫黄化合物の酸素による酸化反応を選択的に収率よく進行させることができるものである。特に金属酸化物を担体として金微粒子を担持させてなる酸化触媒が、特に収率良く、選択性高く、酸素を酸化物とした有機硫黄化合物の酸化反応を行うことができ、好ましいものである。 The oxidation catalyst of the present invention can selectively advance an oxidation reaction of an organic sulfur compound with oxygen with high yield. In particular, an oxidation catalyst in which gold fine particles are supported using a metal oxide as a carrier is preferable because it can perform an oxidation reaction of an organic sulfur compound using oxygen as an oxide with particularly high yield and high selectivity.
以下、本発明についてさらに詳細に説明する。
本発明（第１発明）の有機硫黄化合物の酸化触媒は、特定の金属酸化物であることを特徴とする。
以下詳述する。
Hereinafter, the present invention will be described in more detail.
The organic sulfur compound oxidation catalyst of the present invention (first invention) is a specific metal oxide.
This will be described in detail below.
＜有機硫黄化合物及び酸化剤＞
本発明の酸化触媒が酸化の対象とする上記有機硫黄化合物は、硫黄原子を含み酸化可能な有機化合物であれば特に制限なく用いることができるが、具体的には以下の化合物等を挙げることができる。
メチルフェニルスルフィド、4−メトキシチオアニソール、4−フルオロチオアニソール、４−ブロモチオアニソール、４−クロロチオアニソール、メチル（4−メチルフェニル）スルフィド、エチルフェニルスルフィド、ジフェニルスルフィド、テトラヒドロチオフェン、ジブチルスルフィド
上記有機硫黄化合物の酸化に用いられる酸化剤は、酸素であるのが好ましい。
<Organic sulfur compounds and oxidizing agents>
The organic sulfur compound to be oxidized by the oxidation catalyst of the present invention can be used without particular limitation as long as it contains a sulfur atom and can be oxidized, and specific examples thereof include the following compounds. it can.
Methyl phenyl sulfide, 4-methoxythioanisole, 4-fluorothioanisole, 4-bromothioanisole, 4-chlorothioanisole, methyl (4-methylphenyl) sulfide, ethylphenyl sulfide, diphenyl sulfide, tetrahydrothiophene, dibutyl sulfide The oxidizing agent used for the oxidation of the organic sulfur compound is preferably oxygen.
＜金属酸化物＞
本発明の酸化触媒である上記の特定の金属酸化物は、下記式で表される化合物、ＣｕＭｎ２Ｏ４及びＶ2Ｏ5からなる群より選択される金属酸化物の１種以上である。
式：ＭｎxＯy
（式中、ｘは１〜１０の整数を、ｙは１〜２０の整数を示し、ｙ≧ｘ、２≧ｙ／ｘ≧１である）
ｘ及びｙが上記範囲外であると、酸化触媒としての機能が低減する。
上記式で表される化合物としては、具体的には、ＭｎＯ、Ｍｎ３Ｏ４、Ｍｎ２Ｏ３、ＭｎＯ２ 等を挙げることができ、これらの２種以上を混合して用いてもよい。
<Metal oxide>
The specific metal oxide is an oxidation catalyst of the present invention is a compound represented by the following formula is at least one metal oxide selected from the group consisting of CuMn 2 O 4 and V 2 O 5.
Formula: Mn x O y
(Wherein x represents an integer of 1 to 10, y represents an integer of 1 to 20, and y ≧ x, 2 ≧ y / x ≧ 1)
When x and y are out of the above ranges, the function as an oxidation catalyst is reduced.
Specific examples of the compound represented by the above formula include MnO, Mn 3 O 4 , Mn 2 O 3 , and MnO 2 , and two or more of these may be used in combination.
本発明の酸化触媒又は上記担体としての金属酸化物の形状は、球状、板状、フラワー状、ロッド（棒）状等種々形態とすることができる。
また、本発明において上記担体としての金属酸化物の大きさは、平均粒子径で５ｎｍ〜１μｍであるのが好ましく、１０ｎｍから１，０００ｎｍであることがさらに好ましい。また、担持される上記金微粒子の粒子径の４〜２０倍であるのが好ましい。
また、板状、フラワー状、ロッド（棒）状である場合には、厚さが５ｎｍ〜１００ｎｍとするのが好ましい。
The shape of the oxidation catalyst of the present invention or the metal oxide as the carrier can be various forms such as a spherical shape, a plate shape, a flower shape, and a rod (rod) shape.
In the present invention, the size of the metal oxide as the carrier is preferably 5 nm to 1 μm as an average particle diameter, and more preferably 10 nm to 1,000 nm. Moreover, it is preferable that it is 4 to 20 times the particle diameter of the gold fine particles carried.
Moreover, when it is plate shape, flower shape, and rod (bar) shape, it is preferable that thickness shall be 5 nm-100 nm.
本発明においては上記金属酸化物として上記式で表される化合物、すなわち酸化マンガンを最も好ましく用いることができる。
酸化マンガンは、上述の具体的に例示した化合物をそれぞれ単独で用いてもよいが、２種以上混合して用いてもよい。特に好ましくは、ＭｎＯとＭｎ２Ｏ３とを、１：０．１〜１：１０で混合してなる酸化マンガン混合物を用いるのが好ましい。
酸化マンガンの結晶構造は特に制限されず、α型（ホーランダイト型）、β型（ルチル型）、γ型、δ型、λ型（スピネル型）、及びラムスデライト型の結晶構造を採用することができる。
In the present invention, the compound represented by the above formula, that is, manganese oxide can be most preferably used as the metal oxide.
As the manganese oxide, the compounds specifically exemplified above may be used singly or in combination of two or more. It is particularly preferable to use a manganese oxide mixture obtained by mixing MnO and Mn 2 O 3 in a ratio of 1: 0.1 to 1:10.
The crystal structure of manganese oxide is not particularly limited, and α-type (hollandite type), β-type (rutile type), γ-type, δ-type, λ-type (spinel type), and ramsdellite type crystal structures should be adopted. Can do.
