JP2007260588A - Method for producing catalyst for methacrylic acid production and method for producing methacrylic acid - Google Patents
Method for producing catalyst for methacrylic acid production and method for producing methacrylic acid Download PDFInfo
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- JP2007260588A JP2007260588A JP2006090552A JP2006090552A JP2007260588A JP 2007260588 A JP2007260588 A JP 2007260588A JP 2006090552 A JP2006090552 A JP 2006090552A JP 2006090552 A JP2006090552 A JP 2006090552A JP 2007260588 A JP2007260588 A JP 2007260588A
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- methacrylic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 14
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000001282 iso-butane Substances 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 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
- 229910052742 iron Inorganic materials 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
- 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
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 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
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000010304 firing Methods 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 150000008043 acidic salts Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000002036 drum drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000004715 keto acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- -1 oxo acid salt Chemical class 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 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
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide 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
Abstract
Description
本発明は、メタクリル酸製造用触媒を製造する方法に関するものである。また、本発明は、この方法により得られた触媒を用いて、メタクリル酸を製造する方法にも関係している。 The present invention relates to a method for producing a catalyst for producing methacrylic acid. The present invention also relates to a method for producing methacrylic acid using the catalyst obtained by this method.
メタクロレイン等の気相接触酸化反応によりメタクリル酸を製造する際に用いる触媒としては、リン及びモリブデンを含むヘテロポリ酸やその塩からなるものが有効であることが知られている。この触媒は、通常、触媒原料の水性混合液を乾燥した後、焼成することにより製造され、その際、該水性混合液の乾燥には、蒸発乾固法、噴霧乾燥法、ドラム乾燥法、気流乾燥法等が用いられる（例えば特許文献１〜４参照）。また、特許文献２には、この乾燥により得られる乾燥物の粒子径を１〜２５０μｍとすることで、触媒性能が向上することが開示されている。 As a catalyst used when producing methacrylic acid by a gas phase catalytic oxidation reaction such as methacrolein, it is known that a catalyst comprising a heteropolyacid containing phosphorus and molybdenum or a salt thereof is effective. This catalyst is usually produced by drying and calcining an aqueous mixed solution of catalyst raw materials. In this case, the aqueous mixed solution can be dried by evaporation to dryness, spray drying, drum drying, airflow A drying method or the like is used (see, for example, Patent Documents 1 to 4). Patent Document 2 discloses that the catalyst performance is improved by setting the particle size of the dried product obtained by this drying to 1 to 250 μm.
メタクリル酸を長期間にわたり生産性良く製造するには、触媒活性の持続性、すなわち触媒寿命の点で優れる触媒が求められるが、従来の方法により得られる触媒は、その点で必ずしも満足できるものではなかった。そこで、本発明の目的は、優れた触媒寿命を有するメタクリル酸製造用触媒を製造しうる方法を提供することにある。そして、この方法により得られた触媒を用いて、長期間にわたり生産性良くメタクリル酸を製造しうる方法を提供することにある。 In order to produce methacrylic acid over a long period of time with good productivity, a catalyst that is excellent in sustaining catalytic activity, that is, in terms of catalyst life, is required. However, catalysts obtained by conventional methods are not necessarily satisfactory in that respect. There wasn't. Then, the objective of this invention is providing the method which can manufacture the catalyst for methacrylic acid manufacture which has the outstanding catalyst lifetime. And it is providing the method which can manufacture methacrylic acid with high productivity over a long period of time using the catalyst obtained by this method.
