JP2002233760A - Catalyst for producing methacrylic acid, coated catalyst and its producing method - Google Patents
Catalyst for producing methacrylic acid, coated catalyst and its producing methodInfo
- Publication number
- JP2002233760A JP2002233760A JP2001281720A JP2001281720A JP2002233760A JP 2002233760 A JP2002233760 A JP 2002233760A JP 2001281720 A JP2001281720 A JP 2001281720A JP 2001281720 A JP2001281720 A JP 2001281720A JP 2002233760 A JP2002233760 A JP 2002233760A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- coated
- producing
- coated catalyst
- methacrolein
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 209
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 60
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 25
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 24
- 239000004480 active ingredient Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims description 82
- 239000000203 mixture Substances 0.000 claims description 79
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 33
- 230000003197 catalytic effect Effects 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical group 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011964 heteropoly acid Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910052776 Thorium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 78
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 42
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 32
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 32
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 30
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 26
- 239000008187 granular material Substances 0.000 description 25
- 239000005749 Copper compound Substances 0.000 description 22
- 150000001880 copper compounds Chemical class 0.000 description 22
- 239000000843 powder Substances 0.000 description 22
- 235000011007 phosphoric acid Nutrition 0.000 description 21
- 229960004643 cupric oxide Drugs 0.000 description 19
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 238000010992 reflux Methods 0.000 description 13
- 239000007921 spray Substances 0.000 description 13
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229940000488 arsenic acid Drugs 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940076286 cupric acetate Drugs 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 101710192523 30S ribosomal protein S9 Proteins 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- -1 methyl ethyl ketone Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin 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
【０００１】[0001]
【発明の属する技術分野】本発明は、寿命が長くかつ高
活性、高選択性を有する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ための触媒及びその製造方
法に関する。The present invention relates to a catalyst for producing methacrylic acid by subjecting methacrolein having a long life, having high activity and high selectivity to gas phase catalytic oxidation, and a method for producing the same.
【０００２】[0002]
【従来の技術】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ために使用される触媒としては数多
くの触媒が提案されている。これら触媒の大部分はモリ
ブデン、リンを主成分とするもので、ヘテロポリ酸及び
／又はその塩の構造を有するものである。しかしなが
ら、メタクロレインの気相接触酸化反応と同様の反応と
して知られているアクロレインの酸化によるアクリル酸
を製造するために提案されているモリブデン−バナジウ
ム系触媒と比較すると、反応活性は低く、目的物質への
選択性も低く、寿命も短いため、提案されている触媒は
一部工業化されているものの、これら触媒性能の改良が
求められている。2. Description of the Related Art Numerous catalysts have been proposed as catalysts for producing methacrylic acid by subjecting methacrolein to gas-phase catalytic oxidation. Most of these catalysts are mainly composed of molybdenum and phosphorus, and have a structure of a heteropolyacid and / or a salt thereof. However, when compared to a molybdenum-vanadium-based catalyst proposed for producing acrylic acid by oxidation of acrolein, which is known as a reaction similar to the gas phase catalytic oxidation reaction of methacrolein, the reaction activity is low, and the target substance is low. Because of low selectivity to catalysts and a short service life, some of the proposed catalysts have been industrialized, but there is a demand for improvements in their performance.
【０００３】本発明者らは、先に従来のメタクロレイン
気相接触酸化触媒の低活性、低選択性、短寿命の改良を
試み、Ｍｏ、Ｖ、Ｐに種々の元素を添加したメタクロレ
イン気相接触酸化触媒が、ヘテロポリ酸（塩）構造を有
し、高活性、高選択性で特に寿命的に安定した触媒であ
ることを見出し、特公昭５８−１１４１６、特公昭５９
−２４１４０、特公昭６２−１４５３５、特公昭６２−
３０１７７記載の触媒を提案している。The present inventors have previously attempted to improve the low activity, low selectivity, and short life of the conventional methacrolein gas phase catalytic oxidation catalyst, and have investigated the addition of various elements to Mo, V, and P. It has been found that the phase contact oxidation catalyst has a heteropolyacid (salt) structure, is highly active, has high selectivity, and is particularly stable over its life, and is disclosed in JP-B-58-11416 and JP-B-59.
-24140, JP-B 62-14535, JP-B 62-
No. 30177 is proposed.
