JP3982978B2 - Catalyst for selective oxidation reaction of rhenium oxide - Google Patents
Catalyst for selective oxidation reaction of rhenium oxide Download PDFInfo
- Publication number
- JP3982978B2 JP3982978B2 JP2000177972A JP2000177972A JP3982978B2 JP 3982978 B2 JP3982978 B2 JP 3982978B2 JP 2000177972 A JP2000177972 A JP 2000177972A JP 2000177972 A JP2000177972 A JP 2000177972A JP 3982978 B2 JP3982978 B2 JP 3982978B2
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- Prior art keywords
- catalyst
- oxide
- lower alcohol
- phase catalytic
- methanol
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- 239000003054 catalyst Substances 0.000 title claims description 54
- 238000007254 oxidation reaction Methods 0.000 title claims description 46
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 title claims description 23
- 229910003449 rhenium oxide Inorganic materials 0.000 title claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 123
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 35
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical group COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 31
- 230000003197 catalytic effect Effects 0.000 claims description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims description 19
- 150000004706 metal oxides Chemical class 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- -1 hydrocarbon nitriles Chemical class 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- 229910000859 α-Fe Inorganic materials 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000012808 vapor phase Substances 0.000 claims description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001566 austenite Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 239000007809 chemical reaction catalyst Substances 0.000 description 10
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 7
- 239000001282 iso-butane Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 235000013980 iron oxide Nutrition 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 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 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、酸化レニウム、特に金属酸化物担体に担持された酸化レニウムを活性成分とする選択酸化反応用触媒や、かかる選択酸化反応用触媒を用いたメタノール等の低級アルコールからジメトキシメタン等の低級アルコール部分酸化物及び低級炭化水素からの低級炭化水素ニトリル化物の製造方法に関する。
【０００２】
【従来の技術】
従来、ジメトキシメタンは、メタノールとホルムアルデヒドとを原料とし、酸性触媒を用いて水溶液中で反応させることにより製造されており、これら酸性触媒としては、例えば、塩酸、硫酸などの鉱酸、ＦｅＣｌ3、ＡｌＣｌ3などのルイス酸、強酸性陽イオン交換樹脂、無機固体酸などが使用されている（ドイツ特許明細書第８００３９９号、ドイツ特許明細書第１１７７１２６号、ドイツ特許明細書第１１５５７８０号、特開昭４７−２９３０９号公報及び特開昭５８−１６２５４６号公報）。しかし、原料となるホルムアルデヒドは、メタノールを酸化することにより調製されており、上記方法は、メタノールから調製されたホルムアルデヒドをメタノールと反応させる二段階プロセスであるためその生産性に問題があった。