本発明者らは、鋭意研究を行った結果、触媒原料の水性混合液の乾燥により、所定の黄色味を有する乾燥物を得、これを成形した後、焼成することにより、上記目的を達成できることを見出し、本発明を完成するに至った。すなわち、本発明は、リン及びモリブデンを含むヘテロポリ酸化合物からなるメタクリル酸製造用触媒の製造方法であって、触媒原料の水性混合液を乾燥して、ｂ値が６．０以上である乾燥物を得、この乾燥物を成形した後、焼成することを特徴とするメタクリル酸製造用触媒の製造方法を提供するものである。また、本発明は、こうして得られる触媒の存在下に、メタクロレイン、イソブチルアルデヒド、イソブタン及びイソ酪酸から選ばれる化合物を気相接触酸化反応に付すことにより、メタクリル酸を製造する方法にも関係している。 As a result of diligent research, the present inventors have obtained a dried product having a predetermined yellowishness by drying an aqueous mixed solution of catalyst raw materials, and can achieve the above-mentioned object by molding the product and then firing it. As a result, the present invention has been completed. That is, the present invention relates to a method for producing a catalyst for producing methacrylic acid comprising a heteropolyacid compound containing phosphorus and molybdenum, and a dried product having a b value of 6.0 or more by drying an aqueous mixed solution of catalyst raw materials. And providing a method for producing a catalyst for methacrylic acid production, characterized in that the dried product is molded and then calcined. The present invention also relates to a method for producing methacrylic acid by subjecting a compound selected from methacrolein, isobutyraldehyde, isobutane and isobutyric acid to a gas phase catalytic oxidation reaction in the presence of the catalyst thus obtained. ing.
本発明によれば、優れた触媒寿命を有するメタクリル酸製造用触媒を製造することができ、こうして得られた触媒を用いることにより、メタクリル酸を長期間にわたり生産性良く製造することができる。 According to the present invention, a catalyst for producing methacrylic acid having an excellent catalyst life can be produced. By using the catalyst thus obtained, methacrylic acid can be produced with a high productivity over a long period of time.
以下、本発明を詳細に説明する。本発明が製造の対象とするメタクリル酸製造用触媒は、リン及びモリブデンを必須とするヘテロポリ酸化合物からなるものであり、遊離のヘテロポリ酸からなるものであってもよいし、ヘテロポリ酸の塩からなるものであってもよい。中でも、ヘテロポリ酸の酸性塩（部分中和塩）からなるものが好ましく、さらに好ましくはケギン型ヘテロポリ酸の酸性塩からなるものである。 Hereinafter, the present invention will be described in detail. The catalyst for methacrylic acid production to be produced by the present invention is composed of a heteropolyacid compound essentially containing phosphorus and molybdenum, and may be composed of a free heteropolyacid or from a salt of a heteropolyacid. It may be. Especially, what consists of an acidic salt (partially neutralized salt) of heteropolyacid is preferable, More preferably, it consists of an acidic salt of Keggin type heteropolyacid.
上記触媒には、リン及びモリブデン以外の元素として、バナジウムが含まれるのが望ましく、また、カリウム、ルビジウム、セシウム及びタリウムから選ばれる少なくとも１種の元素（以下、Ｘ元素ということがある）や、銅、ヒ素、アンチモン、ホウ素、銀、ビスマス、鉄、コバルト、ランタン及びセリウムから選ばれる少なくとも１種の元素（以下、Ｙ元素ということがある）が含まれるのが望ましい。通常、モリブデン１２原子に対して、リン、バナジウム、Ｘ元素及びＹ元素が、それぞれ３原子以下の割合で含まれる触媒が、好適に用いられる。 The catalyst preferably contains vanadium as an element other than phosphorus and molybdenum, and at least one element selected from potassium, rubidium, cesium and thallium (hereinafter sometimes referred to as X element), It is desirable that at least one element selected from copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium (hereinafter sometimes referred to as Y element) is included. Usually, a catalyst containing phosphorus, vanadium, X element and Y element at a ratio of 3 atoms or less to 12 atoms of molybdenum is preferably used.