上述の各金属酸化物はそれぞれ常法に従って得ることができる。
たとえば上記酸化マンガンは、例えば下記の反応式を満たす反応を行うことにより得ることができる。
2 KMnO4 + 3 Mn(NO3)2 +
6 NaOH → 5 MnO2 + 2 KOH + 6 NaNO3 + 2 H2O (1)
Mn(NO3)2 空気焼成→Mn2O3 (2)
Mn(NO3)2 + Na2CO3
→ MnO + 2 NaNO3 + 2 CO2 (3)
具体的にはたとえば、硝酸マンガン六水和物を蒸留水に溶解し、この水溶液を炭酸ナトリウム水溶液等に加え、反応させて、乾燥させた後、焼成を行うことにより得ることができる。
また、本発明の酸化触媒には、上述の担体及び金微粒子以外に本発明の所望の効果を損なわない範囲で他の成分を配合してもよい。
このようにして得られる本発明の酸化触媒の使用方法については後述する。
また酸化触媒の比表面積は、５０〜２００m2/gであるのが好ましい。
Each of the above metal oxides can be obtained according to a conventional method.
For example, the manganese oxide can be obtained, for example, by performing a reaction that satisfies the following reaction formula.
2 KMnO 4 + 3 Mn (NO 3 ) 2 +
6 NaOH → 5 MnO 2 + 2 KOH + 6 NaNO 3 + 2 H 2 O (1)
Mn (NO 3 ) 2 air firing → Mn 2 O 3 (2)
Mn (NO 3 ) 2 + Na 2 CO 3
→ MnO + 2 NaNO 3 + 2 CO 2 (3)
Specifically, for example, it can be obtained by dissolving manganese nitrate hexahydrate in distilled water, adding this aqueous solution to a sodium carbonate aqueous solution, reacting, drying, and then baking.
Moreover, you may mix | blend another component with the oxidation catalyst of this invention in the range which does not impair the desired effect of this invention other than the above-mentioned support | carrier and gold fine particle.
A method for using the oxidation catalyst of the present invention thus obtained will be described later.
The specific surface area of the oxidation catalyst is preferably 50 to 200 m 2 / g.
次いで、本発明（第２発明）の酸化触媒について説明する。有機硫黄化合物及び酸化剤については上述の第１発明と同じである。
本発明（第２発明）の酸化触媒は、担体に金微粒子が担持されてなる、有機硫黄化合物の酸化触媒であって、上記担体が、特定の金属酸化物であることを特徴とする。
＜金微粒子＞
本発明において用いられる金微粒子は、金原子が８〜１，０００個凝集してなる原子集合体を形成して担持されている。
上記金微粒子各々の粒子径（原子集合体の径）は、０．８〜１０ｎｍであるのが反応性の点で好ましい。
粒子径は、球状粒子の場合は直径、楕円形粒子の場合は長径であり、走査型電子顕微鏡（ＳＥＭ）観察あるいは透過型電子顕微鏡（ＴＥＭ）観察から、粒子径分布を作り、平均値を計算することで求めることができる。
また、粒子径の分布は上述の好ましい粒子径の範囲内にあるのが好ましい。
金微粒子の製造方法については、後述の酸化触媒の製造方法の欄において説明する。
Next, the oxidation catalyst of the present invention (second invention) will be described. The organic sulfur compound and the oxidizing agent are the same as those in the first invention.
The oxidation catalyst of the present invention (second invention) is an organic sulfur compound oxidation catalyst in which gold fine particles are supported on a carrier, wherein the carrier is a specific metal oxide.
<Gold fine particles>
The gold fine particles used in the present invention are supported by forming an atomic aggregate formed by aggregating 8 to 1,000 gold atoms.
The particle diameter of each gold fine particle (the diameter of the atomic aggregate) is preferably 0.8 to 10 nm from the viewpoint of reactivity.
The particle diameter is the diameter for spherical particles, and the long diameter for elliptical particles. From the observation with a scanning electron microscope (SEM) or transmission electron microscope (TEM), a particle diameter distribution is created and the average value is calculated. You can ask for it.
The particle size distribution is preferably within the above-mentioned preferable particle size range.
The method for producing the gold fine particles will be described in the column for the method for producing the oxidation catalyst described later.
＜担体＞
本発明において担体として用いられる上記の特定の金属酸化物は、下記式で表される化合物、ＣｕＭｎ２Ｏ４、Ｖ2Ｏ5、Ｃｏ3Ｏ4及びＣｅＯ2からなる群より選択される金属酸化物の１種以上である。
式：ＭｎxＯy
（式中、ｘは１〜１０の整数を、ｙは１〜２０の整数を示し、ｙ≧ｘ、２≧ｙ／ｘ≧１である）
ｘ及びｙが上記範囲外であると酸化触媒としての機能が低減する。
上記式で表される化合物としては、具体的には、ＭｎＯ、Ｍｎ３Ｏ４、Ｍｎ２Ｏ３、ＭｎＯ２ 等を挙げることができ、これらの２種以上を混合して用いてもよい。
<Carrier>
The specific metal oxide used as a carrier in the present invention is a metal oxide selected from the group consisting of a compound represented by the following formula, CuMn 2 O 4 , V 2 O 5 , Co 3 O 4 and CeO 2. One or more of the objects.
Formula: Mn x O y
(Wherein x represents an integer of 1 to 10, y represents an integer of 1 to 20, and y ≧ x, 2 ≧ y / x ≧ 1)
When x and y are out of the above ranges, the function as an oxidation catalyst is reduced.
Specific examples of the compound represented by the above formula include MnO, Mn 3 O 4 , Mn 2 O 3 , and MnO 2 , and two or more of these may be used in combination.