【０００３】
一方、ホルムアルデヒドを用いることなく、メタノールから直接ジメトキシメタンを製造する方法として、例えば、酸化銅を含む触媒を用いる方法（特開平５−２３７３８７号公報）や、イオン伝導体上に異なる二種類以上の金属種からなる金属及び／又はこれらの金属化合物を存在させた触媒を用いる方法（特開平６−６５１２３号公報）が知られているが、前者の酸化銅を含む触媒を用いたジメトキシメタンの製造方法では反応に要する時間が長く、その収率も必ずしも満足するものではなく、後者の触媒を用いたジメトキシメタンの製造方法ではギ酸メチルの選択率は高いもののジメトキシメタンの選択率が７％と低く、いずれの方法も実用性の面において解決すべき問題があった。
【０００４】
【発明が解決しようとする課題】
ジメトキシメタンはホルムアルデヒドジメチルアセタールあるいはメチラールとも呼ばれ、主として医薬品、香料、樹脂の原料として用いられる有用な化合物として知られている。かかる有用化合物をメタノールの直接酸化により選択的かつ効率よく製造することができる固体触媒として、本発明者らは先にレニウム・アンチモン複合酸化物触媒を提案している（特願平１１−２６９４８０号）。本発明の課題は、メタノール等の低級アルコールの直接酸化により選択的かつ効率よくジメトキシメタン等の低級アルコール部分酸化物をより選択的かつ効率よく製造することができる選択酸化反応用触媒や、かかる選択酸化反応用触媒を用いたメタノール等の低級アルコールからジメトキシメタン等の低級アルコール部分酸化物を選択的かつ効率よく製造する方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意研究した結果、酸化レニウム、特に金属酸化物担体に担持された酸化レニウムを活性成分とする触媒がメタノール等の低級アルコールの酸化反応に優れた触媒活性を示し、かかる酸化レニウムを活性成分とする触媒を用いるとジメトキシメタン等の低級アルコール部分酸化物を選択的かつ効率よく製造しうることを見い出し、本発明を完成するに至った。
【０００６】
すなわち本発明は、酸化レニウムを活性成分とすることを特徴とする低級アルコールの気相接触酸化用触媒（請求項１）や、酸化レニウムが金属酸化物からなる担体に担持されていることを特徴とする請求項１記載の低級アルコールの気相接触酸化用触媒（請求項２）や、金属酸化物が、鉄、チタン、ジルコニウム、ケイ素、アルミニウム又はバナジウムの酸化物であることを特徴とする請求項２記載の低級アルコールの気相接触酸化用触媒（請求項３）や鉄酸化物がα−Ｆｅ 2 Ｏ 3 又はγ−Ｆｅ 2 Ｏ 3 であることを特徴とする請求項３記載の低級アルコールの気相接触酸化用触媒（請求項４）や、酸化レニウムを活性成分とすることを特徴とする低級炭化水素の気相接触アンモ酸化用触媒（請求項５）や、酸化レニウムが金属酸化物からなる担体に担持されていることを特徴とする請求項５記載の低級炭化水素の気相接触アンモ酸化用触媒（請求項６）や、金属酸化物が、鉄、チタン、ジルコニウム、ケイ素、アルミニウム又はバナジウムの酸化物であることを特徴とする請求項６記載の低級炭化水素の気相接触アンモ酸化用触媒（請求項７）や、鉄酸化物がα−Ｆｅ 2 Ｏ 3 又はγ−Ｆｅ 2 Ｏ 3 であることを特徴とする請求項７記載の低級炭化水素の気相接触アンモ酸化用触媒（請求項８）に関する。
【０００７】
また本発明は、請求項１〜４のいずれか記載の触媒の存在下、低級アルコールを分子状酸素含有ガスにより気相接触酸化することを特徴とする低級アルコール部分酸化物の製造方法（請求項９）や、気相接触酸化が、２００〜４００℃の温度下で行われることを特徴とする請求項９記載の低級アルコール部分酸化物の製造方法（請求項１０）や、低級アルコールが、メタノールであることを特徴とする請求項９又は１０記載の低級アルコール部分酸化物の製造方法（請求項１１）や、低級アルコール部分酸化物が、ジメトキシメタンであることを特徴とする請求項９〜１１のいずれか記載の低級アルコール部分酸化物の製造方法（請求項１２）や、請求項５〜８のいずれか記載の触媒の存在下、低級炭化水素を分子状酸素及びアンモニアを含有するガスにより気相接触アンモ酸化することを特徴とする低級炭化水素ニトリル化物の製造方法（請求項１３）に関する。
【０００８】
【発明の実施の形態】
本発明の選択酸化反応用触媒としては、酸化レニウムを活性成分とする酸化反応用触媒であれば特に制限されるものではないが、酸化レニウムが金属酸化物等の担体に担持された酸化反応用触媒が好ましい。上記酸化レニウムとしては、一般式ＲｅＯX（Ｘ＝２〜３．５）で表されるものを例示することができ、これらは、ＮＨ4ＲｅＯ4を４００℃で加熱分解することによって得ることができる。また、上記金属酸化物としては、γ−Ｆｅ2Ｏ3、α−Ｆｅ2Ｏ3、Ｆｅ2Ｏ3等の鉄酸化物、ルチル型又はアナターゼ型ＴｉＯ2等のチタン酸化物、ＺｒＯ2等のジルコニウム酸化物、ＳｉＯ2等のケイ素酸化物、Ａｌ2Ｏ3等のアルミニウム酸化物、Ｖ2Ｏ3等のバナジウム酸化物、ＭｏＯ3等のモリブデン酸化物を具体的に例示することができるが、α−Ｆｅ2Ｏ3、γ−Ｆｅ2Ｏ3、ＴｉＯ2等が、メタノール等の低級アルコールからジメトキシメタン等の低級アルコール部分酸化物を選択的かつ効率よく製造することができる点で好ましい。
【０００９】
酸化レニウムを金属酸化物等からなる担体に担持させる方法としては特に制限されるものではないが、例えば、ＮＨ4ＲｅＯ4を担体上に含浸させ、１１０℃で一晩乾燥させた後、ヘリウムガス流通下、昇温速度４℃／分で４００℃まで昇温し、４００℃で６時間加熱することにより得ることができる。また、担体へのレニウムの担持量としては特に制限されるものではないが、金属酸化物等の担体当たり０．１〜２０重量％、特に１〜１０重量％担持させることが好ましい。担持量が約１〜３重量％のとき通常反応速度が最大となり、約２〜１０重量％のとき通常選択率が最大となる。本発明の選択酸化反応用触媒は個体触媒であり、その形状としては、粉末状、顆粒状、ペレット上、球状、ハニカム状等を例示することができる。