上記触媒の原料としては、通常、上記触媒に含まれる各元素を含む化合物、例えば、各元素のオキソ酸、オキソ酸塩、酸化物、硝酸塩、炭酸塩、水酸化物、ハロゲン化物等が、所望の原子比を満たすような割合で用いられる。例えば、リンを含む化合物としては、リン酸、リン酸塩等が用いられ、モリブデンを含む化合物としては、モリブデン酸、モリブデン酸塩、酸化モリブデン、塩化モリブデン等が用いられ、バナジウムを含む化合物としては、バナジン酸、バナジン酸塩、酸化バナジウム、塩化バナジウム等が用いられる。また、Ｘ元素を含む化合物としては、酸化物、硝酸塩、炭酸塩、水酸化物、ハロゲン化物等が用いられ、Ｙ元素を含む化合物としては、オキソ酸、オキソ酸塩、硝酸塩、炭酸塩、水酸化物、ハロゲン化物等が用いられる。 As the raw material of the catalyst, a compound containing each element contained in the catalyst, for example, an oxo acid, an oxo acid salt, an oxide, a nitrate, a carbonate, a hydroxide, a halide, or the like of each element is desired. It is used at a ratio that satisfies the atomic ratio of For example, phosphoric acid, phosphate, etc. are used as the compound containing phosphorus, and molybdic acid, molybdate, molybdenum oxide, molybdenum chloride, etc. are used as the compound containing molybdenum, and as the compound containing vanadium, Vanadic acid, vanadate, vanadium oxide, vanadium chloride and the like are used. In addition, oxides, nitrates, carbonates, hydroxides, halides and the like are used as the compounds containing the X element, and oxo acids, oxoacid salts, nitrates, carbonates, water, and the like as the compounds containing the Y element. Oxides, halides and the like are used.
本発明の触媒の製造方法は、上記の触媒原料の水性混合液を乾燥した後、成形し、次いで焼成することからなるものである。この水性混合液は、触媒原料を水中で混合することにより調製でき、水溶液であってもよいし、水性スラリーであってもよい。そして、この水性混合液の乾燥により、ｂ値が６．０以上である乾燥物を得、これを成形した後、焼成することにより、優れた触媒寿命を有する触媒を製造することができる。 The method for producing a catalyst of the present invention comprises drying the above aqueous mixture of catalyst raw materials, molding, and then firing. This aqueous mixture can be prepared by mixing the catalyst raw material in water, and may be an aqueous solution or an aqueous slurry. Then, by drying this aqueous mixed solution, a dried product having a b value of 6.0 or more is obtained, and after molding this, it is possible to produce a catalyst having an excellent catalyst life.
ここで、ｂ値は、Ｌａｂ表色系における色相を表す指標の１つで、ハンターの色差式における色座標の１つであり、プラス側で値が大きいほど黄色味が強いことを表し、マイナス側で値が大きいほど青味が強いことを表すものである。具体的には、ＪＩＳ Ｚ８７２２に規定されるＸＹＺ表色系における三刺激値Ｘ、Ｙ及びＺのうち、Ｙ及びＺを用いて、式「ｂ＝７．０（Ｙ−０．８４７Ｚ）／Ｙ1/2」により計算される。 Here, the b value is one of the indices representing the hue in the Lab color system, and is one of the color coordinates in the Hunter's color difference formula. The larger the value on the positive side, the stronger the yellowness, The larger the value on the side, the stronger the blueness. Specifically, among the tristimulus values X, Y, and Z in the XYZ color system defined in JIS Z8722, using Y and Z, the expression “b = 7.0 (Y−0.847Z) / Y Calculated by 1/2 ".