本発明の酸化触媒又は上記担体としての金属酸化物の形状は、球状、板状、フラワー状、ロッド（棒）状等種々形態とすることができる。
また、本発明において上記担体としての金属酸化物の大きさは、平均粒子径で０．５ｎｍ〜１μｍであるのが好ましく、１０ｎｍから１，０００ｎｍであることがさらに好ましい。また、担持される上記金微粒子の粒子径の４〜２０倍であるのが好ましい。
また、板状、フラワー状、ロッド（棒）状である場合には、厚さを５ｎｍ〜１００ｎｍとするのが好ましい。
The shape of the oxidation catalyst of the present invention or the metal oxide as the carrier can be various forms such as a spherical shape, a plate shape, a flower shape, and a rod (rod) shape.
In the present invention, the average size of the metal oxide as the carrier is preferably 0.5 nm to 1 μm, and more preferably 10 nm to 1,000 nm. Moreover, it is preferable that it is 4 to 20 times the particle diameter of the gold fine particles carried.
In the case of a plate shape, a flower shape, or a rod (rod) shape, the thickness is preferably 5 nm to 100 nm.
本発明においては上記金属酸化物として上記式で表される化合物、すなわち酸化マンガンを最も好ましく用いることができる。
酸化マンガンは、上述の具体的に例示した化合物をそれぞれ単独で用いてもよいが、２種以上混合して用いてもよい。特に好ましくは、ＭｎＯとＭｎ２Ｏ３とを、１：０．１〜１：１０で混合してなる酸化マンガン混合物を用いるのが好ましい。
酸化マンガンの結晶構造は特に制限されず、α型（ホーランダイト型）、β型（ルチル型）、γ型、δ型、λ型（スピネル型）、及びラムスデライト型の結晶構造を採用することができる。
In the present invention, the compound represented by the above formula, that is, manganese oxide can be most preferably used as the metal oxide.
As the manganese oxide, the compounds specifically exemplified above may be used singly or in combination of two or more. It is particularly preferable to use a manganese oxide mixture obtained by mixing MnO and Mn 2 O 3 in a ratio of 1: 0.1 to 1:10.
The crystal structure of manganese oxide is not particularly limited, and α-type (hollandite type), β-type (rutile type), γ-type, δ-type, λ-type (spinel type), and ramsdellite type crystal structures should be adopted. Can do.
上記酸化マンガンは、常法に従い製造することができ、例えば下記の反応式を満たす反応を行うことにより得ることができる。
2KMnO4 + 3Mn(NO3)2 +6NaOH
→5MnO2 +2KOH+6NaNO3 +2H2O(1)
Mn(NO3)2 空気焼成→Mn2O3 (2)
Mn(NO3)2 +Na2CO3→
MnO +2NaNO3 +2CO2 (3)
具体的にはたとえば、硝酸マンガン六水和物を蒸留水に溶解し、この水溶液を炭酸ナトリウム水溶液等に加え、反応させて、乾燥させた後、焼成を行うことにより得ることができる。
The said manganese oxide can be manufactured in accordance with a conventional method, for example, can be obtained by performing reaction which satisfy | fills the following reaction formula.
2KMnO 4 + 3Mn (NO 3 ) 2 + 6NaOH
→ 5MnO 2 + 2KOH + 6NaNO 3 + 2H 2 O (1)
Mn (NO 3 ) 2 air firing → Mn 2 O 3 (2)
Mn (NO 3 ) 2 + Na 2 CO 3 →
MnO + 2NaNO 3 + 2CO 2 (3)
Specifically, for example, it can be obtained by dissolving manganese nitrate hexahydrate in distilled water, adding this aqueous solution to a sodium carbonate aqueous solution, reacting, drying, and then baking.
＜金微粒子の含有形態及び割合＞
本発明の酸化触媒において、上記金微粒子は、たとえば担体が板状の場合には、その表裏両面に複数個規則的に配置されているのが好ましい。
上記担体と上記金微粒子との重量割合は、担体１００重量部に対して、上記金微粒子０．１〜１０重量部であるのが好ましい。
また酸化触媒の比表面積は、５０〜２００m2/gであるのが好ましい。
<Contained form and proportion of fine gold particles>
In the oxidation catalyst of the present invention, it is preferable that a plurality of the gold fine particles are regularly arranged on both the front and back surfaces, for example, when the carrier is plate-shaped.
The weight ratio of the carrier to the gold fine particles is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the carrier.
The specific surface area of the oxidation catalyst is preferably 50 to 200 m 2 / g.
＜第３成分＞
また、本発明の酸化触媒には、上述の担体及び金微粒子以外に本発明の所望の効果を損なわない範囲で他の成分を配合してもよい。
<Third component>
Moreover, you may mix | blend another component with the oxidation catalyst of this invention in the range which does not impair the desired effect of this invention other than the above-mentioned support | carrier and gold fine particle.
＜製造方法＞
第２発明の酸化触媒は、金属酸化物表面に金微粒子を分散・固定させる方法として従来公知の手法を特に制限なく採用して製造することができる。
たとえば、析出沈殿法の他、共沈法、析出還元法、気相グラフティング、固相混合法などが挙げられる。
例えば、析出沈殿法により製造する方法を示すと、金属酸化物粒子粉末を板状、球状、円筒状、蜂の巣状などの支持体に担持させて成形された成形体を金化合物の水溶液に懸濁するかまたは浸漬させ、アルカリを加えてｐＨを７〜１０の範囲に調整し、金水酸化物を金属酸化物表面上に析出沈殿させる。水溶液の金化合物濃度を後述の範囲に調整すると共に、ｐＨを上述の範囲に、温度を好ましくは０〜９０℃、特に好ましくは３０℃から７０℃までの範囲に調整して、攪拌を１時間以上続けることにより金水酸化物が表面に分散・固定化された金属酸化物が得られる。これを水洗し、乾燥後、３００℃以上で空気焼成することによって、金微粒子が担体表面に担持された酸化触媒が得られる。
<Manufacturing method>
The oxidation catalyst of the second invention can be produced by employing a conventionally known method without any limitation as a method for dispersing and fixing gold fine particles on the surface of the metal oxide.
