JP3710944B2 - Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid - Google Patents
Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid Download PDFInfo
- Publication number
- JP3710944B2 JP3710944B2 JP01028399A JP1028399A JP3710944B2 JP 3710944 B2 JP3710944 B2 JP 3710944B2 JP 01028399 A JP01028399 A JP 01028399A JP 1028399 A JP1028399 A JP 1028399A JP 3710944 B2 JP3710944 B2 JP 3710944B2
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- Prior art keywords
- catalyst
- methacrylic acid
- producing
- producing methacrylic
- pore volume
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- 239000003054 catalyst Substances 0.000 title claims description 60
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000011148 porous material Substances 0.000 claims description 59
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Chemical group 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Chemical group 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Chemical group 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 21
- 238000003756 stirring Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
Landscapes
- 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、メタクロレインを気相接触酸化してメタクリル酸を製造する際に使用する触媒、その製造法およびメタクリル酸の製造方法に関する。
【０００２】
【従来の技術】
従来、メタクロレインを気相接触酸化してメタクリル酸を製造する方法や、その製造の際に用いられる触媒およびその触媒の製造法に関しては数多くの提案がなされている。これらの中には、触媒成形方法や成形条件により、触媒の表面積、細孔容積、細孔分布等の触媒の微細構造を調節したものがある。例えば、特定の範囲に制御した細孔径分布を持つ触媒を製造する方法としては、特開昭６３−３１５１４８号公報では遠心流動コーティング装置を用いて、細孔直径が１〜１０μｍおよび０．１〜１μｍの範囲にそれぞれ集中して分布を有する触媒を製造する方法、特開平３−８６２４２号公報および特開平４−９０８５３号公報では不活性担体に触媒活性成分を担持する担持成形法で、触媒活性物質層の細孔径分布において、全細孔容積に対する割合が１〜１０μｍの細孔が２０〜７０％、０．５〜１μｍ未満の細孔が２０％以下、０．１〜０．５μｍ未満の細孔が２０〜７０％である触媒を製造する方法が提案されている。
【０００３】
【発明が解決しようとする課題】
しかしながら、工業的にはより反応成績の優れた触媒の開発が望まれているのが現状である。
本発明の目的は、メタクロレインを気相接触酸化してメタクリル酸を高収率で製造できる触媒、その製造法、およびメタクリル酸の製造方法を提供することにある。
【０００４】
【課題を解決するための手段】
すなわち本発明は、メタクロレインを気相接触酸化してメタクリル酸を製造するのに用いられる少なくともモリブデン、リンおよびバナジウムを含む触媒であって、細孔径半径０．００５〜１０μｍの細孔の細孔容積に対する細孔径半径０．００５〜０．０５μｍの細孔の細孔容積の割合が２０％以上であるメタクリル酸製造用触媒である。
【０００５】
【発明の実施の形態】
本発明のメタクリル酸製造用触媒は、少なくともモリブデン、リンおよびバナジウムを含むものである。特に下記の一般式で表わされる組成を有する触媒が好ましい。
ＰaＭｏbＶcＣｕdＦｅeＸfＹgＺhＯi