【０００４】また、工業用触媒として固定床反応器に充
填して用いる場合は、触媒層前後での反応ガスの圧力損
失を少なくするために、ある一定の大きさに触媒を成型
する事が必要である。そのため、通常は触媒粉末を柱状
物、錠剤、リング状、球状等に成型するか、活性触媒物
質を不活性担体に含浸あるいは被覆させて用いる方法も
知られている。この不活性担体を芯とする被覆触媒の利
点としては、 触媒活性成分の有効利用率を上げることができる、 反応物質の触媒内での滞留時間分布が均一となり選択
性の向上が期待できる、 触媒の熱伝導率向上あるいは不活性担体の希釈効果に
よって反応熱の除去が容易となる、 等が挙げられ、従って発熱の大きな選択的酸化反応への
適用の例が多い。一方、被覆触媒製造上の技術的困難点
としては、 被覆層の剥離、ひび割れが起こり易く機械的強度の強
い触媒が得られ難い、 多量に活性触媒物質を担体上に被覆する事が難しい、 不活性物質が入るために活性の高い触媒を得ることが
難しい 等を挙げることができる。かかる点を克服する方法は活
性触媒物質の性状とも関わり、汎用的な技術はなく触媒
個々に解決するというのが現状である。When an industrial catalyst is used by filling it in a fixed bed reactor, it is necessary to mold the catalyst to a certain size in order to reduce the pressure loss of the reaction gas before and after the catalyst layer. It is. For this reason, there is also known a method in which the catalyst powder is usually formed into a column, a tablet, a ring, a sphere, or the like, or an active catalyst substance is impregnated or coated with an inert carrier. The advantages of this coated catalyst having an inert carrier as a core are that it can increase the effective utilization rate of the catalytically active component, uniform the distribution of the residence time of the reactants in the catalyst, and can be expected to improve selectivity. And the removal of heat of reaction is facilitated by the effect of improving the thermal conductivity or the effect of diluting the inert carrier. Therefore, there are many examples of application to a selective oxidation reaction that generates a large amount of heat. On the other hand, the technical difficulties in the production of coated catalysts are that peeling and cracking of the coating layer easily occur, it is difficult to obtain a catalyst with high mechanical strength, it is difficult to coat a large amount of the active catalyst substance on the carrier, It is difficult to obtain a highly active catalyst due to the active substance. The method of overcoming this point is related to the properties of the active catalyst substance, and there is no general-purpose technique, and the present situation is that the catalyst is individually solved.
【０００５】[0005]
【発明が解決しようとする課題】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高収率、高選択
的に製造する触媒及びその製法を提供することを目的と
する。SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst for producing methacrylic acid with high yield and high selectivity by subjecting methacrolein to gas-phase catalytic oxidation and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記問題
点を解決する方法として、従来のメタクロレイン用気相
接触酸化触媒の低活性、低選択性、短寿命の改良を試
み、Ｍｏ、Ｖ、Ｐ、Ｃｕを必須成分とする触媒を調製す
る際、即ち、該必須成分を含むヘテロポリ酸及び／又は
その塩を調製する際に、Ｃｕ（銅）成分を酢酸銅として
添加した場合に高活性、高選択性で特に寿命的に安定し
た高性能な工業化触媒が得られることを見いだし、本発
明を完成させた。すなわち、本発明は、（１）Ｍｏ、
Ｖ、Ｐ及びＣｕを必須の活性成分とする触媒において、
該触媒の調製用Ｃｕ原料として、その必要量の全部又は
一部に酢酸銅を使用したものであることを特徴とするメ
タクロレインの気相接触酸化によるメタクリル酸製造用
触媒、（２）Ｍｏ、Ｖ、Ｐ及びＣｕを必須の活性成分と
する触媒において、酢酸銅の全部又は一部が、水性溶液
とされることなく、固体のまま配合されたものであるこ
とを特徴とする上記（１）項に記載の触媒、（３）固体
酢酸銅と、Ｍｏ、Ｖ及びＰを含有するスラリー乾燥体と
を混合したものであることを特徴とする上記（２）項に
記載の触媒、（４）触媒が更にＡｓを活性成分として含
有する上記（１）項ないし（３）項のいずれか一項に記
載の触媒、（５）触媒活性成分の組成が下記式（１） Ｍｏ１０ＶａＰｂＣｕｃＡｓｄＸｅＹｆＯg （１） （式中、Ｍｏ、Ｖ、Ｐ、Ｃｕ、Ａｓ、Ｏはそれぞれモリ
ブデン、バナジウム、リン、銅、ヒ素及び酸素を表し、
ＸはＡｇ、Ｍｇ、Ｚｎ、Ａｌ、Ｂ、Ｇｅ、Ｓｎ、Ｐｂ、
Ｔｉ、Ｚｒ、Ｓｂ、Ｃｒ、Ｒｅ、Ｂｉ、Ｗ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｅ及びＴｈからなる群から選ばれる少なく
とも一種の元素を表し、ＹはＫ、Ｒｂ及びＣｓからなる
群より選ばれた少なくとも一種の元素を表す。ａ、ｂ、
ｃ、ｄ、ｅ、ｆ及びｇは各元素の原子比を表し、ａは
０．１≦ａ≦６、ｂは０．５≦ｂ≦６、ｃは０＜ｃ≦
３、ｄは０≦ｄ≦３、ｅは０≦ｅ≦３、ｆは０≦ｆ≦
１、ｇは他の元素の原子価ならびに原子比により定まる
値である。）で表される上記（１）項ないし（３）項の
いずれか一項に記載の触媒、（６）Ａｓを活性成分とし
て含有する上記（５）項に記載の触媒、（７）（ａ）Ｍ
ｏ、Ｖ、Ｐを含む化合物と酢酸銅を水と混合し、これら
の化合物の水溶液又は水分散体（以下、両者を含めてス
ラリー液という）を調製する工程、（ｂ）工程（ａ）で
得られたスラリー液を乾燥してスラリー乾燥体を得る工
程、（ｃ）工程（ｂ）で得られたスラリー乾燥体を、バ
インダーを用いて担体に被覆する工程、（ｄ）工程
（ｃ）で得られた被覆成型物を焼成する工程、からなる
被覆触媒の製法であって、前記バインダーとして水及び
１気圧下での沸点が１５０℃以下である有機化合物から
なる群から選ばれる少なくとも１種を用いることを特徴
とするメタクロレインの気相接触酸化によるメタクリル
酸製造用被覆触媒の製法、（８）（ａ）Ｍｏ、Ｖ、Ｐを
含む化合物を水と混合し、これら化合物の水溶液又は水
分散体（以下、両者を含めてスラリー液という）を調製
する工程、（ｂ）工程（ａ）で得られたスラリー液を乾
燥してスラリー乾燥体を得る工程、（ｂ’）工程（ｂ）
で得られたスラリー乾燥体に固体酢酸銅を混合する工
程、（ｃ）工程（ｂ’）で得られた混合物をバインダー
を用いて担体に被覆する工程、（ｄ）工程（ｃ）で得ら
れた被覆成型物を焼成する工程、からなる被覆触媒の製
法であって、前記バインダーとして水及び１気圧下での
沸点が１５０℃以下である有機化合物からなる群から選
ばれる少なくとも１種を用いることを特徴とするメタク
ロレインの気相接触酸化によるメタクリル酸製造用被覆
触媒の製法、（９）工程（ａ）においてスラリー液の原
料として更にＡｓ含有化合物を用いる上記（７）項又は
（８）項に記載の被覆触媒の製法、（１０）工程（ａ）
においてスラリー液の原料として、更に酸化銅を用いる
上記（７）項又は（８）項に記載の被覆触媒の製法、
（１１）工程（ａ）においてスラリー液の原料として、
更にＡｓ含有化合物及び酸化銅を用いる上記（７）項又
は（８）項に記載の被覆触媒の製法、（１２）バインダ
ーとしてエタノールを使用する上記（７）項ないし（１
１）項のいずれか一項に記載の被覆触媒の製法、（１
３）バインダーがエタノール／水＝１０／０〜５／５
（質量比）である上記（１２）項に記載の被覆触媒の製
法、（１４）上記（７）項ないし（１３）項のいずれか
一項に記載の製法により得られる被覆触媒、（１５）Ｍ
ｏ、Ｖ、Ｐ及びＣｕを必須の活性成分とする触媒が、担
体上に触媒組成物を被覆した被覆触媒であって、該触媒
組成物を調製する際のＣｕ原料の全部又は一部に酢酸銅