【００１０】
本発明の低級アルコール部分酸化物の製造方法は、酸化レニウムや金属酸化物等の担体に担持されている酸化レニウムを活性成分とする上記選択酸化反応用触媒の存在下、低級アルコールを分子状酸素含有ガスにより気相接触酸化することを特徴とする。本発明において低級アルコールとは、Ｃ１〜４のアルコール、すなわちメタノール、エタノール、プロパノール、ブタノールをいい、これらの中でも特にメタノールがアルコール転化率の点で好ましい。また、本発明における低級アルコール部分酸化物としては、例えば、ジメトキシメタン等のジアルコキシメタンやジメチルエーテル等のジアルキルエーテルを具体的に例示することができる。
【００１１】
また、上記分子状酸素含有ガスとしては、純酸素ガス、空気等酸素含有ガスを挙げることができ、本発明の選択酸化反応用触媒の存在下における気相接触酸化は、例えば低級アルコールに、分子状酸素含有ガスと希釈ガスを添加した混合ガスからなる原料ガスを前記触媒が収納された固定床反応器内に導入することにより行うことができる。希釈ガスとしては、窒素や、二酸化炭素や、ヘリウム、アルゴン等の希ガスや、水蒸気等の不活性ガス及びこれらの混合ガスを例示することができる。
【００１２】
また、本発明の選択酸化反応用触媒を用いたメタノール等の低級アルコールの酸化反応におけるメタノール等の低級アルコール濃度や酸素濃度は、ジメトキシメタン等の目的とする低級アルコール部分酸化物の生成効率を低下させない範囲であれば特に制限されることはない。また、酸化反応における反応温度は、原料低級アルコールの種類や、目的とする低級アルコール部分酸化物の種類、酸化レニウムを担持する担体の種類等によって異なるが、例えばメタノールを部分酸化してジメトキシメタンを製造する場合は２００〜４００℃で約８０〜９９％の選択率でジメトキシメタンを得ることができる。
【００１３】
本発明の選択酸化反応用触媒は、低級アルコールの選択酸化反応を触媒するばかりでなく、脂肪族炭化水素のアンモ酸化用の触媒としても使用することができる。本発明の低級炭化水素ニトリル化物の製造方法としては、本発明の選択酸化反応用触媒の存在下、低級炭化水素を分子状酸素及びアンモニアを含有するガスにより気相接触アンモ酸化する方法であれば特に制限されないが、上記選択酸化反応用触媒の存在下、イソブタン等の低級脂肪族炭化水素を分子状酸素含有ガス及びアンモニアと約４００℃で気相接触アンモ酸化することにより、メタクリロニトリル等の不飽和ニトリルを製造する方法を具体的に例示することができる。
【００１４】
【実施例】
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はかかる実施例により限定されるものではない。なお、メタノール酸化による各種生成物を例にとって、実施例における転化率、選択率を説明すると、これらはそれぞれ以下の式で表される。
メタノール転化率＝（反応したメタノールのモル数）／（供給したメタノールのモル数）×１００
ジメトキシメタン選択率＝（生成したジメトキシメタンのモル数）×３／（反応したメタノールのモル数）×３×１００
ホルムアルデヒド選択率＝（生成したホルムアルデヒドのモル数）／（反応したメタノールのモル数）×１００
ジメチルエーテル選択率＝（生成したジメチルエーテルのモル数）／（反応したメタノールのモル数）×２×１００
ギ酸メチル選択率＝（生成したギ酸メチルのモル数）／（反応したメタノールのモル数）×２×１００
ギ酸選択率＝（生成したギ酸のモル数）／（反応したメタノールのモル数）×１００
一酸化炭素＋二酸化炭素の選択率＝（生成した一酸化炭素＋二酸化炭素のモル数）／（反応したメタノールのモル数）×１００
【００１５】
実施例１（選択酸化反応用触媒の調製）
ＲｅＯ3及びＲｅＯ2は市販品（添川社製、純度９９％）を用いた。ＲｅＯXは、ＮＨ4ＲｅＯ4を１１０℃で一晩乾燥させた後、ヘリウムガス流通下、昇温速度４℃／分で４００℃まで昇温し、４００℃で６時間加熱することにより調製した。このＲｅＯXのＸＲＤパターンをＸ線回折装置（理学社製「ＸＰＳ−７０００」）を用いて調べたところ、主に単斜晶系のＲｅＯ2であることがわかった。また、アモルファス型Ｆｅ2Ｏ3は、Ｆｅ（ＮＯ3）3の溶液に、ＮＨ4ＯＨ（和光純薬社製；純度９９．９％）の溶液を加え、濾過後に脱イオン水で洗浄し、１２０℃で乾燥して４００℃で４時間空気中で焼成することにより調製した。
【００１６】
また、触媒担持担体金属酸化物としては、α−Ｆｅ2Ｏ3（添川社製、純度９９％）、γ−Ｆｅ2Ｏ3（添川社製、純度９９％）、上記調製したアモルファス型Ｆｅ2Ｏ3、ルチル型ＴｉＯ2（添川社製、純度９９％）、アナターゼ型ＴｉＯ2（添川社製、純度９９％）、ＺｒＯ2（添川社製、純度９９％）、ＳｉＯ2（日本エアロジル社製、純度９９％）、α−Ａｌ2Ｏ3（添川社製、純度９９％）、Ｖ2Ｏ5（添川社製、純度９９％）、ＭｏＯ3（添川社製、純度９９％）を用いた。担体担持触媒は、これら金属酸化物担体上にＮＨ4ＲｅＯ4を含浸し、得られた固形物を１１０℃で一晩乾燥させた後、ヘリウムガス流通下、昇温速度４℃／分で４００℃まで昇温し、４００℃で６時間加熱することにより調製した。各担体におけるレニウムの担持量は担体の１０重量％であった。
【００１７】
実施例２（選択酸化反応用触媒によるメタノールの選択酸化反応）
表１に示された各種複合酸化物触媒又は含浸触媒０．２ｇを石英製反応管に充填し、触媒をＨｅガスにて３００℃で前処理した後、前記反応管へＨｅ／Ｏ2／ＭｅＯＨ［８６．３／９．７／４．０（ｍｏｌ％）］からなる混合ガスをＧＨＳＶ＝４０，０００ｍｌ／（ｈ・ｇ-cat）の流速で導入しながら２４０℃でメタノールの酸化反応を行った。この反応は固定層流動反応系の装置を用い、生成物をＴＣＤ検出器を備えたガスクロマトグラフィー（ＧＣ）を用いて分析した。このガスクロマトグラフィー用カラムとしては、メタノール、ジメチルエーテル、ジメトキシメタン、ホルムアルデヒド、ギ酸メチルの分離定量にはPolapack-N（３ｍ）を、ＣＯ及びＣＯ2の分離定量にはUnibeads C（３ｍ）をそれぞれ用いて分析した。