上記水性混合液の乾燥には、この分野で通常用いられている方法、例えば、蒸発乾固法、噴霧乾燥法、ドラム乾燥法、気流乾燥法等を適用できるが、中でも噴霧乾燥法が好ましく用いられる。この噴霧乾燥法は、上記水性混合液と熱風を噴霧乾燥機（スプレードライヤー）に供給して、該水性混合液を熱風中に噴霧することにより実施でき、その際、該水性混合液の噴霧は、例えば、回転円盤方式により行ってもよいし、圧力ノズル方式により行ってもよい。また、熱風としては、空気等の酸化性ガスを用いてもよいし、窒素等の非酸化性ガスを用いてもよい。そして、得られる乾燥物のｂ値は、上記水性混合液に対する熱風の供給割合が高いほど、また熱風の温度が高いほど、高くなる傾向にあるので、これらを調整して、乾燥物のｂ値が６．０以上となるようにすればよい。通常、上記水性混合液に対する熱風の供給割合は、単位時間あたりでの該水性混合液の液供給量（Ｌ）に対する熱風の標準状態（０℃、１気圧）でのガス供給量（Ｎｍ3）で表して、１０〜２０Ｎｍ3／Ｌの範囲で調整すればよく、また、熱風温度は、乾燥機入口の温度として、２００〜２５０℃の範囲で調整すればよい。ｂ値が６．０に満たなかった場合には、加熱処理等により、ｂ値が６．０以上になるまで、追加の乾燥を行えばよく、その際の温度は通常５０〜１５０℃程度である。なお、乾燥物のｂ値は、好ましくは７．０以上であり、また、上限については特に限定されないが、通常２０以下である。 For the drying of the aqueous mixed solution, a method usually used in this field, for example, an evaporation to dryness method, a spray drying method, a drum drying method, an airflow drying method and the like can be applied, and among these, the spray drying method is preferably used. It is done. This spray drying method can be carried out by supplying the aqueous mixture and hot air to a spray dryer (spray dryer), and spraying the aqueous mixture into hot air. For example, it may be performed by a rotating disk method or a pressure nozzle method. Further, as the hot air, an oxidizing gas such as air may be used, or a non-oxidizing gas such as nitrogen may be used. And since the b value of the obtained dried product tends to increase as the supply ratio of hot air to the aqueous mixture is higher and the temperature of the hot air is higher, the b value of the dried product is adjusted. May be set to 6.0 or more. Usually, the supply ratio of hot air to the aqueous mixture is determined as follows: gas supply amount (Nm 3 ) in the standard state (0 ° C., 1 atm) of hot air with respect to the liquid supply amount (L) of the aqueous mixture per unit time expressed in, may be adjusted in a range of: 10 to 20 nm 3 / L, also hot air temperature, the temperature of the dryer inlet may be adjusted in the range of 200 to 250 ° C.. When the b value is less than 6.0, additional drying may be performed until the b value becomes 6.0 or more by heat treatment, and the temperature at that time is usually about 50 to 150 ° C. is there. The b value of the dried product is preferably 7.0 or more, and the upper limit is not particularly limited, but is usually 20 or less.
なお、乾燥物のｂ値を６．０以上とすることで、得られる触媒の寿命が向上する理由については明らかでないが、乾燥物をＸＰＳ（Ｘ線光電子分光法）により分析すると、６価のモリブンデン（２３２．５ｅＶ付近に観測）に対する５価のモリブデン（２３１．２ｅＶ付近に観測）のピーク面積比（Ｍｏ5+／Ｍｏ6+）が小さいほど、ｂ値が大きくなる傾向にあり、また、バナジウムを含有する場合、乾燥物をＥＳＲ（電子スピン共鳴法）により分析すると、４価のバナジウム（３４４５〜３５００Ｇ付近に観測）のピーク面積が小さいほど、ｂ値が大きくなる傾向にあることから、乾燥物の酸化還元状態が、得られる触媒の寿命に影響していると考えられる。 The reason why the life of the resulting catalyst is improved by setting the b value of the dried product to 6.0 or more is not clear, but when the dried product is analyzed by XPS (X-ray photoelectron spectroscopy), The smaller the peak area ratio (Mo 5+ / Mo 6+ ) of pentavalent molybdenum (observed near 231.2 eV) to Molybdenden (observed near 232.5 eV), the b value tends to increase. When vanadium is contained, when the dried product is analyzed by ESR (electron spin resonance method), the b value tends to increase as the peak area of tetravalent vanadium (observed in the vicinity of 3445 to 3500 G) decreases. It is thought that the redox state of the dried product affects the life of the resulting catalyst.