を使用したものであることを特徴とする被覆触媒、（１
６）触媒がヘテロポリ酸（塩）構造を有しているもので
ある上記（１５）の被覆触媒に関するものである。As a method for solving the above problems, the present inventors have attempted to improve the low activity, low selectivity and short life of the conventional gas phase catalytic oxidation catalyst for methacrolein, and , V, P, when preparing a catalyst containing essential components, that is, when preparing a heteropolyacid and / or a salt thereof containing the essential components, when a Cu (copper) component is added as copper acetate. The present inventors have found that a high-performance industrialized catalyst having high activity, high selectivity, and particularly stable in life can be obtained, and completed the present invention. That is, the present invention provides (1) Mo,
In a catalyst containing V, P and Cu as essential active components,
A catalyst for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein, characterized in that copper acetate is used for all or a part of a required amount thereof as a Cu raw material for preparing the catalyst; (2) Mo, (1) A catalyst comprising V, P and Cu as essential active components, wherein all or a part of copper acetate is compounded as a solid without being converted into an aqueous solution. (3) The catalyst according to the above (2), wherein the catalyst is a mixture of solid copper acetate and a dried slurry containing Mo, V and P. it is the (1) claim further contains as as the active ingredient a catalyst (3) a catalyst according to any one of claims, (5) the composition of the catalytically active component is represented by the following formula (1) Mo 10 V a P b Cu c As d X e Y f O g (1) ( wherein, Mo , V, P, Cu, As, O represent molybdenum, vanadium, phosphorus, copper, arsenic and oxygen, respectively.
X is Ag, Mg, Zn, Al, B, Ge, Sn, Pb,
Ti, Zr, Sb, Cr, Re, Bi, W, Fe, C
Y represents at least one element selected from the group consisting of o, Ni, Ce and Th, and Y represents at least one element selected from the group consisting of K, Rb and Cs. a, b,
c, d, e, f and g represent the atomic ratio of each element, a is 0.1 ≦ a ≦ 6, b is 0.5 ≦ b ≦ 6, and c is 0 <c ≦
3, d is 0 ≦ d ≦ 3, e is 0 ≦ e ≦ 3, f is 0 ≦ f ≦
1, g is a value determined by the valence and atomic ratio of another element. The catalyst according to any one of the above items (1) to (3), (6) the catalyst according to the above (5) containing As as an active ingredient, (7) (a) ) M
mixing a compound containing o, V, and P and copper acetate with water to prepare an aqueous solution or an aqueous dispersion of these compounds (hereinafter, referred to as a slurry liquid including both); (b) Step (a) Drying the obtained slurry liquid to obtain a dried slurry, (c) coating the dried slurry obtained in the step (b) on a carrier using a binder, and (d) step (c). Baking the obtained coated molded article, wherein the binder comprises at least one selected from the group consisting of water and an organic compound having a boiling point at 150 ° C. or less at 1 atm. A method for producing a coated catalyst for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, which is characterized by using (8) (a) mixing a compound containing Mo, V and P with water and dispersing an aqueous solution or dispersion of these compounds in water. Body (hereinafter, both Preparing a Umate of slurry), (b) step (step of obtaining a dried slurry and drying the resulting slurry in a), (b ') step (b)
Mixing the dried slurry obtained in the above with solid copper acetate, (c) coating the mixture obtained in the step (b ′) on a carrier using a binder, and (d) obtaining the mixture in the step (c). Baking the coated molded article, wherein at least one selected from the group consisting of water and an organic compound having a boiling point at 150 ° C. or less at 1 atm is used as the binder. (9) A method for producing a coated catalyst for producing methacrylic acid by gas phase catalytic oxidation of methacrolein, (9) The above item (7) or (8), wherein an As-containing compound is further used as a raw material of the slurry in step (a). (10) Step (a)
The method for producing a coated catalyst according to the above item (7) or (8), wherein copper oxide is further used as a raw material of the slurry liquid in
(11) In step (a), as a raw material of the slurry liquid,
Further, the method for producing a coated catalyst according to the above item (7) or (8) using an As-containing compound and copper oxide, (12) the above items (7) to (1) using ethanol as a binder.