（式中、Ｐ、Ｍｏ、Ｖ、Ｃｕ、ＦｅおよびＯはそれぞれリン、モリブデン、バナジウム、銅、鉄および酸素を示し、Ｘはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、珪素、タングステンおよびホウ素からなる群より選ばれた少なくとも１種類の元素を、Ｙは亜鉛、クロム、マグネシウム、タンタル、コバルト、マンガン、バリウム、ガリウム、セリウムおよびランタンからなる群より選ばれた少なくとも１種類の元素を、Ｚはカリウム、ルビジウム、セシウムおよびタリウムからなる群より選ばれた少なくとも１種類の元素をそれぞれ示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、およびｈは各元素の原子比率を示し、ｂ＝１２のときａ＝０．５〜３、ｃ＝０．０１〜３、ｄ＝０．０１〜２、ｅ＝０．０１〜２、ｆ＝０〜３、ｇ＝０〜３、ｈ＝０．０１〜３であり、ｉは前記各成分の原子価を満足するのに必要な酸素原子比率である。）
【０００６】
本発明のメタクリル酸製造用触媒を製造するための原料は特に限定されず、各元素の硝酸塩、炭酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物等を組み合わせて使用することができる。例えばモリブデン原料としてはパラモリブデン酸アンモニウム、三酸化モリブデン、モリブデン酸、塩化モリブデン等、バナジウム原料としてはメタバナジン酸アンモニウム、五酸化バナジウム、塩化バナジウム等が使用できる。
【０００７】
本発明のメタクリル酸製造用触媒は、細孔径半径０．００５〜１０μｍの細孔の細孔容積（以下、全細孔容積という。）に対する細孔径半径０．００５〜０．０５μｍの細孔の細孔容積の割合が２０％以上である。
【０００８】
ここで細孔容積は水銀圧入法により測定されたものである。水銀圧入法による細孔容積の測定方法を、水銀圧入式ポロシメーター（ＣＡＲＬＯＥＬＢＡ社製２０００型）を用いた具体例で説明する。
【０００９】
水銀圧入式ポロシメーター（ＣＡＲＬＯＥＬＢＡ社製２０００型）を用いて、１３２Ｐａ〜大気圧は手動バルブにより段階的に昇圧し、大気圧〜１９９ＭＰａは平均昇圧速度０．０１〜０．３ＭＰａ／秒で昇圧し、細孔径半径０．００５〜１０μｍの範囲について細孔径半径とその細孔径半径以上の細孔容積を表すチャートを得る。このチャートから得られる細孔径半径０．００５μｍ以上の細孔容積と細孔径半径０．０５μｍ以上の細孔容積の差が、細孔径半径０．００５〜０．０５μｍの細孔の有する細孔容積となる。また、細孔径半径０．００５μｍ以上の細孔容積が全細孔容積となる。
【００１０】
本発明のメタクリル酸製造用触媒では、全細孔容積に対する細孔径半径０．００５〜０．０５μｍの細孔の細孔容積の割合が２０％以上であり、好ましくは２２〜３０％である。この割合が大きくなるとメタクロレインの気相接触酸化によるメタクリル酸収率が向上する。
【００１１】
以下、本発明のメタクリル酸製造用触媒の製造法の一例について詳しく説明するが、本発明の触媒はここで説明する製造法により得られたものに限定されるものではない。
【００１２】
まず触媒の原料を水に混合あるいは懸濁させる。この溶液または懸濁液を攪拌しながら加熱し、８０℃以上としてから１〜５０時間攪拌を継続する（以下、この工程を加熱攪拌という。）。加熱攪拌中の溶液または懸濁液温度は８０℃以上であれば特に限定されない。この際、蒸発により水が減少することを防ぐため、溶液または懸濁液の入った容器の頭部に冷却器等を取り付けてもよい。また、攪拌速度についても特に限定はなく、溶液または懸濁液が均一に混合または懸濁した状態になるよう任意に決められる。
【００１３】
加熱攪拌終了後、この溶液または懸濁液を８０℃以上で１〜２４時間、好ましくは１〜１０時間静置する。静置中の溶液または懸濁液の温度は、加熱攪拌中の溶液または懸濁液の温度と同じであっても、異なっていてもよいが、８０〜９５℃が好ましい。
【００１４】
触媒組成に銅、鉄、上記Ｘ、ＹおよびＺの元素を含む触媒を製造する場合、これらの元素の添加時期は、モリブデン、リンおよびバナジウムの混合溶液または懸濁液の加熱前、８０℃以上としてからの攪拌中、加熱攪拌終了直後、静置終了後のいずれでもよい。加熱攪拌終了後または静置終了後に触媒の原料を加える際の溶液または懸濁液の温度は、特に制限されず任意である。また、加熱攪拌終了後または静置終了後に触媒の原料を加えた場合、添加後に溶液または懸濁液を任意の温度で数分〜数時間攪拌しても構わない。
【００１５】
このようにして得られた溶液または懸濁液は、種々の方法を用いて乾燥し、乾燥物とする。具体的な乾燥方法としては、例えば、蒸発乾固法、噴霧乾燥法、ドラム乾燥法等が挙げられる。
【００１６】
得られた乾燥物は、打錠成形機、押出し成形機、転動造粒機等の一般的な粉体用成形機等を用いて、球状、リング状、円柱状等任意の形状の成形物としてもよい。尚、成形に際しては、公知の添加剤、例えばグラファイト、タルク等を少量添加してもよい。
【００１７】