For example, in addition to the precipitation method, a coprecipitation method, a precipitation reduction method, a gas phase grafting method, a solid phase mixing method, and the like can be given.
For example, a method for producing by precipitation method is shown: a molded body formed by supporting metal oxide particle powder on a plate-like, spherical, cylindrical, or honeycomb-like support is suspended in an aqueous solution of a gold compound. Or dipping and adding an alkali to adjust the pH to a range of 7 to 10 to precipitate and precipitate the gold hydroxide on the surface of the metal oxide. While adjusting the gold compound concentration of the aqueous solution to the range described later, the pH is adjusted to the above-mentioned range, the temperature is preferably adjusted to 0 to 90 ° C., particularly preferably from 30 ° C. to 70 ° C., and stirring is performed for 1 hour. By continuing the above, a metal oxide in which gold hydroxide is dispersed and immobilized on the surface can be obtained. This is washed with water, dried, and then fired at 300 ° C. or higher to obtain an oxidation catalyst in which gold fine particles are supported on the surface of the carrier.
上記金化合物としては、特に制限されないが、例えば、四塩化金酸（ＨＡｕＣｌ4）、四塩化金酸塩（例えばＮａＡｕＣｌ4）、シアン化金（ＡｕＣＮ）、シアン化金カリウム｛Ｋ［Ａｕ（ＣＮ）2］｝、三塩化ジエチルアミン金酸［（Ｃ2Ｈ5）2ＮＨ・ＡｕＣｌ3］、エチレンジアミン金錯体（例えば、塩化物錯体｛Ａｕ［Ｃ2Ｈ4（ＮＨ2）2］2Ｃｌ3｝）、ジメチル金β‐ジケトン誘導体錯体（例えば、ジメチル金アセチルアセトナート｛（ＣＨ3）2Ａｕ［ＣＨ3ＣＯＣＨＣＯＣＨ3］｝）や、その他、水や有機溶媒に溶解できる金の塩や錯体などが挙げられる。 Examples of the gold compound is not particularly limited, for example, tetrachloroauric acid (HAuCl 4), tetrachloroauric acid salts (e.g., NaAuCl 4), gold cyanide (AuCN), potassium gold cyanide {K [Au (CN ) 2 ]}, diethylamine trichloride gold acid [(C 2 H 5 ) 2 NH · AuCl 3 ], ethylenediamine gold complex (for example, chloride complex {Au [C 2 H 4 (NH 2 ) 2 ] 2 Cl 3 }) ), Dimethylgold β-diketone derivative complexes (for example, dimethylgold acetylacetonate {(CH 3 ) 2 Au [CH 3 COCHCOCH 3 ]}), and other gold salts and complexes that can be dissolved in water or organic solvents. Can be mentioned.
金化合物の水溶液中の濃度は、希薄すぎると金が金属酸化物上に水酸化物として析出できなくなり、濃厚すぎると金属酸化物上だけでなく溶液中でも金水酸化物の沈殿が起こってしまうので、０．１ｍｍｏｌ／Ｌから１０ｍｍｏｌ／Ｌまでの範囲が望ましく、０．５ｍｍｏｌ／Ｌから２ｍｍｏｌ／Ｌまでの範囲がより望ましい。
ｐＨ調整用のアルカリとしては、アルカリ金属の水酸化物や炭酸塩、アルカリ土類金属の水酸化物や炭酸塩、アンモニア、尿素などを使うことができる。上記溶液のｐＨは、好ましくは５〜１３、さらに好ましくは６〜１０であり、金の水酸化物の溶解度が相対的に低い範囲を選ぶことが肝要である。
If the concentration of the gold compound in the aqueous solution is too dilute, gold cannot be deposited as a hydroxide on the metal oxide, and if it is too thick, the gold hydroxide precipitates not only on the metal oxide but also in the solution. The range from 0.1 mmol / L to 10 mmol / L is desirable, and the range from 0.5 mmol / L to 2 mmol / L is more desirable.
As the alkali for pH adjustment, alkali metal hydroxide or carbonate, alkaline earth metal hydroxide or carbonate, ammonia, urea or the like can be used. The pH of the solution is preferably 5 to 13, more preferably 6 to 10, and it is important to select a range in which the solubility of gold hydroxide is relatively low.
＜使用方法（第１発明及び第２発明共通）＞
本発明の酸化触媒は、有機硫黄化合物の酸化反応に用いられるものであり、その反応形態は特に制限されないが、具体的にはたとえば以下の有機硫黄酸化物の製造方法に適用することができる。
有機硫黄化合物と、酸化剤としての酸素と、本発明の酸化触媒とを、好ましくは反応温度５０〜２００℃、さらに好ましくは８０〜１４０℃で、好ましくは１０〜４０時間、酸素圧力が好ましくは１〜１５atm(ゲージ圧０．０〜１．４MPa)、好ましくは３〜１１atm(ゲージ圧０．２〜１．０MPa)の反応条件で、無溶媒又は下記反応溶媒中で反応させる製造方法。
反応溶媒：トルエン、キシレン、クロロベンゼン、1,2-ジクロロベンゼンなどの芳香族炭化水素溶媒、N,N-ジメチルホルムアミドや1，4−ジオキサンなどの高極性溶媒等、中でも特に1,2-ジクロロベンゼンが効果的である。
また、酸化触媒の使用量は特に制限されないが、上記有機硫黄化合物１００重量部に対して０．１〜５００重量部とするのが好ましい。
<How to use (common to the first and second inventions)>
The oxidation catalyst of the present invention is used for an oxidation reaction of an organic sulfur compound, and the reaction form is not particularly limited. Specifically, for example, the oxidation catalyst can be applied to the following method for producing an organic sulfur oxide.