(1) The method for producing a coated catalyst according to any one of (1), (1)
3) The binder is ethanol / water = 10/0 to 5/5
(15) a method for producing the coated catalyst according to the above (12), which is (mass ratio); (14) a coated catalyst obtained by the method according to any one of the above items (7) to (13); M
A catalyst containing o, V, P and Cu as essential active components is a coated catalyst in which a catalyst composition is coated on a carrier, and acetic acid is added to all or a part of the Cu raw material when preparing the catalyst composition. A coated catalyst characterized by using copper, (1
6) The coated catalyst according to the above (15), wherein the catalyst has a heteropolyacid (salt) structure.
【０００７】[0007]
【発明の実施の形態】本発明の触媒を得る好ましい方法
の１つは、Ｍｏ、Ｖ、Ｐ及びＣｕ並びに必要によりその
他の元素をそれぞれ若しくは複数含有する複数の化合物
（以下場合により「活性成分を含有する化合物」を「活
性成分含有化合物」とも言う）を水に溶解及び／又は分
散（工程（ａ））させ、スラリー液を調製する際に、銅
化合物として酢酸銅を使用し、得られたスラリー液を乾
燥（工程（ｂ））する方法である。また他の好ましい方
法は、前記スラリー液を調製する際に使用した酢酸銅の
一部若しくは全部を、固形酢酸銅（通常紛状若しくは顆
粒状）として、スラリー乾燥後に配合する方法である。
尚、スラリー液を得る際の原料としてアルカリ金属を含
有する化合物を使用した場合、スラリーの乾燥によって
得られる触媒はヘテロポリ酸塩を触媒活性成分として含
むこととなる。酢酸銅以外の、本発明においてスラリー
液調製用に用いられる活性成分含有化合物は、乾燥（工
程（ｂ））又は焼成（工程（ｄ））によりヘテロポリ酸
（塩）となる化合物が好ましい。該化合物としては活性
成分元素の、塩化物、硫酸塩、硝酸塩、アンモニウム
塩、酸化物又は酢酸塩等が挙げられる。好ましい化合物
をより具体的に例示すると硝酸カリウム、硝酸コバルト
又は硝酸セシウム等の硝酸塩、酸化モリブデン、五酸化
バナジウム、三酸化アンチモン、酸化セリウム、酸化亜
鉛又は酸化ゲルマニウム等の酸化物、正リン酸、リン
酸、ヒ酸、硼酸、リン酸アルミニウム又は１２タングス
トリン酸等の酸（又はその塩）等が挙げられる。これら
は単独で使用してもよいし、２種以上を混合して使用し
てもよい。尚、上記活性成分含有化合物のうちアンモニ
ウム塩の場合、アンモニウム基も触媒活性成分の構成の
一部となり、触媒活性に寄与するが、得られる触媒の長
期の反応安定性を低下させる場合があるので、それを使
用する場合には注意が必要である。通常はアンモニウム
塩以外の化合物が使用される。BEST MODE FOR CARRYING OUT THE INVENTION One of the preferred methods for obtaining the catalyst of the present invention is a plurality of compounds each containing one or more of Mo, V, P and Cu and, if necessary, other elements (hereinafter, in some cases, "active ingredient The "compound to be contained" is also obtained by dissolving and / or dispersing the "active compound containing compound" in water (step (a)) to prepare a slurry liquid, using copper acetate as a copper compound. This is a method of drying the slurry liquid (step (b)). Another preferable method is a method in which part or all of the copper acetate used in preparing the slurry liquid is converted into solid copper acetate (usually in a powder or granular form) and then mixed after drying the slurry.
When a compound containing an alkali metal is used as a raw material for obtaining a slurry liquid, the catalyst obtained by drying the slurry contains a heteropolyacid salt as a catalytically active component. The active ingredient-containing compound other than copper acetate used for preparing a slurry liquid in the present invention is preferably a compound that becomes a heteropoly acid (salt) upon drying (step (b)) or firing (step (d)). Examples of the compound include chlorides, sulfates, nitrates, ammonium salts, oxides and acetates of the active ingredient elements. More specifically, preferred compounds include nitrates such as potassium nitrate, cobalt nitrate and cesium nitrate, oxides such as molybdenum oxide, vanadium pentoxide, antimony trioxide, cerium oxide, zinc oxide and germanium oxide, orthophosphoric acid and phosphoric acid. (Or salts thereof) such as arsenic acid, boric acid, aluminum phosphate or 12-tungstophosphoric acid. These may be used alone or as a mixture of two or more. In the case of an ammonium salt among the above active ingredient-containing compounds, the ammonium group also becomes a part of the constitution of the catalytically active ingredient and contributes to the catalytic activity, but may reduce the long-term reaction stability of the obtained catalyst. Be careful when using it. Usually, compounds other than ammonium salts are used.