【００１８】
【表１】
表１に各種触媒を用いた場合のメタノールの選択酸化反応におけるメタノールの転化率と、ジメトキシメタン、ホルムアルデヒド、ジメチルエーテル、ギ酸メチル、ＣＯX（ＣＯ＋ＣＯ2）の各選択率を示す。これらの結果から、ＲｅＯ3触媒を用いた場合、ジメトキシメタンの選択率は９９％と非常に高く、また、ＲｅＯX／α−Ｆｅ2Ｏ3やＲｅＯX／γ−Ｆｅ2Ｏ3のＦｅ酸化物担持ＲｅＯX触媒を用いた場合でもジメトキシメタンの選択率は９０％以上と高いことがわかった。しかし、α−Ｆｅ2Ｏ3のみの触媒を用いた場合ではメタノールの選択酸化反応は全く起こらなかった。また、Ｖ2Ｏ5、ＴｉＯ2−ルチル、ＺｒＯ2、α−Ａｌ2Ｏ3、ＭｏＯ3等の担体を担持させたＲｅＯX触媒を用いた場合でもジメトキシメタンの選択率はいずれも８０％以上であり、特にＲｅＯX／Ｖ2Ｏ5は９３．７％と非常に高いジメトキシメタンの選択率を示した。
【００２０】
実施例３（Ｒｅ担持Ｆｅ酸化物触媒におけるＲｅの担持量の影響）
実施例１と同様の条件で、Ｒｅの担持量が０．５重量％、１．０重量％、２．０重量％、３．０重量％、６．０重量％、１０．０重量％の各ＲｅＯX／α−Ｆｅ2Ｏ3触媒を調製し、これらの触媒を用いて実施例２と同様の条件でメタノールの選択酸化反応を行った。その結果を図１に示す。図１中、（◆）はメタノールの転化率を、（◇）はジメトキシメタンの選択率を、（●）はジメトキシメタンの反応速度をそれぞれ示す。この結果から、メタノールの転化率はＲｅの担持量を増加するにつれ徐々に増加し、Ｒｅの担持量が２〜３重量％以上で定常期に達し、ジメトキシメタンの選択率を９０％以上に維持しうることがわかった。また、Ｒｅの担持量が１〜３重量％において反応速度が最大となることもわかった。
【００２１】
実施例４（選択酸化反応用触媒によるイソブタンのアンモ酸化反応）
ＲｅＯ2とＲｅ／α−Ｆｅ2Ｏ3をそれぞれ酸化反応用触媒とし、固定層流動反応系の装置を用いてイソブタンのアンモ酸化反応を行った。これら触媒０．１５ｇをそれぞれ充填した石英製反応管を４００℃に調整した後、イソブタン／ＮＨ3／Ｏ2／Ｈｅ［１０／１５／２５／５０（ｍｏｌ％）］からなる混合ガスをＧＨＳＶ＝５，０００ｍｌ／（ｈ・ｇ-cat）の流速で導入しながらアンモ酸化反応を行った。反応生成物をガスクロマトグラフィーにより分析し、各反応時間におけるイソブタンの転化率、メタクリロニトリルの選択率、イソブチレンの選択率、アセトニトリルの選択率をそれぞれ求めた。触媒としてＲｅＯ2を用いた場合の結果を図４に、Ｒｅ／α−Ｆｅ2Ｏ3を用いた場合の結果を図５にそれぞれ示す。
【００２２】
【発明の効果】
本発明において、酸化レニウム、特に金属酸化物担体に担持された酸化レニウムをメタノール等の低級アルコールの選択酸化反応用触媒として用いることにより、メタノール等の低級アルコールからジメトキシメタン等の低級アルコール部分酸化物を選択的かつ効率よく製造することができる。
【図面の簡単な説明】
【図１】本発明のＲｅ／α−Ｆｅ2Ｏ3触媒を用いたメタノール選択酸化反応におけるＲｅの担持量の影響を示す図である。
【図２】本発明のＲｅＯ2触媒を用いたイソブタンのアンモ酸化反応におけるメタクリロニトリル等の選択率を示す図である。
【図３】本発明のＲｅ／α−Ｆｅ2Ｏ3触媒を用いたイソブタンのアンモ酸化反応におけるメタクリロニトリル等の選択率を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst for selective oxidation reaction using rhenium oxide, particularly rhenium oxide supported on a metal oxide support as an active component, and a lower alcohol such as dimethoxymethane from a lower alcohol such as methanol using such a catalyst for selective oxidation reaction. The present invention relates to a method for producing a lower hydrocarbon nitrile from an alcohol partial oxide and a lower hydrocarbon.
[0002]
[Prior art]
Conventionally, dimethoxymethane has been produced by reacting methanol and formaldehyde as raw materials and using an acidic catalyst in an aqueous solution. Examples of these acidic catalysts include mineral acids such as hydrochloric acid and sulfuric acid, FeCl 3 , Lewis acids such as AlCl 3 , strong acid cation exchange resins, inorganic solid acids and the like are used (German Patent Specification No. 80000399, German Patent Specification No. 1177126, German Patent Specification No. 1155780, JP, Sho 47-29309 and JP 58-162546). However, formaldehyde as a raw material is prepared by oxidizing methanol, and the above method has a problem in productivity because it is a two-stage process in which formaldehyde prepared from methanol is reacted with methanol.