The organic sulfur compound, oxygen as an oxidizing agent, and the oxidation catalyst of the present invention are preferably reacted at a temperature of 50 to 200 ° C., more preferably 80 to 140 ° C., preferably 10 to 40 hours, preferably an oxygen pressure. A production method in which the reaction is carried out in the absence of a solvent or in the following reaction solvent under reaction conditions of 1 to 15 atm (gauge pressure 0.0 to 1.4 MPa), preferably 3 to 11 atm (gauge pressure 0.2 to 1.0 MPa).
Reaction solvent: aromatic hydrocarbon solvents such as toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, highly polar solvents such as N, N-dimethylformamide and 1,4-dioxane, especially 1,2-dichlorobenzene Is effective.
The amount of the oxidation catalyst used is not particularly limited, but is preferably 0.1 to 500 parts by weight with respect to 100 parts by weight of the organic sulfur compound.
なお、本発明において、「選択的」とは、酸化対象物の特定基を特定の価数で反応させることを意味する。 In the present invention, “selective” means that a specific group of an oxidation target is reacted at a specific valence.
以下、本発明を実施例及び比較例によりさらに具体的に説明するが、本発明はこれらに制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not restrict | limited to these.
〔実施例1〕 ＭｎＯｘの調製（３００ ℃、４時間焼成)
硝酸マンガン六水和物 （１１．５ ｇ,０．０４ｍｏｌ）を４００ｍＬの蒸留水に溶解した。得られた水溶液を０．１Ｍ炭酸ナトリウム水溶液４８０ｍＬに一気に加え、室温で1時間撹拌した。生じた沈殿物を上澄み液のpHが安定するまで、蒸留水で洗浄し、吸引ろ過して沈殿物のみを取り出し、得られた沈殿物を１２０℃で一晩乾燥した後、空気中３００℃で４時間焼成を行い、粉末の焼成物を得た。
得られた焼成物についてＸＲＤパターンを測定したところ、ＭｎＯ２とＭｎ２Ｏ３の混合物であった。
[Example 1] Preparation of MnOx (calcined at 300 ° C for 4 hours)
Manganese nitrate hexahydrate (11.5 g, 0.04 mol) was dissolved in 400 mL of distilled water. The obtained aqueous solution was added all at once to 480 mL of a 0.1 M aqueous sodium carbonate solution and stirred at room temperature for 1 hour. The resulting precipitate is washed with distilled water until the pH of the supernatant is stabilized, suction filtered to remove only the precipitate, and the resulting precipitate is dried at 120 ° C. overnight and then at 300 ° C. in air. Firing was performed for 4 hours to obtain a powder fired product.
When the XRD pattern was measured about the obtained baked product, it was a mixture of MnO 2 and Mn 2 O 3 .
〔実施例2〕 ＭｎＯｘの調製（２００℃,２時間水素還元)
実施例１で得られた粉末をＵ字管に充填して、水素１０ｖｏｌ％を含む窒素ガスを流通させてから２００℃に昇温して２時間還元処理を行った。
得られた粉末についてＸＲＤパターンを測定したところ、Ｍｎ２Ｏ３とＭｎ３Ｏ４、ＭｎＯの混合物であることがわかった。
〔実施例３〕 ＭｎＯｘの調製（３００℃,１０時間水素還元)
実施例１で得られた粉末をＵ字管に充填して、水素１０ｖｏｌ％を含む窒素ガスを流通させてから３００℃に昇温して10時間還元処理を行った。
得られた粉末についてＸＲＤパターンを測定したところ、Ｍｎ３Ｏ４とＭｎＯの混合物であることがわかった。
〔実施例４〕ＭｎＯ２の調製
硝酸マンガン六水和物(２１．５ｇ,０．０７５ｍｏｌ)を１２５ｍＬの蒸留水に溶解して、得られた水溶液を過マンガン酸カリウム（７．９
ｇ,０．０５０ｍｏｌ）と水酸化カリウム（６．０ｇ,０．１５ｍｏｌ）との水溶液１２５
ｍＬに一気に加え、その後室温で１時間撹拌した。ここで、生じた沈殿物を上澄み液のｐＨが安定するまで蒸留水で洗浄した後、吸引ろ過し、１２０℃で一晩乾燥した。乾燥終了後、空気中３００℃で４時間焼成を行い、粉体の焼成物を得た。
得られた粉末についてＸＲＤパターンを測定したところ、ＭｎＯ2担体であることがわかった。
[Example 2] Preparation of MnOx (hydrogen reduction at 200 ° C for 2 hours)
The powder obtained in Example 1 was filled in a U-shaped tube, and after flowing nitrogen gas containing 10 vol% of hydrogen, the temperature was raised to 200 ° C. and reduction treatment was performed for 2 hours.
The obtained powder of a XRD pattern was measured and found to be a mixture of Mn 2 O 3 and Mn 3 O 4, MnO.
Example 3 Preparation of MnOx (hydrogen reduction at 300 ° C. for 10 hours)
The powder obtained in Example 1 was filled in a U-shaped tube, and after nitrogen gas containing 10 vol% of hydrogen was circulated, the temperature was raised to 300 ° C. and reduction treatment was performed for 10 hours.
The obtained powder of a XRD pattern was measured and found to be a mixture of Mn 3 O 4 and MnO.
Example 4 Preparation of MnO 2 Manganese nitrate hexahydrate (21.5 g, 0.075 mol) was dissolved in 125 mL of distilled water, and the resulting aqueous solution was dissolved in potassium permanganate (7.9).
g, 0.050 mol) and potassium hydroxide (6.0 g, 0.15 mol) 125
The mixture was added to mL at once, and then stirred at room temperature for 1 hour. Here, the resulting precipitate was washed with distilled water until the pH of the supernatant was stabilized, then suction filtered and dried at 120 ° C. overnight. After the completion of drying, firing was performed in air at 300 ° C. for 4 hours to obtain a powdered fired product.
The obtained powder of a XRD pattern was measured and found to be MnO 2 carrier.