次に、このようにして得られた乾燥物または成形物を熱処理して触媒とする。熱処理する方法や熱処理の条件は、公知の方法および条件を使用することができる。用いる触媒原料、触媒組成、製造法、流通ガス等により最適な熱処理条件は異なるが、例えば空気等の含酸素ガス流通下、あるいは窒素等の不活性ガスの流通下で２００〜５００℃、好ましくは３００〜４５０℃で処理する方法が挙げられる。熱処理の時間は通常０．５時間以上必要であり、好ましくは１〜４０時間である。
【００１８】
本発明の触媒を用いてメタクロレインを気相接触酸化してメタクリル酸を製造するに際し、原料ガス中のメタクロレインの濃度は広い範囲で変えることができるが、容量で１〜２０％が適当であり、特に３〜１０％の範囲が好ましい。原料ガスには、低級飽和アルデヒド等の不純物を反応に実質的な影響を与えない程度含んでいてもよい。
【００１９】
原料ガス中には酸素が必要で、酸素源としては空気を用いるのが経済的に有利であるが、必要ならば純酸素で富化した空気等も用いうる。原料ガス中の酸素量は、メタクロレインに対して０．３〜４倍モル、特に０．４〜２．５倍モルの範囲が好ましい。原料ガスには窒素、水蒸気、炭酸ガス等の不活性ガスが含まれていてもよい。
【００２０】
メタクロレインからメタクリル酸を製造する反応の圧力は、常圧から数気圧までがよい。反応温度は２３０〜４５０℃の範囲で選ぶことができ、特に２５０〜４００℃が好ましい。反応は固定床でも流動床でも行うことができる。
【００２１】
【実施例】
以下、本発明による触媒の製造法およびそれを用いての反応例を具体的に説明する。説明中「部」は重量部を意味する。細孔容積は水銀圧入式ポロシメーター（ＣＡＲＬＯＥＬＢＡ社製２０００型）を用いて前記の方法で測定した。メタクリル酸製造反応の生成物はガスクロマトグラフィーにより分析した。メタクロレインの反応率、生成するメタクリル酸の選択率および単流収率は以下のように定義される。
メタクロレインの反応率（％）＝Ａ／Ｂ×１００
メタクリル酸の選択率（％）＝Ｃ／Ａ×１００
メタクリル酸の単流収率（％）＝Ｃ／Ｂ×１００
ここで、Ａは反応したメタクロレインのモル数、Ｂは供給したメタクロレインのモル数、Ｃは生成したメタクリル酸のモル数を表わす。
【００２２】
［実施例１］
パラモリブデン酸アンモニウム１００部、メタバナジン酸アンモニウム２．８部、８５重量％リン酸８．２部を純水３０部に溶解した溶液、硝酸銅１．１部を純水３０部に溶解した溶液および硝酸鉄３．８部を純水１０部に溶解した溶液を純水２００部に加え、これを攪拌しながら９０℃まで加熱し、液温を９０℃に保ちつつ５時間加熱攪拌した。次に、液温を８５℃としてこれを保ちつつ３時間静置し、ついで硝酸セシウム９．２部を純水１００部に溶解した溶液をこれに加え、混合液を加熱攪拌しながら蒸発乾固した。得られた固形物を１３０℃で１６時間乾燥後、加圧成形し、空気流通下に３８０℃で６時間熱処理して触媒を得た。
【００２３】
得られた触媒の酸素以外の元素の組成はＭｏ12Ｐ1.5Ｖ0.5Ｃｕ0.1Ｆｅ0.2Ｃｓ1.0であった。この触媒の全細孔容積に対する細孔径半径０．００５〜０．０５μｍの細孔の細孔容積の割合は２３．７％であった。
【００２４】
この触媒を反応管に充填し、メタクロレイン５％、酸素１０％、水蒸気３０％、窒素５５％（容量％）の混合ガスを反応温度２９０℃、接触時間３．６秒で通じた。生成物を捕集し、ガスクロマトグラフィーで分析したところ、メタクロレイン反応率８３．８％、メタクリル酸選択率８２．９％、メタクリル酸単流収率６９．５％であった。
【００２５】
［比較例１］
実施例１において静置を行わず、加熱攪拌終了後すぐに硝酸セシウムの水溶液を加えた点以外は、実施例１と同様にして触媒を製造し、メタクリル酸の製造反応を行ない、表１の結果を得た。
【００２６】
［実施例２］
実施例１において、加熱攪拌時の液温を１００℃にした点以外は、実施例１と同様にして触媒を製造し、メタクリル酸の製造反応を行ない、表１の結果を得た。
【００２７】
［比較例２］
実施例１において、加熱攪拌時の液温を７０℃にした点以外は、実施例１と同様にして触媒を製造し、メタクリル酸の製造反応を行ない、表１の結果を得た。
【００２８】
［実施例３］
実施例１において、加熱攪拌の時間を２０時間にした点以外は、実施例１と同様にして触媒を製造し、メタクリル酸の製造反応を行ない、表１の結果を得た。
【００２９】
［比較例３］
実施例１において、加熱攪拌の時間を０．５時間にした点以外は、実施例１と同様にして触媒を製造し、メタクリル酸の製造反応を行ない、表１の結果を得た。
【００３０】
［比較例４］
実施例１において、加熱攪拌を行わず、液温を９０℃とした後すぐに硝酸セシウムの水溶液を加えた点以外は、実施例１と同様にして触媒を製造し、メタクリル酸の製造反応を行ない、表１の結果を得た。
【００３１】
［実施例４］
実施例１において、硝酸鉄を加えなかった点以外は、実施例１と同様にして触媒を製造し、メタクリル酸の製造反応を行った。この触媒の酸素以外の元素の組成はＭｏ12Ｐ1.5Ｖ0.5Ｃｕ0.1Ｃｓ1.0であった。この触媒の全細孔容積に対する細孔径半径０．００５〜０．０５μｍの細孔の細孔容積の割合、および反応結果を表１に示した。
【００３２】
［比較例５］