[0003]
On the other hand, as a method for producing dimethoxymethane directly from methanol without using formaldehyde, for example, a method using a catalyst containing copper oxide (JP-A-5-237387) or two or more different types on an ion conductor A method using a metal comprising a metal species and / or a catalyst in which these metal compounds are present (Japanese Patent Laid-Open No. 6-65123) is known, but the former production of dimethoxymethane using a catalyst containing copper oxide In this method, the reaction takes a long time and the yield is not always satisfactory. In the latter method of producing dimethoxymethane, the selectivity of methyl formate is high, but the selectivity of dimethoxymethane is as low as 7%. Both methods have problems to be solved in terms of practicality.
[0004]
[Problems to be solved by the invention]
Dimethoxymethane is also called formaldehyde dimethyl acetal or methylal, and is known as a useful compound mainly used as a raw material for pharmaceuticals, fragrances and resins. The present inventors have previously proposed a rhenium / antimony composite oxide catalyst as a solid catalyst capable of selectively and efficiently producing such useful compounds by direct oxidation of methanol (Japanese Patent Application No. 11-269480). ). An object of the present invention is to provide a selective oxidation reaction catalyst capable of selectively and efficiently producing a lower alcohol partial oxide such as dimethoxymethane more selectively and efficiently by direct oxidation of a lower alcohol such as methanol, and such a selection. It is an object of the present invention to provide a method for selectively and efficiently producing a lower alcohol partial oxide such as dimethoxymethane from a lower alcohol such as methanol using an oxidation reaction catalyst.
[0005]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventors have found that a catalyst containing rhenium oxide, particularly rhenium oxide supported on a metal oxide support, as an active component is excellent in the oxidation reaction of lower alcohols such as methanol. It has been found that when a catalyst having catalytic activity and such rhenium oxide as an active component is used, a lower alcohol partial oxide such as dimethoxymethane can be selectively and efficiently produced, and the present invention has been completed.