〔実施例５〕 １ｗｔ％（Ａｕの重量がＭｎＯxの重量の１％、以下同じ）Ａｕ／ＭｎＯｘの調製（析出沈殿法）
２１．５ｍｇのエチレンジアミン金錯体｛Ａｕ［Ｃ2Ｈ4（ＮＨ2）2］2Ｃｌ3｝を水に溶解して得られた１×１０−３ Ｍの水溶液５０ｍＬを７０ ℃に加熱した。これに０．１ Ｍ 水酸化ナトリウム水溶液を添加してｐＨ７付近に調整し、担体として実施例１で得られたＭｎＯ２とＭｎ２Ｏ３の混合物１．０ｇを加え、７０℃で１時間撹拌した後、沈殿物を上澄み液のｐＨが安定するまで、蒸留水で洗浄した。吸引ろ過して沈殿物を分離し、得られた沈殿物を１２０℃で一晩乾燥した後、空気中３００℃で４時間焼成を行い、目的とする金微粒子が担持された本発明の酸化触媒を得た。
〔実施例６〕 １ｗｔ％Ａｕ／ＭｎＯ２の調製
（析出沈殿法）
担体として実施例4で得たＭｎＯ２を用いた以外は実施例５と同様にして本発明の酸化触媒を得た。
〔実施例７〕 １ｗｔ％Ａｕ／ＭｎＯｘの調製
（固相混合法）
１６．８ｍｇのジメチル金アセチルアセトナートを秤量し、実施例１で得たＭｎＯ２とＭｎ２Ｏ３の混合物１．０ｇと一緒に乳鉢で磨砕混合を２０分間行った。その後、混合粉末を空気中３００℃で４時間焼成
を行い、酸化触媒を得た。
〔実施例８〕１ｗｔ％Ａｕ／ＭｎＯ２の調製（固相混合法）
担体として、実施例４で得たＭｎＯ２を用いた以外は実施例７と同様にして酸化触媒を得た。
〔実施例９〕１ｗｔ％Ａｕ／Ｖ２Ｏ５の調製
（固相混合法）
担体として、Ｖ２Ｏ５（実施例９）を用いた以外は実施例７と同様にして酸化触媒を得た。
[Example 5] 1 wt% (Au weight is 1% of MnOx weight, the same applies hereinafter) Preparation of Au / MnOx (precipitation precipitation method)
50 mL of a 1 × 10 −3 M aqueous solution obtained by dissolving 21.5 mg of ethylenediamine gold complex {Au [C 2 H 4 (NH 2 ) 2 ] 2 Cl 3 } in water was heated to 70 ° C. A 0.1 M aqueous sodium hydroxide solution was added thereto to adjust the pH to around 7, and 1.0 g of a mixture of MnO 2 and Mn 2 O 3 obtained in Example 1 was added as a carrier, followed by stirring at 70 ° C. for 1 hour. After that, the precipitate was washed with distilled water until the pH of the supernatant was stabilized. The precipitate is separated by suction filtration, and the resulting precipitate is dried at 120 ° C. overnight and then calcined in air at 300 ° C. for 4 hours to carry the target gold fine particles supported by the present invention. Got.
[Example 6] Preparation of 1 wt% Au / MnO 2 (precipitation precipitation method)
An oxidation catalyst of the present invention was obtained in the same manner as in Example 5 except that MnO 2 obtained in Example 4 was used as the carrier.
[Example 7] Preparation of 1 wt% Au / MnOx (solid phase mixing method)
16.8 mg of dimethyl gold acetylacetonate was weighed and ground and mixed in a mortar with 1.0 g of the mixture of MnO 2 and Mn 2 O 3 obtained in Example 1 for 20 minutes. Thereafter, the mixed powder was calcined in air at 300 ° C. for 4 hours to obtain an oxidation catalyst.
[Example 8] Preparation of 1 wt% Au / MnO 2 (solid phase mixing method)
An oxidation catalyst was obtained in the same manner as in Example 7 except that MnO 2 obtained in Example 4 was used as the carrier.
Preparation of Example 9 1wt% Au / V 2 O 5 ( solid mixing method)
An oxidation catalyst was obtained in the same manner as in Example 7 except that V 2 O 5 (Example 9) was used as the carrier.
〔実施例１０〕 Ａｕ／Ｃｏ３Ｏ４の調製（Ａｕ／Ｃｏ＝１／１９重量比)（共沈法）
３．２Ｍの四塩化金酸０．２ｍＬと硝酸コバルト六水和物３．５８ｇを１２９ｍＬの蒸留水に溶解した。この溶液を０．１Ｍ炭酸ナトリウム水溶液１６３ｍＬに一気に加え、室温で３時間撹拌した。生じた沈殿物を上澄み液のｐＨが安定するまで、蒸留水で洗浄した。吸引ろ過、１２０℃で一晩乾燥した後、空気中４００℃で５時間焼成を行った。
〔実施例１１〕 １ｗｔ％Ａｕ／ＣｅＯ２の調製（析出沈殿法）
金化合物として四塩化金酸を、担体としてＣｅＯ２を用いた以外は実施例５と同様にして触媒を得た。
[Example 10] Preparation of Au / Co 3 O 4 (Au / Co = 1/19 weight ratio) (coprecipitation method)
3.2 mL of 3.2 M tetrachloroauric acid and 3.58 g of cobalt nitrate hexahydrate were dissolved in 129 mL of distilled water. This solution was added all at once to 163 mL of a 0.1 M aqueous sodium carbonate solution and stirred at room temperature for 3 hours. The resulting precipitate was washed with distilled water until the pH of the supernatant was stabilized. After suction filtration and drying at 120 ° C. overnight, calcination was performed in air at 400 ° C. for 5 hours.
Preparation of Example 11 1wt% Au / CeO 2 (deposition precipitation method)
A catalyst was obtained in the same manner as in Example 5 except that tetrachloroauric acid was used as the gold compound and CeO 2 was used as the carrier.