こうして得られるｂ値が６．０以上である乾燥物を、必要に応じて成形助剤を用いて、円柱状、球状、リング状等に成形し、次いで、この成形体を焼成することで、触媒が得られる。この焼成は、酸素等の酸化性ガスの雰囲気下に行ってもよいし、窒素等の非酸化性ガスの雰囲気下に行ってもよいが、非酸化性ガスの雰囲気下に４００〜５００℃の温度で行うのが好ましく、また、この非酸化性ガスによる焼成の前には、酸化性ガス雰囲気又は非酸化性ガスの雰囲気下に１８０〜３００℃程度の温度で保持して、熱処理（前焼成）を行うのが好ましい。そして、この熱処理の際に、ケギン型ヘテロポリ酸塩の構造が形成されるようにするのがよく、このためには、触媒原料としてアンモニウム化合物を用いたり、アンモニアやアンモニウム塩を添加したりして、アンモニウム根を含む水性混合液を得、これを乾燥したものを成形するのがよい。さらに、上記非酸化性ガスによる焼成の後に、酸化性ガスの雰囲気下に３００〜４００℃程度の温度で追加の焼成（後焼成）を行うのも有効である。なお、各焼成の時間は、それぞれ適宜調整されるが、通常１〜３０時間程度である。また、各焼成は、雰囲気ガスとして使用されるガスを流通させながら行うのが好ましい。 By forming a dry product having a b value of 6.0 or more thus obtained into a cylindrical shape, a spherical shape, a ring shape or the like using a molding aid as necessary, and then firing the molded body, A catalyst is obtained. This calcination may be performed in an atmosphere of an oxidizing gas such as oxygen or in an atmosphere of a non-oxidizing gas such as nitrogen, but is performed at 400 to 500 ° C. in an atmosphere of a non-oxidizing gas. It is preferable to carry out the heat treatment, and before firing with this non-oxidizing gas, heat treatment (pre-firing) is performed by holding at a temperature of about 180 to 300 ° C. in an oxidizing gas atmosphere or a non-oxidizing gas atmosphere. ) Is preferably performed. In this heat treatment, a Keggin heteropolyacid salt structure is preferably formed. For this purpose, an ammonium compound is used as a catalyst raw material, or ammonia or an ammonium salt is added. It is preferable to obtain an aqueous mixed solution containing ammonium roots and mold the dried one. It is also effective to perform additional baking (post-baking) at a temperature of about 300 to 400 ° C. in an oxidizing gas atmosphere after baking with the non-oxidizing gas. In addition, although the time of each baking is each adjusted suitably, it is about 1 to 30 hours normally. Moreover, it is preferable to perform each baking, distribute | circulating the gas used as atmospheric gas.
こうして得られるメタクリル酸製造用触媒は、優れた触媒寿命を有しており、この触媒を用いて、メタクロレイン、イソブチルアルデヒド、イソブタン、イソ酪酸等の原料化合物を気相接触酸化反応させることにより、メタクリル酸を長期間にわたり生産性良く製造することができる。 The methacrylic acid production catalyst thus obtained has an excellent catalyst life, and by using this catalyst, a raw material compound such as methacrolein, isobutyraldehyde, isobutane, isobutyric acid is subjected to a gas phase catalytic oxidation reaction, Methacrylic acid can be produced with good productivity over a long period of time.
メタクリル酸の製造は、通常、固定床多管式反応器に触媒を充填し、これに原料化合物と酸素を含む原料ガスを供給することにより行われるが、流動床や移動床のような反応形式を採用することもできる。酸素源としては、通常、空気が用いられ、また原料ガス中には、原料化合物及び酸素以外の成分として、窒素、二酸化炭素、一酸化炭素、水蒸気等が含まれうる。 The production of methacrylic acid is usually carried out by filling a fixed bed multi-tubular reactor with a catalyst and supplying a raw material gas containing a raw material compound and oxygen to this. It can also be adopted. As the oxygen source, air is usually used, and the raw material gas may contain nitrogen, carbon dioxide, carbon monoxide, water vapor and the like as components other than the raw material compound and oxygen.