実施例４において静置を行わず、加熱攪拌終了後すぐに硝酸セシウムの水溶液を加えた点以外は、実施例４と同様にして触媒を製造し、メタクリル酸の製造反応を行ない、表１の結果を得た。
【００３３】
［比較例６］
実施例４において、加熱攪拌を行わず、液温を９０℃とした後すぐに硝酸セシウムの水溶液を加えた点以外は、実施例４と同様にして触媒を製造し、メタクリル酸の製造反応を行ない、表１の結果を得た。
【００３４】
［実施例５］
三酸化モリブデン１００部、五酸化バナジウム２．６部、８５重量％リン酸６．７部を純水３０部に溶解した溶液、硝酸銅１．４部および硝酸鉄２．３部を純水８００部に加え、これを攪拌しながら９０℃まで加熱し、液温を９０℃に保ちつつ５時間加熱攪拌した。次に、液温を８５℃としてこれを保ちつつ３時間静置し、ついで重炭酸セシウム１１．２部を純水１００部に溶解した溶液をこれに加えた後、混合液を加熱して蒸発乾固した。得られた固形物を１３０℃で１６時間乾燥後、加圧成形し、空気流通下に３８０℃で６時間熱処理して触媒を得た。
【００３５】
得られた触媒の酸素以外の元素の組成はＭｏ12Ｐ1.0Ｃｕ0.1Ｖ0.5Ｆｅ0.1Ｃｓ1.0であった。この触媒の全細孔容積に対する細孔径半径０．００５〜０．０５μｍの細孔の細孔容積の割合、およびこの触媒を用いて実施例１と同じ条件でメタクリル酸の製造反応を行った結果を表１に示す。
【００３６】
【表１】
【発明の効果】
本発明の触媒を用いてメタクロレインを気相接触酸化すると、高収率でメタクリル酸を製造することができる。特に、一般式ＰaＭｏbＶcＣｕdＦｅeＸfＹgＺhＯi（式中の記号の意味は前記と同じ。）を用いることで、より高収率でメタクリル酸を製造することができる。
また本発明のメタクリル酸製造用触媒の製造法により、このような高収率でメタクリル酸を製造できる触媒が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst used for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, a method for producing the catalyst, and a method for producing methacrylic acid.
[0002]
[Prior art]
Conventionally, many proposals have been made regarding a method for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, a catalyst used in the production thereof, and a method for producing the catalyst. Among these, there are those in which the fine structure of the catalyst such as the surface area, pore volume, and pore distribution of the catalyst is adjusted by the catalyst molding method and molding conditions. For example, as a method for producing a catalyst having a pore size distribution controlled within a specific range, Japanese Patent Application Laid-Open No. 63-315148 uses a centrifugal flow coating apparatus to make pore diameters of 1 to 10 μm and 0.1 to 0.1 μm. In the method of producing a catalyst having a distribution concentrated in the range of 1 μm, in JP-A-3-86242 and JP-A-4-90853, there is a support molding method in which a catalytically active component is supported on an inert carrier. In the pore size distribution of the substance layer, the proportion of the pores with respect to the total pore volume is 20 to 70%, the pores less than 0.5 to 1 μm are 20% or less, and less than 0.1 to 0.5 μm. A method for producing a catalyst having 20 to 70% pores has been proposed.