[0006]
That is, the present invention is characterized in that a catalyst for vapor-phase catalytic oxidation of a lower alcohol characterized by using rhenium oxide as an active component (Claim 1) or rhenium oxide is supported on a carrier made of a metal oxide. The catalyst for vapor phase catalytic oxidation of lower alcohol according to claim 1 (claim 2) or the metal oxide is an oxide of iron, titanium, zirconium, silicon, aluminum or vanadium. lower alcohol according to
[0007]
The present invention is a manufacturing method of
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The catalyst for selective oxidation reaction of the present invention is not particularly limited as long as it is a catalyst for oxidation reaction containing rhenium oxide as an active component, but for oxidation reaction in which rhenium oxide is supported on a support such as a metal oxide. A catalyst is preferred. Examples of the rhenium oxide include those represented by the general formula ReO x (X = 2 to 3.5), which can be obtained by thermally decomposing NH 4 ReO 4 at 400 ° C. it can. Examples of the metal oxide include iron oxides such as γ-Fe 2 O 3 , α-Fe 2 O 3 , and Fe 2 O 3 , titanium oxides such as rutile or anatase TiO 2 , and ZrO 2 . zirconium oxide, silicon oxide such as SiO 2, aluminum oxides such as Al 2 O 3, vanadium oxide such as V 2 O 3, can be specifically exemplified molybdenum oxide such as MoO 3, α-Fe 2 O 3 , γ-Fe 2 O 3 , TiO 2 and the like are preferable in that a lower alcohol partial oxide such as dimethoxymethane can be selectively and efficiently produced from a lower alcohol such as methanol.
[0009]
A method for supporting rhenium oxide on a support made of a metal oxide or the like is not particularly limited. For example, NH 4 ReO 4 is impregnated on a support and dried at 110 ° C. overnight, and then helium gas is used. It can be obtained by raising the temperature to 400 ° C. at a heating rate of 4 ° C./min under heating and heating at 400 ° C. for 6 hours. The amount of rhenium supported on the carrier is not particularly limited, but it is preferably 0.1 to 20% by weight, particularly 1 to 10% by weight, based on the carrier such as a metal oxide. When the loading amount is about 1 to 3% by weight, the normal reaction rate becomes maximum, and when it is about 2 to 10% by weight, the normal selectivity becomes maximum. The selective oxidation reaction catalyst of the present invention is a solid catalyst, and examples of the shape thereof include powder, granules, pellets, spheres, and honeycombs.
[0010]
The method for producing a lower alcohol partial oxide according to the present invention comprises the step of converting a lower alcohol into molecular oxygen in the presence of the catalyst for selective oxidation reaction comprising rhenium oxide supported on a carrier such as rhenium oxide or metal oxide as an active component. It is characterized by vapor phase catalytic oxidation with a contained gas. In the present invention, the lower alcohol refers to a C1-4 alcohol, that is, methanol, ethanol, propanol, and butanol. Among these, methanol is particularly preferable in terms of alcohol conversion. Specific examples of the lower alcohol partial oxide in the present invention include dialkoxymethane such as dimethoxymethane and dialkyl ether such as dimethyl ether.
[0011]
Examples of the molecular oxygen-containing gas include pure oxygen gas and oxygen-containing gas such as air. Gas phase catalytic oxidation in the presence of the catalyst for selective oxidation reaction of the present invention can be performed by, for example, converting a lower alcohol to a molecular It can be carried out by introducing a raw material gas comprising a mixed gas to which a gaseous oxygen-containing gas and a dilution gas are added into a fixed bed reactor in which the catalyst is accommodated. Examples of the dilution gas include nitrogen, carbon dioxide, rare gases such as helium and argon, inert gases such as water vapor, and mixed gases thereof.
[0012]
In addition, the lower alcohol concentration or oxygen concentration of methanol or the like in the oxidation reaction of lower alcohol such as methanol using the selective oxidation reaction catalyst of the present invention reduces the production efficiency of the desired lower alcohol partial oxide such as dimethoxymethane. If it is the range which is not made, it will not be restrict | limited in particular. The reaction temperature in the oxidation reaction varies depending on the type of raw material lower alcohol, the type of target lower alcohol partial oxide, the type of carrier supporting rhenium oxide, etc., for example, by partially oxidizing methanol to dimethoxymethane. In the case of production, dimethoxymethane can be obtained at a selectivity of about 80 to 99% at 200 to 400 ° C.