【０００８】本発明においてＣｕを含有する化合物（以
下単に銅化合物という）として使用する酢酸銅は、触媒
に必要な銅化合物の全量であっても、また一部であって
もよい。酢酸銅を使用した場合に触媒の性能が優れる理
由は確かではないが、酢酸銅はヘテロポリ酸（塩）を調
製する際の活性成分の還元状態を最適にする効果がある
と推定される。酢酸銅としては含水塩、無水塩のどちら
でも特に限定はなく、酢酸第一銅、酢酸第二銅、塩基性
酢酸銅のいずれも使用可能であるが、銅が２価である化
合物が好ましく、酢酸第二銅が特に好ましい。また、銅
化合物として酢酸銅を使用する限り、他の銅化合物を銅
成分として併用しても特に支障はなく、酸化銅、好まし
くは酸化第二銅を併用すると好ましい結果を与えること
がある。酢酸銅以外の銅化合物を併用する場合、酢酸銅
とそれ以外の銅化合物の総使用量はそれらの化合物中の
銅原子の合計量（原子比）がモリブデン原子１０に対し
て、通常０より大きく３以下、好ましくは０．０１以上
で、１以下の範囲であれば特に制限はない。通常酢酸銅
中の銅原子：それ以外の銅化合物中の銅原子＝２５：１
００〜１００：０の範囲内であるのが好ましい。In the present invention, the copper acetate used as a compound containing Cu (hereinafter simply referred to as a copper compound) may be the whole or a part of the copper compound necessary for the catalyst. The reason why the performance of the catalyst is excellent when copper acetate is used is not certain, but it is presumed that copper acetate has an effect of optimizing the reduced state of the active component when preparing a heteropolyacid (salt). The copper acetate is not particularly limited to any of hydrated salts and anhydrous salts, and any of cuprous acetate, cupric acetate, and basic copper acetate can be used, but a compound in which copper is divalent is preferable. Cupric acetate is particularly preferred. Further, as long as copper acetate is used as the copper compound, there is no particular problem even when another copper compound is used in combination with the copper component, and when copper oxide, preferably cupric oxide, is used in combination, favorable results may be obtained. When a copper compound other than copper acetate is used in combination, the total amount of copper acetate and the other copper compound is generally larger than 0, with the total amount (atomic ratio) of copper atoms in the compound being 10 or more relative to molybdenum atom 10. There is no particular limitation as long as it is in the range of 3 or less, preferably 0.01 or more and 1 or less. Normally, copper atoms in copper acetate: copper atoms in other copper compounds = 25: 1
It is preferably in the range of 00 to 100: 0.
【０００９】本発明において使用する酢酸銅の添加はス
ラリー液調製の際に、他の活性成分含有化合物と共に、
スラリー液用の原料として添加してもよいし、また、固
体の酢酸銅を水溶液とすることなく、好ましくは粉末状
若しくは顆粒状の酢酸銅の形で、スラリー液乾燥体（好
ましくは顆粒状若しくは粉体）にその必要量を添加して
もよい（工程ｂ’）。後者の方法は、場合により前者の
方法と併用してもよく、例えば酢酸銅の一部をスラリー
原料として使用し、残部を固体の酢酸銅としてスラリー
乾燥後に添加することもできる。後者の方法を実施する
場合、使用する酢酸銅の内、スラリー液の原料として添
加する酢酸銅とスラリー乾燥体に固体状で混合する酢酸
銅の割合は０：１００〜１００：２５の範囲であるのが
好ましい。固体酢酸銅はスラリー乾燥体と均一に混合で
きるものであれば特に形状、大きさ等は限定されない
が、通常混合がより均一にしやすいという観点から、該
スラリー乾燥体の粒度と同程度が好ましく、顆粒状若し
くは粉末状が好ましく、より好ましくは粉末状である。
また、固体酢酸銅の顆粒若しくは粉末における粒度は通
常粒径２ｍｍ以下であり、より好ましくは１ｍｍ以下、
更に好ましく５００μｍ以下、３００μｍ以下が最も好
ましい。下限は特にないがあまり微粉にしても、メリッ
トはないので、通常１０μｍ以上、好ましくは３０μｍ
以上で十分である。[0009] The addition of copper acetate used in the present invention, together with other active ingredient-containing compounds during the preparation of the slurry liquid,
It may be added as a raw material for a slurry liquid, or, without converting solid copper acetate into an aqueous solution, preferably in the form of powdery or granular copper acetate, a dried slurry liquid (preferably granular or (Powder) may be added in the required amount (step b ′). The latter method may optionally be used in combination with the former method. For example, a part of copper acetate may be used as a slurry raw material, and the remainder may be added as solid copper acetate after drying the slurry. When performing the latter method, the ratio of copper acetate to be added as a raw material of the slurry liquid and copper acetate to be mixed in a solid state with the dried slurry is in the range of 0: 100 to 100: 25. Is preferred. Solid copper acetate is not particularly limited in shape, size, etc. as long as it can be uniformly mixed with the dried slurry, but from the viewpoint that mixing is more likely to be uniform, it is preferably about the same as the particle size of the dried slurry, Granular or powdery forms are preferred, and more preferably powdery forms.
The particle size of the solid copper acetate granules or powder is usually 2 mm or less, more preferably 1 mm or less,
More preferably, it is 500 μm or less, most preferably 300 μm or less. There is no particular lower limit, but there is no merit even if the powder is too fine, so it is usually 10 μm or more, preferably 30 μm.
That's enough.