[0003]
[Problems to be solved by the invention]
However, the present situation is that industrial development of catalysts with better reaction results is desired.
An object of the present invention is to provide a catalyst that can produce methacrylic acid in high yield by gas phase catalytic oxidation of methacrolein, a method for producing the catalyst, and a method for producing methacrylic acid.
[0004]
[Means for Solving the Problems]
That is, the present invention is a catalyst containing at least molybdenum, phosphorus and vanadium used for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, and having pores with pore diameters of 0.005 to 10 μm. A catalyst for producing methacrylic acid, in which the ratio of the pore volume of pores having a pore diameter radius of 0.005 to 0.05 μm to the volume is 20% or more.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The catalyst for producing methacrylic acid of the present invention contains at least molybdenum, phosphorus and vanadium. In particular, a catalyst having a composition represented by the following general formula is preferred.
P a Mo b V c Cu d F e X f Y g Z h O i
(Wherein, P, Mo, V, Cu, Fe and O represent phosphorus, molybdenum, vanadium, copper, iron and oxygen, respectively, X represents antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon. , At least one element selected from the group consisting of tungsten and boron, Y is at least one element selected from the group consisting of zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium and lanthanum Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, a, b, c, d, e, f, g and h are atomic ratios of the respective elements When b = 12, a = 0.5-3, c = 0.01-3, d = 0.01-2, e = 0.01-2 f = 0~3, g = 0~3, a h = 0.01 to 3, i is an oxygen atom ratio required for satisfying the valency of each component.)
[0006]
The raw material for producing the catalyst for producing methacrylic acid of the present invention is not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides and the like of each element can be used in combination. For example, ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride, etc. can be used as the molybdenum raw material, and ammonium metavanadate, vanadium pentoxide, vanadium chloride, etc. can be used as the vanadium raw material.
[0007]
The catalyst for producing methacrylic acid of the present invention has a pore diameter of 0.005 to 0.05 μm with respect to the pore volume of pores having a pore diameter of 0.005 to 10 μm (hereinafter referred to as total pore volume). The proportion of the pore volume is 20% or more.
[0008]
Here, the pore volume is measured by mercury porosimetry. A method for measuring the pore volume by the mercury intrusion method will be described using a specific example using a mercury intrusion porosimeter (carloelba type 2000).
[0009]
Using a mercury intrusion porosimeter (carloelba type 2000), the pressure from 132 Pa to atmospheric pressure was increased stepwise by a manual valve, and atmospheric pressure to 199 MPa was increased at an average pressure increase rate of 0.01 to 0.3 MPa / second. A chart representing the pore diameter radius and the pore volume equal to or larger than the pore diameter radius in the range of the pore diameter radius of 0.005 to 10 μm is obtained. The difference between the pore volume having a pore diameter of 0.005 μm or more obtained from this chart and the pore volume having a pore diameter of 0.05 μm or more is the pore volume possessed by pores having a pore diameter of 0.005 to 0.05 μm. It becomes. A pore volume having a pore diameter radius of 0.005 μm or more is the total pore volume.
[0010]
In the methacrylic acid production catalyst of the present invention, the ratio of the pore volume of pores having a pore diameter radius of 0.005 to 0.05 μm to the total pore volume is 20% or more, preferably 22 to 30%. As this ratio increases, the yield of methacrylic acid by gas phase catalytic oxidation of methacrolein is improved.
[0011]
Hereinafter, although an example of the manufacturing method of the catalyst for methacrylic acid manufacture of this invention is demonstrated in detail, the catalyst of this invention is not limited to what was obtained by the manufacturing method demonstrated here.
[0012]
First, the catalyst raw material is mixed or suspended in water. This solution or suspension is heated with stirring, and the stirring is continued for 1 to 50 hours after reaching 80 ° C. or higher (hereinafter, this step is referred to as heating and stirring). The temperature of the solution or suspension during heating and stirring is not particularly limited as long as it is 80 ° C. or higher. At this time, in order to prevent water from being reduced by evaporation, a cooler or the like may be attached to the head of the container containing the solution or suspension. Further, the stirring speed is not particularly limited, and can be arbitrarily determined so that the solution or suspension is uniformly mixed or suspended.