得られた酸化触媒及び触媒を用いてスルフィドの酸素酸化反応を行い、効果を確認した。
〔試験例１〕触媒の選択(金担持金属酸化物および金属酸化物)
撹拌子を付したオートクレーブにメチルフェニルスルフィド(表１の1で示す化合物) （５８．８μＬ,０．５ｍｍｏｌ）、実施例１で得られた酸化触媒又は触媒（９８．５ ｇ）、トルエン（５ｍＬ）を投入し、さらに。酸素を室温で６ａｔｍ(ゲージ圧０．５ ＭＰａ)となる様に封入した。その後、１００℃に昇温し２４時間撹拌した。撹拌終了後、常温に戻し、内部標準としてメシチレン（３４．８μＬ,０．２５ｍｍｏｌ）を加え、クロロホルムで希釈し、反応終了物を得た。得られた反応終了物をろ過して触媒を除去し、反応生成物溶液を得た。得られた反応生成物溶液を少量取り出しＣＤＣｌ３で希釈したものを１Ｈ−ＮＭＲ測定(日本電子製３００ＭＨｚＮＭＲ)し、収率及び選択性を求めた。その結果を表２に示す。
また、実施例１、５、６、８で得られた酸化触媒について比表面積を測定した。比表面積の測定はTristar 3000（商品名、島津製作所）を用いて窒素吸着により行った。また測定前処理として、真空下で200℃2時間焼成を行ってから測定した。
その結果、実施例１：１３３m2/g、実施例5：１３４ m2/g、実施例６：８６m2/g、実施例８：６９m2/gであった。
Using the obtained oxidation catalyst and catalyst, oxygen oxidation reaction of sulfide was performed to confirm the effect.
[Test Example 1] Selection of catalyst (gold-supported metal oxide and metal oxide)
In an autoclave equipped with a stirrer, methylphenyl sulfide (compound represented by 1 in Table 1) (58.8 μL, 0.5 mmol), the oxidation catalyst or catalyst obtained in Example 1 (98.5 g), toluene (5 mL) ) And further. Oxygen was sealed at room temperature so that the pressure was 6 atm (gauge pressure 0.5 MPa). Then, it heated up at 100 degreeC and stirred for 24 hours. After completion of the stirring, the temperature was returned to room temperature, mesitylene (34.8 μL, 0.25 mmol) was added as an internal standard, and diluted with chloroform to obtain a reaction finished product. The obtained reaction product was filtered to remove the catalyst, thereby obtaining a reaction product solution. A small amount of the obtained reaction product solution was taken out and diluted with CDCl 3 , and subjected to 1 H-NMR measurement (300 MHz NMR manufactured by JEOL Ltd.) to determine yield and selectivity. The results are shown in Table 2.
Further, the specific surface area of the oxidation catalysts obtained in Examples 1, 5, 6, and 8 was measured. The specific surface area was measured by nitrogen adsorption using Tristar 3000 (trade name, Shimadzu Corporation). Further, as a pretreatment for measurement, measurement was performed after firing at 200 ° C. for 2 hours under vacuum.
As a result, Example 1 was 133 m 2 / g, Example 5 was 134 m 2 / g, Example 6 was 86 m 2 / g, and Example 8 was 69 m 2 / g.
〔試験例２〜７〕
それぞれ実施例１で得られた触媒に変えて実施例２〜７で得られた触媒を用いた以外は試験例１と同様にして試験を行い、収率と選択性とを確認した。
[Test Examples 2 to 7]
Tests were conducted in the same manner as in Test Example 1 except that the catalysts obtained in Examples 2 to 7 were used in place of the catalyst obtained in Example 1, and the yield and selectivity were confirmed.
〔比較例１〜４〕
担体として、ＴｉＯ２（比較例１）、Ｆｅ２Ｏ３（比較例２）、ＮｉＯ（比較例３）、ＣｕＯ（比較例４）及びＺｎＯ（比較例５）を用いた以外は実施例５と同様にして金微粒子が担持された触媒を得た。
得られた酸化触媒及び触媒を用いてスルフィドの酸素酸化反応を行い、効果を確認した。
〔試験例８〕触媒の選択 (金担持金属酸化物および金属酸化物)
表３に示す金属酸化物に金微粒子が担持されてなる酸化触媒を用いて上記化学式の酸化反応を試験例１と同様にして行い、収率と選択性を確認した。なお、ＭｎＯｘについては上述の試験例５と同じである。結果を表３に示す。
表３に示す結果から明らかなように、酸化ヴァナジウム、酸化マンガン、酸化コバルト、酸化セリウムを担体とする酸化触媒では酸素酸化反応が進行し、特に酸化マンガン担体が好ましいことがわかる。
[Comparative Examples 1-4]
Example 5 except that TiO 2 (Comparative Example 1), Fe 2 O 3 (Comparative Example 2), NiO (Comparative Example 3), CuO (Comparative Example 4) and ZnO (Comparative Example 5) were used as the carrier. Similarly, a catalyst carrying gold fine particles was obtained.
Using the obtained oxidation catalyst and catalyst, oxygen oxidation reaction of sulfide was performed to confirm the effect.
[Test Example 8] Selection of catalyst (gold-supported metal oxide and metal oxide)
The oxidation reaction of the above chemical formula was carried out in the same manner as in Test Example 1 using an oxidation catalyst in which gold fine particles were supported on the metal oxide shown in Table 3, and the yield and selectivity were confirmed. Note that MnO x is the same as Test Example 5 described above. The results are shown in Table 3.
As is clear from the results shown in Table 3, it can be seen that an oxidation catalyst using vanadium oxide, manganese oxide, cobalt oxide and cerium oxide as a carrier causes an oxygen oxidation reaction, and a manganese oxide carrier is particularly preferable.
〔試験例９〕
また、酸化マンガンからなる（金微粒子の担持なし）酸化触媒について触媒活性を確認した。試験は上記試験例１と同様に行った。
また、酸化マンガン以外の金属酸化物（Ｖ２Ｏ５,Ｃｏ３Ｏ４,ＣｅＯ２）についても試験を行った。酸化ヴァナジウムでも反応が進行した（Ｃｏｎｖ.１１％、スルホキシド2: １０％、スルホン３：０％）。Ｖ２Ｏ５は、ＮＨ４ＶＯ３を３００℃で、４時間空気中で焼成することにより得られた。
[Test Example 9]
Further, the catalytic activity of an oxidation catalyst made of manganese oxide (no gold fine particles supported) was confirmed. The test was performed in the same manner as in Test Example 1 above.