【００１０】上記の方法の中、後者の固体酢酸銅をスラ
リー乾燥体に添加する方法がより好ましい。後者の方法
により得られた触媒は、酢酸銅の全量をスラリー原料と
して使用して得られた前者の触媒に比して、より活性が
高い。 従って後者の触媒を使用して、メタクロレイン
からメタクリル酸を製造した場合、前者の触媒を用いた
場合に比べて、同じ反応温度ではより高収率（より高い
転化率及び同程度の選択率）でメタクリ酸を得ることが
でき、また、同程度の高収率（転化率及び選択率とも同
程度）であれば、より低い反応温度で達成することがで
きる。触媒寿命の観点からは反応温度を低くできること
は非常に好ましい。[0010] Of the above methods, the latter method of adding solid copper acetate to the dried slurry is more preferable. The catalyst obtained by the latter method has higher activity than the former catalyst obtained by using the entire amount of copper acetate as a slurry raw material. Therefore, when methacrylic acid is produced from methacrolein using the latter catalyst, a higher yield (higher conversion and similar selectivity) is obtained at the same reaction temperature than when the former catalyst is used. The methacrylic acid can be obtained at a lower reaction temperature if the yield is as high as the conversion (the conversion and the selectivity are the same). It is very preferable that the reaction temperature can be lowered from the viewpoint of catalyst life.
【００１１】本発明において、Ｍｏ、Ｖ、Ｐ及びＣｕ以
外の活性成分としては、Ａｓ、Ａｇ、Ｍｇ、Ｚｎ、Ａ
ｌ、Ｂ、Ｇｅ、Ｓｎ、Ｐｂ、Ｔｉ、Ｚｒ、Ｓｂ、Ｃｒ、
Ｒｅ、Ｂｉ、Ｗ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｅ、Ｔｈ、Ｋ、
Ｒｂ、Ｃｓ等が挙げられ、Ａｓ、Ａｇ、Ｍｇ、Ｚｎ、Ａ
ｌ、Ｂ、Ｇｅ、Ｓｎ、Ｐｂ、Ｔｉ、Ｚｒ、Ｓｂ、Ｃｒ、
Ｒｅ、Ｂｉ、Ｗ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｅ、Ｔｈ、Ｋ、
Ｒｂ、Ｃｓからなる群から選ばれる１種以上が好まし
く、Ａｓが特に好ましい。またＡｓを活性成分として含
有する場合、Ｃｓを活性成分として併用すると好ましい
結果を与えることもある。In the present invention, the active components other than Mo, V, P and Cu are As, Ag, Mg, Zn, A
1, B, Ge, Sn, Pb, Ti, Zr, Sb, Cr,
Re, Bi, W, Fe, Co, Ni, Ce, Th, K,
Rb, Cs and the like, and As, Ag, Mg, Zn, A
1, B, Ge, Sn, Pb, Ti, Zr, Sb, Cr,
Re, Bi, W, Fe, Co, Ni, Ce, Th, K,
One or more selected from the group consisting of Rb and Cs is preferable, and As is particularly preferable. When As is contained as an active ingredient, when Cs is used in combination as an active ingredient, preferable results may be obtained.
【００１２】本発明における触媒の各活性成分の割合
は、その原子比がモリブデン１０に対して、バナジウム
が通常０．１以上で６以下、好ましくは、０．３以上で
２．０以下、リンが通常０．５以上で６以下、好ましく
は０．５以上で３以下、銅が通常０より大きく３以下、
好ましくは０．０１以上で１以下である。必要により用
いるその他の活性成分の種類及びその使用割合は、その
触媒の使用条件等に合わせて、最適な性能を示す触媒が
得られるように、適宜決定される。通常の条件で使用さ
れる好ましい触媒は、下記式（１） Ｍｏ１０ＶａＰｂＣｕｃＡｓｄＸｅＹｆＯg （１） （式中、Ｍｏ、Ｖ、Ｐ、Ｃｕ、Ａｓ、Ｏはそれぞれモリ
ブデン、バナジウム、リン、銅、ヒ素及び酸素を表し、
又、ＸはＡｇ、Ｍｇ、Ｚｎ、Ａｌ、Ｂ、Ｇｅ、Ｓｎ、Ｐ
ｂ、Ｔｉ、Ｚｒ、Ｓｂ、Ｃｒ、Ｒｅ、Ｂｉ、Ｗ、Ｆｅ、
Ｃｏ、Ｎｉ、Ｃｅ及びＴｈからなる群から選ばれる少な
くとも一種の元素を表し、ＹはＫ、Ｒｂ及びＣｓからな
る群より選ばれた少なくとも一種の元素を表す。ａ、
ｂ、ｃ、ｄ、ｅ、ｆ、及びｇは各元素の原子比を表し、
ａは通常０．１≦ａ≦６、好ましくは０．３≦ａ≦２、
ｂは通常０．５≦ｂ≦６、好ましくは０．５≦ｂ≦３、
ｃは通常０＜ｃ≦３、好ましくは０．０１≦ｃ≦１、ｄ
は通常０≦ｄ≦３、好ましくは０．０１≦ｄ≦１、ｅは
通常０≦ｅ≦３、好ましくは０．０１≦ｅ≦１、ｆは０
≦ｆ≦１、好ましくは０≦ｆ≦０．０６の値をとる。ま
た、ｇは酸素以外の他の元素の原子価ならびに原子比に
より定まる値であり、通常３５≦ｇ≦８０である。）で
示される活性成分組成を有するものである。The ratio of each active component of the catalyst in the present invention is such that the atomic ratio of vanadium to molybdenum 10 is usually 0.1 or more and 6 or less, preferably 0.3 or more and 2.0 or less, Is usually 0.5 or more and 6 or less, preferably 0.5 or more and 3 or less, copper is usually more than 0 and 3 or less,
Preferably it is 0.01 or more and 1 or less. The types of the other active components used as necessary and their usage ratio are appropriately determined according to the conditions of use of the catalyst and the like so that a catalyst having optimum performance can be obtained. Preferred catalysts to be used in normal conditions, the following formula (1) Mo 10 V a P b Cu c As d X e Y f O g (1) ( wherein, Mo, V, P, Cu , As, O Represents molybdenum, vanadium, phosphorus, copper, arsenic and oxygen, respectively.