例えば、メタクロレインを原料として用いる場合、通常、原料ガス中のメタクロレイン濃度は１〜１０容量％、メタクロレインに対する酸素のモル比は１〜５、空間速度は５００〜５０００ｈ-1（標準状態基準）、反応温度は２５０〜３５０℃、反応圧力は０．１〜０．３ＭＰａ、の条件下に反応が行われる。なお、原料のメタクロレインは必ずしも高純度の精製品である必要はなく、例えば、イソブチレンやｔ−ブチルアルコールの気相接触酸化反応により得られたメタクロレインを含む反応生成ガスを用いることもできる。 For example, when methacrolein is used as a raw material, the concentration of methacrolein in the raw material gas is usually 1 to 10% by volume, the molar ratio of oxygen to methacrolein is 1 to 5, and the space velocity is 500 to 5000 h −1 (standard condition standard ), The reaction temperature is 250 to 350 ° C., and the reaction pressure is 0.1 to 0.3 MPa. The raw material methacrolein is not necessarily a highly purified product, and for example, a reaction product gas containing methacrolein obtained by a gas phase catalytic oxidation reaction of isobutylene or t-butyl alcohol can be used.
また、イソブタンを原料として用いる場合、通常、原料ガス中のイソブタン濃度は１〜８５容量％、水蒸気濃度は３〜３０容量％、イソブタンに対する酸素のモル比は０．０５〜４、空間速度は４００〜５０００ｈ-1（標準状態基準）、反応温度は２５０〜４００℃、反応圧力は０．１〜１ＭＰａ、の条件下に反応が行われる。イソ酪酸やイソブチルアルデヒドを原料として用いる場合には、通常、メタクロレインを原料として用いる場合と、ほぼ同様の反応条件が採用される。 When isobutane is used as a raw material, the isobutane concentration in the raw material gas is usually 1 to 85% by volume, the water vapor concentration is 3 to 30% by volume, the molar ratio of oxygen to isobutane is 0.05 to 4, and the space velocity is 400. The reaction is carried out under conditions of ˜5000 h −1 (standard condition standard), reaction temperature of 250 to 400 ° C., and reaction pressure of 0.1 to 1 MPa. When isobutyric acid or isobutyraldehyde is used as a raw material, generally the same reaction conditions are employed as when methacrolein is used as a raw material.
以下、本発明の実施例を示すが、本発明はこれらによって限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited thereto.
実施例１〜５、比較例１〜３
（ａ）触媒原料の水性混合液の乾燥
４０℃に加熱したイオン交換水２２４ｋｇに、硝酸セシウム［ＣｓＮＯ3］３８．２ｋｇ、８５重量％オルトリン酸２４．２ｋｇ、及び７０重量％硝酸２５．２ｋｇを溶解し、これをＡ液とした。一方、４０℃に加熱したイオン交換水３３０ｋｇに、モリブデン酸アンモニウム４水和物［(ＮＨ4)6Ｍｏ7Ｏ24・４Ｈ2Ｏ］２９７ｋｇを溶解した後、メタバナジン酸アンモニウム［ＮＨ4ＶＯ3］８．１９ｋｇを懸濁させ、これをＢ液とした。Ａ液とＢ液を４０℃に調整し、攪拌下、Ｂ液にＡ液を滴下した後、密閉容器中で１２０℃にて５．８時間攪拌し、次いで、三酸化アンチモン［Ｓｂ2Ｏ3］１０．２ｋｇ及び硝酸銅３水和物［Ｃｕ(ＮＯ3)2・３Ｈ2Ｏ］１０．２ｋｇを、イオン交換水２３ｋｇに懸濁させて添加した後、密封容器中で１２０℃にて５時間攪拌した。こうして得られたスラリーを、該スラリー１Ｌに対し１５Ｎｍ3の熱風（加熱空気）と共にスプレードライヤーに供給し、乾燥粉末を得た。熱風のスプレードライヤー入口での温度、及び乾燥粉末のｂ値を色差計［日本電色工業（株）製、ＳＱ−２０００］で測定した結果を表１に示す。
Examples 1-5, Comparative Examples 1-3