In addition, tests were also conducted on metal oxides (V 2 O 5 , Co 3 O 4 , CeO 2 ) other than manganese oxide. The reaction also proceeded with vanadium oxide (Conv. 11%, sulfoxide 2: 10%, sulfone 3: 0%). V 2 O 5 was obtained by firing NH 4 VO 3 at 300 ° C. for 4 hours in air.
〔試験例１０〕酸素圧の影響
反応の進行には酸素が必要であるが、酸素の圧力はどの程度であるのが効果的であるかを、表５に示す各圧力で反応させることで確認した。なお、圧力以外の条件は化合物1（５８．５μＬ,０．５ｍｍｏｌ）、触媒としてＭｎＯｘ（９８．５ｍｇ）、溶媒ｔｏｌｕｅｎｅ（５ｍＬ）,反応温度 １００℃、反応時間２４時間とした以外は上記試験例１と同じである。表５に示す結果から明らかなように、圧力コストを勘案すると６気圧が最適であることが分かる。
[Test Example 10] Effect of oxygen pressure Oxygen is required for the progress of the reaction, but it is confirmed by reacting at each pressure shown in Table 5 how effective the pressure of oxygen is. did. The above test examples except that the conditions other than the pressure were Compound 1 (58.5 μL, 0.5 mmol), MnOx (98.5 mg) as a catalyst, solvent toluene (5 mL), reaction temperature 100 ° C., and reaction time 24 hours. Same as 1. As is apparent from the results shown in Table 5, it is understood that 6 atmospheres is optimal when the pressure cost is taken into consideration.
〔試験例１１〕
反応温度と反応時間を表６に示す条件とし、化合物1（５８．５μＬ、０．５ｍｍｏｌ）,酸化触媒ＭｎＯｘ （９８．５ｍｇ）、溶剤量（５ｍＬ）とした以外は試験例１と同様に反応を行った。
その結果を表６に示す。
[Test Example 11]
The reaction was carried out in the same manner as in Test Example 1 except that the reaction temperature and reaction time were as shown in Table 6, except that Compound 1 (58.5 μL, 0.5 mmol), oxidation catalyst MnOx (98.5 mg), and solvent amount (5 mL) were used. Went.
The results are shown in Table 6.
Claims (11)
式：ＭｎxＯy
（式中、ｘは１〜１０の整数を、ｙは１〜２０の整数を示し、ｙ≧ｘ、２≧ｙ／ｘ≧１である） An oxidation catalyst for an organic sulfur compound comprising one or more metal oxides selected from the group consisting of a compound represented by the following formula, CuMn 2 O 4 and V 2 O 5 .
Formula: Mn x O y
(Wherein x represents an integer of 1 to 10, y represents an integer of 1 to 20, and y ≧ x, 2 ≧ y / x ≧ 1)
請求項１記載の酸化触媒。 2. The oxidation catalyst according to claim 1, wherein the metal oxide is a particle having a spherical shape, a plate shape, or a rod shape, and a particle diameter of 0.5 nm to 1 μm.
請求項２記載の酸化触媒。 The oxidation catalyst according to claim 2, wherein the metal oxide is a particle having a plate shape or a rod shape, and a thickness thereof is 5 to 100 nm.
請求項１記載の酸化触媒。 The oxidation catalyst according to claim 1, wherein the oxidizing agent used for oxidizing the organic sulfur compound is oxygen.
請求項１記載の酸化触媒。 The oxidation catalyst according to claim 1, wherein the organic sulfur compound is methylphenyl sulfide, and the product produced by the oxidation reaction is sulfoxide or sulfone.
上記担体が、下記式で表される化合物、ＣｕＭｎ２Ｏ４、Ｖ2Ｏ5、Ｃｏ3Ｏ4及びＣｅＯ2からなる群より選択される１種以上の金属酸化物であることを特徴とする酸化触媒。
式：ＭｎxＯy
（式中、ｘは１〜１０の整数を、ｙは１〜２０の整数を示し、ｙ≧ｘ、２≧ｙ／ｘ≧１である） An oxidation catalyst of an organic sulfur compound, in which gold fine particles are supported on a carrier,
The carrier is one or more metal oxides selected from the group consisting of a compound represented by the following formula, CuMn 2 O 4 , V 2 O 5 , Co 3 O 4 and CeO 2. Oxidation catalyst.
Formula: Mn x O y
(Wherein x represents an integer of 1 to 10, y represents an integer of 1 to 20, and y ≧ x, 2 ≧ y / x ≧ 1)
請求項６記載の酸化触媒。 The oxidation catalyst according to claim 6, wherein the metal oxide is a particle having a spherical shape, a plate shape, or a rod shape, and a particle diameter of 0.5 nm to 1 μm.
請求項７記載の酸化触媒。 The oxidation catalyst according to claim 7, wherein the metal oxide is a particle having a plate shape or a rod shape, and a thickness thereof is 5 to 100 nm.
上記金微粒子各々の粒子径が０．８〜１０ｎｍである
請求項６記載の酸化触媒。 The gold fine particles are supported by forming an atomic aggregate formed by agglomerating 8 to 10,000 atoms,
The oxidation catalyst according to claim 6, wherein each of the gold fine particles has a particle diameter of 0.8 to 10 nm.
請求項６記載の酸化触媒。 The oxidation catalyst according to claim 6, wherein the oxidizing agent used for oxidizing the organic sulfur compound is oxygen.
請求項６記載の酸化触媒。
The oxidation catalyst according to claim 6, wherein the organic sulfur compound is methylphenyl sulfide, and the product produced by the oxidation reaction is sulfoxide or sulfone.
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