[0013]
The catalyst for selective oxidation reaction of the present invention can be used not only as a catalyst for selective oxidation reaction of lower alcohols but also as a catalyst for ammoxidation of aliphatic hydrocarbons. The method for producing the lower hydrocarbon nitrile of the present invention is a method in which the lower hydrocarbon is vapor-phase catalytically ammoxidized with a gas containing molecular oxygen and ammonia in the presence of the selective oxidation reaction catalyst of the present invention. Although not particularly limited, by subjecting a lower aliphatic hydrocarbon such as isobutane or the like to gas phase catalytic ammoxidation with a molecular oxygen-containing gas and ammonia at about 400 ° C. in the presence of the selective oxidation reaction catalyst, methacrylonitrile or the like is obtained. A method for producing an unsaturated nitrile can be specifically exemplified.
[0014]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited by this Example. In addition, taking various products by methanol oxidation as an example, the conversion rate and selectivity in the examples will be described, and these are represented by the following equations, respectively.
Methanol conversion rate = (number of moles of reacted methanol) / (number of moles of supplied methanol) × 100
Dimethoxymethane selectivity = (number of moles of dimethoxymethane produced) × 3 / (number of moles of reacted methanol) × 3 × 100
Formaldehyde selectivity = (number of moles of formaldehyde produced) / (number of moles of reacted methanol) × 100
Dimethyl ether selectivity = (number of moles of dimethyl ether formed) / (number of moles of reacted methanol) × 2 × 100
Methyl formate selectivity = (number of moles of methyl formate produced) / (number of moles of reacted methanol) × 2 × 100
Formic acid selectivity = (number of moles of formic acid produced) / (number of moles of reacted methanol) × 100
Selectivity of carbon monoxide + carbon dioxide = (number of moles of produced carbon monoxide + carbon dioxide) / (number of moles of reacted methanol) × 100
[0015]
Example 1 (Preparation of selective oxidation reaction catalyst)
As ReO 3 and ReO 2 , commercially available products (manufactured by Soekawa, purity 99%) were used. ReO X was prepared by drying NH 4 ReO 4 at 110 ° C. overnight, then heating to 400 ° C. at a heating rate of 4 ° C./min under heating with helium gas, and heating at 400 ° C. for 6 hours. . When this XRD pattern of ReO X was examined using an X-ray diffractometer (“XPS-7000” manufactured by Rigaku Corporation), it was found that it was mainly monoclinic ReO 2 . Amorphous Fe 2 O 3 is added to a solution of Fe (NO 3 ) 3 with a solution of NH 4 OH (manufactured by Wako Pure Chemical Industries, Ltd .; purity 99.9%), washed with deionized water after filtration, It was prepared by drying at 120 ° C. and firing in air at 400 ° C. for 4 hours.
[0016]
Further, as the catalyst-supported carrier metal oxide, α-Fe 2 O 3 (manufactured by Soekawa, purity 99%), γ-Fe 2 O 3 (manufactured by Soekawa, purity 99%), the above prepared amorphous Fe 2 O 3 , rutile TiO 2 (manufactured by Soekawa Co., purity 99%), anatase TiO 2 (manufactured by Soekawa Co., purity 99%), ZrO 2 (manufactured by Soekawa Co., purity 99%), SiO 2 (manufactured by Nippon Aerosil Co., Ltd.) , Purity 99%), α-Al 2 O 3 (manufactured by Soekawa, 99% purity), V 2 O 5 (manufactured by Soekawa, 99% purity), MoO 3 (manufactured by Soekawa, 99% purity). . The carrier-supported catalyst was impregnated with NH 4 ReO 4 on these metal oxide supports, and the resulting solid was dried at 110 ° C. overnight, and then heated at 400 ° C./min under a helium gas flow. The mixture was heated to 400C and heated at 400C for 6 hours. The amount of rhenium supported on each carrier was 10% by weight of the carrier.
[0017]
Example 2 (Selective oxidation reaction of methanol by selective oxidation reaction catalyst)
After filling 0.2 g of various complex oxide catalysts or impregnated catalysts shown in Table 1 into a quartz reaction tube and pretreating the catalyst with He gas at 300 ° C., the reaction tube was filled with He / O 2 / MeOH. While introducing a mixed gas consisting of [86.3 / 9.7 / 4.0 (mol%)] at a flow rate of GHSV = 40,000 ml / (h · g −cat ), methanol was oxidized at 240 ° C. It was. For this reaction, a fixed bed flow reaction system was used, and the product was analyzed by gas chromatography (GC) equipped with a TCD detector. As the gas chromatographic column, using methanol, dimethyl ether, dimethoxymethane, formaldehyde, Polapack-N (3m) in the separation and determination of methyl formate, in the separation and determination of CO and CO 2 Unibeads C a (3m) respectively And analyzed.