(A) Drying of aqueous mixture of catalyst raw material To 224 kg of ion-exchanged water heated to 40 ° C., 38.2 kg of cesium nitrate [CsNO 3 ], 24.2 kg of 85 wt% orthophosphoric acid, and 25.2 kg of 70 wt% nitric acid It melt | dissolved and this was made into the A liquid. On the other hand, after dissolving 297 kg of ammonium molybdate tetrahydrate [(NH 4 ) 6 Mo 7 O 24 · 4H 2 O] in 330 kg of ion-exchanged water heated to 40 ° C., ammonium metavanadate [NH 4 VO 3 ] 8.19 kg was suspended and this was used as B liquid. The liquid A and liquid B were adjusted to 40 ° C., and the liquid A was added dropwise to the liquid B with stirring. The liquid was stirred in a sealed container at 120 ° C. for 5.8 hours, and then antimony trioxide [Sb 2 O 3 ] 10.2 kg and 10.2 kg of copper nitrate trihydrate [Cu (NO 3 ) 2 .3H 2 O] were suspended in 23 kg of ion-exchanged water and then added at 120 ° C. in a sealed container. Stir for hours. The slurry thus obtained was supplied to a spray dryer together with 15 Nm 3 hot air (heated air) with respect to 1 L of the slurry to obtain a dry powder. Table 1 shows the results of measuring the temperature at the inlet of the hot air spray dryer and the b value of the dry powder with a color difference meter [manufactured by Nippon Denshoku Industries Co., Ltd., SQ-2000].
（ｂ）触媒の製造
上記（ａ）で得た乾燥粉末１００重量部に対して、セラミックファイバー［東芝モノフラックス（株）製、ＦＩＢＥＲＦＲＡＸ ＲＦＣ４００ＳＬ］４重量部、硝酸アンモニウム１３重量部、及びイオン交換水９．７重量部を加えて混練し、直径５ｍｍ、高さ６ｍｍの円柱状に押出成形した。この成形体を、温度９０℃、湿度３０％ＲＨにて３時間乾燥した後、空気気流中で２２０℃にて２２時間、空気気流中で２５０℃にて１時間の順に熱処理して、ケギン型ヘテロポリ酸塩からなる触媒前駆体を得た。この前駆体を、窒素気流中で４３５℃にて３時間、空気（水分２容量％）気流中で３９０℃にて３時間の順に焼成し、触媒を得た。この触媒は、リン、モリブデン、バナジウム、アンチモン、銅及びセシウムをそれぞれ１．５、１２、０．５、０．５、０．３及び１．４の原子比で含むケギン型ヘテロポリ酸の酸性塩からなるものであった。
(B) Production of catalyst 4 parts by weight of ceramic fiber [manufactured by Toshiba Monoflux Co., Ltd., FIBERFRAX RFC400SL], 13 parts by weight of ammonium nitrate, and 9 parts of ion-exchanged water with respect to 100 parts by weight of the dry powder obtained in (a) above. .7 parts by weight was added and kneaded and extruded into a cylindrical shape having a diameter of 5 mm and a height of 6 mm. This molded body was dried at a temperature of 90 ° C. and a humidity of 30% RH for 3 hours, and then heat-treated in an air stream at 220 ° C. for 22 hours and in an air stream at 250 ° C. for 1 hour in order. A catalyst precursor comprising a heteropolyacid salt was obtained. This precursor was calcined in an order of 3 hours at 435 ° C. in a nitrogen stream and 3 hours at 390 ° C. in an air (water 2% by volume) stream to obtain a catalyst. This catalyst is an acid salt of a Keggin type heteropolyacid containing phosphorus, molybdenum, vanadium, antimony, copper and cesium in atomic ratios of 1.5, 12, 0.5, 0.5, 0.3 and 1.4, respectively. It consisted of.