[0013]
After completion of heating and stirring, the solution or suspension is allowed to stand at 80 ° C. or higher for 1 to 24 hours, preferably 1 to 10 hours. The temperature of the solution or suspension during standing may be the same as or different from the temperature of the solution or suspension during heating and stirring, but is preferably 80 to 95 ° C.
[0014]
When producing a catalyst containing copper, iron, and the above X, Y and Z elements in the catalyst composition, the addition timing of these elements is 80 ° C. or higher before heating the mixed solution or suspension of molybdenum, phosphorus and vanadium. In the subsequent agitation, it may be either immediately after the end of heating and agitation or after completion of standing. The temperature of the solution or suspension when the catalyst raw material is added after completion of heating and stirring or after standing is not particularly limited. In addition, when the catalyst raw material is added after completion of heating and stirring or after standing, the solution or suspension may be stirred at an arbitrary temperature for several minutes to several hours after the addition.
[0015]
The solution or suspension thus obtained is dried using various methods to obtain a dried product. Specific examples of the drying method include evaporation to dryness, spray drying, and drum drying.
[0016]
The obtained dried product is a molded product having an arbitrary shape such as a spherical shape, a ring shape, or a cylindrical shape using a general powder molding machine such as a tableting molding machine, an extrusion molding machine, a rolling granulator, etc. It is good. In molding, a small amount of known additives such as graphite and talc may be added.
[0017]
Next, the dried product or molded product thus obtained is heat-treated to form a catalyst. Known methods and conditions can be used for the heat treatment method and the heat treatment conditions. The optimum heat treatment conditions vary depending on the catalyst raw material, catalyst composition, production method, flow gas, etc. used, but for example, 200 to 500 ° C., preferably under an oxygen-containing gas flow such as air or an inert gas flow such as nitrogen, preferably The method of processing at 300-450 degreeC is mentioned. The heat treatment time is usually 0.5 hours or more, preferably 1 to 40 hours.
[0018]
In producing methacrylic acid by gas phase catalytic oxidation of methacrolein using the catalyst of the present invention, the concentration of methacrolein in the raw material gas can be varied within a wide range, but 1-20% by volume is appropriate. In particular, the range of 3 to 10% is preferable. The source gas may contain impurities such as lower saturated aldehydes to the extent that they do not substantially affect the reaction.
[0019]
Oxygen is required in the raw material gas, and it is economically advantageous to use air as the oxygen source. However, if necessary, air enriched with pure oxygen can also be used. The amount of oxygen in the raw material gas is preferably in the range of 0.3 to 4 times mol, particularly 0.4 to 2.5 times mol with respect to methacrolein. The source gas may contain an inert gas such as nitrogen, water vapor, or carbon dioxide.
[0020]
The reaction pressure for producing methacrylic acid from methacrolein is preferably from normal pressure to several atmospheres. The reaction temperature can be selected in the range of 230 to 450 ° C, and particularly preferably 250 to 400 ° C. The reaction can be carried out in a fixed bed or a fluidized bed.
[0021]
【Example】
Hereinafter, the method for producing a catalyst according to the present invention and reaction examples using the method will be described in detail. In the description, “parts” means parts by weight. The pore volume was measured by the method described above using a mercury intrusion porosimeter (carloelba type 2000). The product of the methacrylic acid production reaction was analyzed by gas chromatography. The reaction rate of methacrolein, the selectivity of methacrylic acid produced and the single flow yield are defined as follows.
Reaction rate of methacrolein (%) = A / B × 100
Methacrylic acid selectivity (%) = C / A × 100
Single stream yield of methacrylic acid (%) = C / B × 100
Here, A represents the number of moles of reacted methacrolein, B represents the number of moles of methacrolein supplied, and C represents the number of moles of methacrylic acid produced.
[0022]
[Example 1]
100 parts of ammonium paramolybdate, 2.8 parts of ammonium metavanadate, 8.2 parts of 85% by weight phosphoric acid in 30 parts of pure water, a solution of 1.1 parts of copper nitrate in 30 parts of pure water, and A solution prepared by dissolving 3.8 parts of iron nitrate in 10 parts of pure water was added to 200 parts of pure water, and this was heated to 90 ° C. while stirring, and heated and stirred for 5 hours while maintaining the liquid temperature at 90 ° C. Next, the liquid temperature is kept at 85 ° C. and left for 3 hours, and then a solution obtained by dissolving 9.2 parts of cesium nitrate in 100 parts of pure water is added thereto, and the mixture is evaporated to dryness while heating and stirring. did. The obtained solid was dried at 130 ° C. for 16 hours, then pressure-molded, and heat-treated at 380 ° C. for 6 hours under air flow to obtain a catalyst.