X is Ag, Mg, Zn, Al, B, Ge, Sn, P
b, Ti, Zr, Sb, Cr, Re, Bi, W, Fe,
Y represents at least one element selected from the group consisting of Co, Ni, Ce and Th, and Y represents at least one element selected from the group consisting of K, Rb and Cs. a,
b, c, d, e, f, and g represent the atomic ratio of each element,
a is usually 0.1 ≦ a ≦ 6, preferably 0.3 ≦ a ≦ 2,
b is usually 0.5 ≦ b ≦ 6, preferably 0.5 ≦ b ≦ 3,
c is usually 0 <c ≦ 3, preferably 0.01 ≦ c ≦ 1, d
Is usually 0 ≦ d ≦ 3, preferably 0.01 ≦ d ≦ 1, e is usually 0 ≦ e ≦ 3, preferably 0.01 ≦ e ≦ 1, and f is 0
≦ f ≦ 1, preferably 0 ≦ f ≦ 0.06. G is a value determined by the valence and atomic ratio of elements other than oxygen, and usually 35 ≦ g ≦ 80. ).
【００１３】該触媒は以下の手順により得ることができ
る。まず活性成分含有化合物のスラリー液を調製する。
スラリー液は、各活性成分を含有する複数の化合物と溶
媒、好ましくは水とを均一に混合して得ることができ
る。該スラリー液は銅化合物を除き必要な活性成分含有
化合物の全てを、触媒の必要量において含有することが
好ましい。また銅化合物については、これを含まない
か、又は必要量の一部を含むスラリー液とすることも、
また、必要な銅化合物の全量を含むスラリー液とするこ
ともできる。The catalyst can be obtained by the following procedure. First, a slurry of the active ingredient-containing compound is prepared.
The slurry liquid can be obtained by uniformly mixing a plurality of compounds containing each active ingredient and a solvent, preferably water. The slurry liquid preferably contains all the necessary active ingredient-containing compounds except for the copper compound in a required amount of the catalyst. In addition, the copper compound does not include this, or may be a slurry liquid containing a part of the required amount,
Also, a slurry liquid containing the entire amount of the necessary copper compound can be used.
【００１４】本発明の触媒に必要な活性成分含有化合物
全てを含むスラリー液を調製する場合は、銅化合物も一
緒に添加される。銅化合物の必要量の全量を含むスラリ
ー液とする場合は、銅化合物の全て、又は一部として酢
酸銅が使用される。また、このスラリー液中に必要な銅
化合物の一部のみを含ませる場合は、銅化合物として、
酢酸銅を使用してもよいし、また、その含ませる量によ
っては酢酸銅以外の銅化合物のみを使用してもよい。な
お、スラリー液が必要量の銅化合物の一部しか含まない
か、又は全く含まない時は、不足分の銅化合物は後記す
るようにスラリー液乾燥後に、固体酢酸銅で補充する。When preparing a slurry containing all the active ingredient-containing compounds required for the catalyst of the present invention, a copper compound is also added. In the case of preparing a slurry containing the entire required amount of the copper compound, copper acetate is used as all or part of the copper compound. When only a part of the necessary copper compound is contained in the slurry, as the copper compound,
Copper acetate may be used, or only a copper compound other than copper acetate may be used depending on the amount to be contained. When the slurry liquid contains only a part of the required amount of the copper compound or does not contain the copper compound at all, the insufficient copper compound is replenished with solid copper acetate after drying the slurry liquid as described later.
【００１５】尚、本発明においては、スラリー液が水溶
液であるのが好ましい。スラリー液における各活性成分
の化合物の使用割合は、各活性成分の原子比が上記した
範囲であれば特に制限はない。水の使用量は、用いる化
合物の全量を完全に溶解できるか、または均一に混合で
きる量であれば特に制限はないが、下記する乾燥方法や
乾燥条件等を勘案して適宜決定される。通常スラリー調
製用化合物の合計質量１００質量部に対して、２００〜
２０００質量部程度である。水の量は多くてもよいが、
多過ぎると乾燥工程のエネルギーコストが高くなり、ま
た完全に乾燥できない場合も生ずるなどデメリットが多
く、メリットはあまりないので適量が好ましい。In the present invention, the slurry is preferably an aqueous solution. The use ratio of the compound of each active ingredient in the slurry liquid is not particularly limited as long as the atomic ratio of each active ingredient is in the above range. The amount of water to be used is not particularly limited as long as it can completely dissolve the entire amount of the compound to be used or can be uniformly mixed, but is appropriately determined in consideration of the drying method and drying conditions described below. Usually, 200 to 100 parts by mass of the total amount of the compound for slurry preparation, 200 to
It is about 2000 parts by mass. The amount of water can be large,
If the amount is too large, the energy cost of the drying step increases, and complete drying may occur. There are many disadvantages.