[0018]
[Table 1]
Table 1 shows the conversion rate of methanol in the selective oxidation reaction of methanol when various catalysts are used, and the selectivity of each of dimethoxymethane, formaldehyde, dimethyl ether, methyl formate, and CO x (CO + CO 2 ). From these results, when the ReO 3 catalyst was used, the selectivity of dimethoxymethane was as high as 99%, and Fe oxidation of ReO x / α-Fe 2 O 3 and ReO x / γ-Fe 2 O 3 It was found that the selectivity of dimethoxymethane was as high as 90% or more even when the object-supported ReO X catalyst was used. However, in the case of using only the catalyst of α-Fe 2 O 3 , the selective oxidation reaction of methanol did not occur at all. Further, even when a ReO x catalyst supporting a carrier such as V 2 O 5 , TiO 2 -rutile, ZrO 2 , α-Al 2 O 3 , MoO 3 is used, the selectivity of dimethoxymethane is 80% or more. In particular, ReO x / V 2 O 5 showed a very high dimethoxymethane selectivity of 93.7%.
[0020]
Example 3 (Influence of the amount of Re supported on the Re-supported Fe oxide catalyst)
Under the same conditions as in Example 1, the amount of Re supported was 0.5 wt%, 1.0 wt%, 2.0 wt%, 3.0 wt%, 6.0 wt%, 10.0 wt%. ReO x / α-Fe 2 O 3 catalysts were prepared and methanol was subjected to selective oxidation reaction under the same conditions as in Example 2 using these catalysts. The result is shown in FIG. In FIG. 1, (♦) shows the conversion rate of methanol, (）) shows the selectivity of dimethoxymethane, and (●) shows the reaction rate of dimethoxymethane. From this result, the conversion rate of methanol gradually increases as the amount of Re loaded increases, reaches the stationary phase when the amount of Re loaded is 2 to 3% by weight or more, and maintains the selectivity of dimethoxymethane to 90% or more. I knew it was possible. It was also found that the reaction rate was maximum when the amount of Re supported was 1 to 3% by weight.
[0021]
Example 4 (Isobutane ammoxidation reaction using selective oxidation reaction catalyst)
Using ReO 2 and Re / α-Fe 2 O 3 as oxidation reaction catalysts, isobutane ammoxidation was carried out using a fixed bed fluidized reaction system. After adjusting the reaction tube made of quartz filled with 0.15 g of each catalyst to 400 ° C., a mixed gas composed of isobutane / NH 3 / O 2 / He [10/15/25/50 (mol%)] was added to GHSV = The ammoxidation reaction was carried out while introducing at a flow rate of 5,000 ml / (h · g -cat ). The reaction product was analyzed by gas chromatography, and the conversion of isobutane, the selectivity of methacrylonitrile, the selectivity of isobutylene, and the selectivity of acetonitrile were determined for each reaction time. FIG. 4 shows the results when ReO 2 is used as the catalyst, and FIG. 5 shows the results when Re / α-Fe 2 O 3 is used.
[0022]
【The invention's effect】
In the present invention, rhenium oxide, particularly rhenium oxide supported on a metal oxide support is used as a catalyst for selective oxidation reaction of lower alcohols such as methanol, so that lower alcohol partial oxides such as dimethoxymethane from lower alcohols such as methanol. Can be produced selectively and efficiently.
[Brief description of the drawings]
FIG. 1 is a graph showing the influence of the amount of Re supported in a methanol selective oxidation reaction using the Re / α-Fe 2 O 3 catalyst of the present invention.
FIG. 2 is a graph showing the selectivity of methacrylonitrile and the like in isobutane ammoxidation reaction using the ReO 2 catalyst of the present invention.
FIG. 3 is a graph showing the selectivity of methacrylonitrile and the like in an ammoxidation reaction of isobutane using the Re / α-Fe 2 O 3 catalyst of the present invention.
Claims (13)
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| JP5110471B2 (en) * | 2008-04-01 | 2012-12-26 | 独立行政法人産業技術総合研究所 | Method for producing acetal |
| FR2931819B1 (en) * | 2008-06-03 | 2010-06-11 | Arkema France | PROCESS FOR THE SYNTHESIS OF DIACOXYALKANES BY SELECTIVE OXIDATION OF ALCOHOLS |
| CN101428211B (en) * | 2008-12-12 | 2012-07-25 | 中国科学院山西煤炭化学研究所 | Catalyst for producing dimethoxymethane with methanol selective oxidation and preparation method thereof |
| CN101757906B (en) * | 2008-12-23 | 2012-01-18 | 南京大学 | Preparation method for V-Ti-Al-O composite catalyst for methylal synthesis through methanol oxidation |
| JP5600260B2 (en) * | 2009-02-27 | 2014-10-01 | 中国石油化工股▲ふん▼有限公司 | Method for oxidative conversion of methanol |
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