（ｃ）触媒の活性試験
上記（ｂ）で得た触媒９ｇを、内径１５ｍｍのガラス製マイクロリアクターに充填し、この中に、メタクロレイン、空気、スチーム及び窒素を混合して調製したメタクロレイン４容量％、分子状酸素１２容量％、水蒸気１７容量％の組成の原料ガスを、空間速度６７０ｈ-1で供給して、炉温（マイクロリアクターを加熱するための炉の温度）３５５℃にて反応を行い、触媒を強制劣化させた後、上記と同じ組成の原料ガスを、上記と同じ空間速度で供給して、炉温２８０℃にて反応を行い、この反応開始から１時間経過時のメタクロレイン転化率を求めた。この結果を表１に示す。
(C) Catalyst activity test 9 g of the catalyst obtained in (b) above was charged into a glass microreactor having an inner diameter of 15 mm, and methacrolein 4 prepared by mixing methacrolein, air, steam and nitrogen. A raw material gas having a composition of volume%, molecular oxygen 12 volume%, and water vapor 17 volume% is supplied at a space velocity of 670 h −1 and reacted at a furnace temperature (furnace temperature for heating the microreactor) of 355 ° C. After forcibly degrading the catalyst, a raw material gas having the same composition as described above is supplied at the same space velocity as described above, and the reaction is performed at a furnace temperature of 280 ° C. Rain conversion was determined. The results are shown in Table 1.
実施例６〜９
比較例１（ａ）で得た乾燥粉末（ｂ値４．９）を、表２に示す温度にて表２に示す時間、加熱処理し、表２に示すｂ値とした。この加熱処理後の乾燥粉末を用いて、前記（ｂ）と同様に触媒を製造し、前記（ｃ）と同様に活性試験を行った。この結果を比較例１の結果と共に表２に示す。
Examples 6-9
The dry powder (b value 4.9) obtained in Comparative Example 1 (a) was heat-treated at the temperature shown in Table 2 for the time shown in Table 2 to obtain the b value shown in Table 2. Using the dried powder after the heat treatment, a catalyst was produced in the same manner as in the above (b), and an activity test was conducted in the same manner as in the above (c). The results are shown in Table 2 together with the results of Comparative Example 1.
実施例１０、比較例４、５
Ａ液とＢ液を４０℃に調整する代わりに、５０℃に調整し、Ｂ液にＡ液を滴下した液を１２０℃にて５．８時間攪拌する代わりに、同温度にて８．５時間攪拌し、かつ、熱風のスプレードライヤー入口での温度を表３に示す温度とした以外は、前記（ａ）と同様に乾燥粉末を得た。この乾燥粉末のｂ値を表３に示した。この乾燥粉末を用いて、前記（ｂ）と同様に触媒を製造し、前記（ｃ）と同様に活性試験を行った。この結果を表３に示す。
Example 10, Comparative Examples 4, 5
Instead of adjusting the A and B liquids to 40 ° C, the temperature was adjusted to 50 ° C, and the liquid obtained by adding the A liquid to the B liquid was stirred at 120 ° C for 5.8 hours, but at 8.5. A dry powder was obtained in the same manner as in (a) except that the temperature at the inlet of the hot air spray dryer was changed to the temperature shown in Table 3 with stirring for a period of time. The b value of this dry powder is shown in Table 3. Using this dry powder, a catalyst was produced in the same manner as in (b), and an activity test was conducted in the same manner as in (c). The results are shown in Table 3.
比較例６
比較例４（ａ）で得た乾燥粉末（ｂ値−３．３）を、１２０℃にて３０分間、加熱処理し、ｂ値５．２とした。この加熱処理後の乾燥粉末を用いて、前記（ｂ）と同様に触媒を製造し、前記（ｃ）と同様に活性試験を行った。この結果を表３に示す。
Comparative Example 6
The dry powder (b value-3.3) obtained in Comparative Example 4 (a) was heat-treated at 120 ° C. for 30 minutes to obtain a b value of 5.2. Using the dried powder after the heat treatment, a catalyst was produced in the same manner as in the above (b), and an activity test was conducted in the same manner as in the above (c). The results are shown in Table 3.
Claims (3)
A method for producing methacrylic acid, comprising producing a catalyst by the method according to claim 1 or 2, and subjecting a compound selected from methacrolein, isobutyraldehyde, isobutane and isobutyric acid to a gas phase catalytic oxidation reaction in the presence of the catalyst. .
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