[0023]
The composition of elements other than oxygen in the obtained catalyst was Mo 12 P 1.5 V 0.5 Cu 0.1 Fe 0.2 Cs 1.0 . The ratio of the pore volume of pores having a pore diameter of 0.005 to 0.05 μm to the total pore volume of this catalyst was 23.7%.
[0024]
This catalyst was charged into a reaction tube, and a mixed gas of 5% methacrolein, 10% oxygen, 30% water vapor and 55% nitrogen (volume%) was passed at a reaction temperature of 290 ° C. and a contact time of 3.6 seconds. When the product was collected and analyzed by gas chromatography, the reaction rate of methacrolein was 83.8%, the selectivity of methacrylic acid was 82.9%, and the single flow rate of methacrylic acid was 69.5%.
[0025]
[Comparative Example 1]
In Example 1, the catalyst was produced in the same manner as in Example 1 except that an aqueous solution of cesium nitrate was added immediately after completion of heating and stirring, and a reaction for producing methacrylic acid was conducted. The result was obtained.
[0026]
[Example 2]
In Example 1, except that the liquid temperature during heating and stirring was set to 100 ° C., a catalyst was produced in the same manner as in Example 1, and a reaction for producing methacrylic acid was carried out. The results shown in Table 1 were obtained.
[0027]
[Comparative Example 2]
In Example 1, except that the liquid temperature at the time of heating and stirring was set to 70 ° C., a catalyst was produced in the same manner as in Example 1, and a reaction for producing methacrylic acid was performed. The results shown in Table 1 were obtained.
[0028]
[Example 3]
In Example 1, except that the heating and stirring time was 20 hours, a catalyst was produced in the same manner as in Example 1, and a reaction for producing methacrylic acid was carried out. The results shown in Table 1 were obtained.
[0029]
[Comparative Example 3]
In Example 1, except that the time of heating and stirring was changed to 0.5 hour, a catalyst was produced in the same manner as in Example 1, and a reaction for producing methacrylic acid was carried out. The results shown in Table 1 were obtained.
[0030]
[Comparative Example 4]
In Example 1, the catalyst was produced in the same manner as in Example 1 except that the aqueous solution of cesium nitrate was added immediately after the liquid temperature was set to 90 ° C. without heating and stirring, and the reaction for producing methacrylic acid was conducted. The results shown in Table 1 were obtained.
[0031]
[Example 4]
In Example 1, except that iron nitrate was not added, a catalyst was produced in the same manner as in Example 1, and a reaction for producing methacrylic acid was performed. The composition of elements other than oxygen in this catalyst was Mo 12 P 1.5 V 0.5 Cu 0.1 Cs 1.0 . Table 1 shows the ratio of the pore volume of pores having a pore diameter radius of 0.005 to 0.05 μm with respect to the total pore volume of this catalyst, and the reaction results.
[0032]
[Comparative Example 5]
In Example 4, the catalyst was produced in the same manner as in Example 4 except that an aqueous solution of cesium nitrate was added immediately after the heating and stirring, and a reaction for producing methacrylic acid was conducted. The result was obtained.
[0033]
[Comparative Example 6]
In Example 4, the catalyst was produced in the same manner as in Example 4 except that the aqueous solution of cesium nitrate was added immediately after the liquid temperature was set to 90 ° C. without heating and stirring, and the reaction for producing methacrylic acid was carried out. The results shown in Table 1 were obtained.
[0034]
[Example 5]
A solution obtained by dissolving 100 parts of molybdenum trioxide, 2.6 parts of vanadium pentoxide, 6.7 parts of 85% by weight phosphoric acid in 30 parts of pure water, 1.4 parts of copper nitrate and 2.3 parts of iron nitrate were added to 800 parts of pure water. The mixture was heated to 90 ° C. with stirring, and stirred for 5 hours while maintaining the liquid temperature at 90 ° C. Next, the liquid temperature was kept at 85 ° C. and left for 3 hours, and then a solution in which 11.2 parts of cesium bicarbonate was dissolved in 100 parts of pure water was added thereto, and then the mixture was heated to evaporate. Dried to dryness. The obtained solid was dried at 130 ° C. for 16 hours, then pressure-molded, and heat-treated at 380 ° C. for 6 hours under air flow to obtain a catalyst.
[0035]
The composition of elements other than oxygen in the obtained catalyst was Mo 12 P 1.0 Cu 0.1 V 0.5 Fe 0.1 Cs 1.0 . The ratio of the pore volume of pores having a pore radius of 0.005 to 0.05 μm to the total pore volume of this catalyst, and the results of the reaction for producing methacrylic acid under the same conditions as in Example 1 using this catalyst Is shown in Table 1.
[0036]
[Table 1]
【The invention's effect】
When methacrolein is subjected to gas phase catalytic oxidation using the catalyst of the present invention, methacrylic acid can be produced in high yield. In particular, the general formula P a Mo b V c Cu d Fe e X f Y g Z h O it ( meaning of symbols in the formula is the same. As defined above) by using, more producing methacrylic acid in high yield be able to.
Moreover, the catalyst which can manufacture methacrylic acid with such a high yield is obtained by the manufacturing method of the catalyst for methacrylic acid manufacture of this invention.
Claims (4)
ＰaＭｏbＶcＣｕdＦｅeＸfＹgＺhＯi
（式中、Ｐ、Ｍｏ、Ｖ、Ｃｕ、ＦｅおよびＯはそれぞれリン、モリブデン、バナジウム、銅、鉄および酸素を示し、Ｘはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、珪素、タングステンおよびホウ素からなる群より選ばれた少なくとも１種類の元素を、Ｙは亜鉛、クロム、マグネシウム、タンタル、コバルト、マンガン、バリウム、ガリウム、セリウムおよびランタンからなる群より選ばれた少なくとも１種類の元素を、Ｚはカリウム、ルビジウム、セシウムおよびタリウムからなる群より選ばれた少なくとも１種類の元素をそれぞれ示す。ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、およびｈは各元素の原子比率を示し、ｂ＝１２のときａ＝０．５〜３、ｃ＝０．０１〜３、ｄ＝０．０１〜２、ｅ＝０．０１〜２、ｆ＝０〜３、ｇ＝０〜３、ｈ＝０．０１〜３であり、ｉは前記各成分の原子価を満足するのに必要な酸素原子比率である。）The catalyst for methacrylic acid production according to claim 1, which has a composition represented by the following general formula.
P a Mo b V c Cu d F e X f Y g Z h O i
(Wherein, P, Mo, V, Cu, Fe and O represent phosphorus, molybdenum, vanadium, copper, iron and oxygen, respectively, X represents antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon. , At least one element selected from the group consisting of tungsten and boron, Y is at least one element selected from the group consisting of zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium and lanthanum Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, a, b, c, d, e, f, g and h are atomic ratios of the respective elements When b = 12, a = 0.5-3, c = 0.01-3, d = 0.01-2, e = 0.01-2 f = 0~3, g = 0~3, a h = 0.01 to 3, i is an oxygen atom ratio required for satisfying the valency of each component.)
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| JP01028399A JP3710944B2 (en) | 1999-01-19 | 1999-01-19 | Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid |
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| JP01028399A JP3710944B2 (en) | 1999-01-19 | 1999-01-19 | Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid |
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| WO2022163726A1 (en) | 2021-01-27 | 2022-08-04 | 日本化薬株式会社 | Catalyst, and method for producing unsaturated carobxylic acid using same |
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| KR100557640B1 (en) | 2004-01-09 | 2006-03-10 | 주식회사 엘지화학 | Novel Heteropoly Acid Catalyst and Preparing Method Thereof |
| US7649111B2 (en) * | 2005-07-25 | 2010-01-19 | Saudi Basic Industries Corporation | Catalyst for the oxidation of a mixed aldehyde feedstock to methacrylic acid and methods for making and using same |
| JP5020514B2 (en) * | 2006-01-16 | 2012-09-05 | ダイヤニトリックス株式会社 | Method for producing fluidized bed catalyst and method for producing nitriles |
| US7494952B2 (en) * | 2006-01-17 | 2009-02-24 | Saudi Basic Industries Corporation | Process of making mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
| WO2013147041A1 (en) * | 2012-03-30 | 2013-10-03 | 株式会社日本触媒 | Method for producing acrylic acid and acrolein using fixed-bed multitubular reactor |
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