【００１６】次いで上記で得られたスラリー液を乾燥
し、スラリー乾燥体とする。乾燥方法は、スラリー液が
完全に乾燥できる方法であれば特に制限はないが、例え
ばドラム乾燥、凍結乾燥、噴霧乾燥等が挙げられる。こ
れらのうち本発明においては、スラリー液状態から短時
間に粉末又は顆粒に乾燥することができる噴霧乾燥が好
ましい。この場合の乾燥温度はスラリー液の濃度、送液
速度等によって異なるが概ね乾燥機の出口における温度
が８５〜１３０℃である。また、この際得られるスラリ
ー乾燥体の平均粒径が３０〜１５０μｍとなるよう乾燥
するのが好ましい。スラリー乾燥体が塊状もしくは大き
な粒子である場合には適宜粉砕等により上記の粒径の粒
子とするのが好ましい。本発明においてスラリー乾燥体
といった場合、このように粉砕されたものもスラリー乾
燥体に含むものとする。Next, the slurry liquid obtained above is dried to obtain a dried slurry. The drying method is not particularly limited as long as the slurry liquid can be completely dried, and examples thereof include drum drying, freeze drying, and spray drying. Among them, in the present invention, spray drying which can be dried from a slurry liquid state to powder or granules in a short time is preferable. The drying temperature in this case varies depending on the concentration of the slurry liquid, the liquid sending speed, and the like, but the temperature at the outlet of the dryer is generally 85 to 130 ° C. In this case, it is preferable to dry the dried slurry so that the average particle diameter thereof is 30 to 150 μm. When the dried slurry is a lump or large particles, it is preferable to appropriately form particles having the above-mentioned particle size by pulverization or the like. In the present invention, in the case of a dried slurry, such a pulverized product is included in the dried slurry.
【００１７】スラリー液が銅化合物を含まないか若しく
は必要量の一部しか含まなかった場合には、このスラリ
ー乾燥体にその不足分を補う量の酢酸銅を添加混合し、
均一な混合物とする。こうして得られたスラリー乾燥体
又は上記で得られた酢酸銅混合物（以下両者を含めて単
にスラリー乾燥体という）はそのまま触媒として気相接
触酸化反応に供することができるが、前記したように反
応ガスの圧力損失を少なくするために、柱状物、錠剤、
リング状、球状等に成型するのが好ましい。このうち選
択性の向上や反応熱の除去が期待できることから不活性
担体をスラリー乾燥体で被覆し、被覆触媒とするのが特
に好ましい。被覆工程（工程（ｃ））は以下に述べる転
動造粒法が好ましい。この方法は、例えば固定容器内の
底部に、平らなあるいは凹凸のある円盤を有する装置中
で、円盤を高速で回転することにより、容器内の担体を
自転運動と公転運動の繰り返しにより激しく撹拌させ、
ここにバインダーと乾燥粉体並びに必要により他の添加
剤例えば成型助剤及び強度向上材の混合物等を添加する
ことにより該混合物を担体に被覆する方法である。バイ
ンダーの添加方法は、前記混合物に予め混合してお
く、混合物を固定容器内に添加するのと同時に添加、
混合物を固定容器内に添加した後に添加、混合物を
固定容器内に添加する前に添加、混合物とバインダー
をそれぞれ分割し、〜を適宜組み合わせて全量添加
する等の方法が任意に採用しうる。このうちにおいて
は、例えば混合物の固定容器壁への付着、混合物同士の
凝集がなく担体上に所定量が担持されるようオートフィ
ーダー等を用いて添加速度を調節して行うのが好まし
い。When the slurry liquid does not contain a copper compound or contains only a part of the required amount, an amount of copper acetate to make up for the shortage is added to the dried slurry and mixed.
Make a homogeneous mixture. The thus-obtained dried slurry or the copper acetate mixture obtained above (hereinafter simply referred to as a dried slurry) may be used as it is as a catalyst in a gas phase catalytic oxidation reaction. Column, tablets,
It is preferable to mold into a ring shape, a spherical shape or the like. Among them, it is particularly preferable to coat the inert carrier with a dried slurry to obtain a coated catalyst because selectivity and removal of reaction heat can be expected. The coating step (step (c)) is preferably a rolling granulation method described below. In this method, for example, in a device having a flat or uneven disk at the bottom of a fixed container, by rotating the disk at a high speed, the carrier in the container is vigorously stirred by repeating the rotation and the orbital motion. ,
In this method, a carrier is coated by adding a binder, a dry powder, and if necessary, other additives such as a mixture of a molding aid and a strength improving material. The method of adding the binder is previously mixed with the mixture, and added simultaneously with the addition of the mixture in the fixed container,
A method of adding the mixture after adding it to the fixed container, adding the mixture before adding the mixture to the fixed container, dividing the mixture and the binder, respectively, and appropriately combining the above and adding the whole amount can be arbitrarily adopted. Among these, it is preferable to adjust the addition rate by using an auto feeder or the like so that the mixture is not adhered to the wall of the fixed container and the mixture is not aggregated, and the predetermined amount is supported on the carrier.
【００１８】バインダーは水及びその標準状態（１気圧
下）での沸点が１５０℃以下の有機化合物からなる群か
ら選ばれる少なくとも１種であれば特に制限はないが、
被覆後の乾燥等を考慮すると沸点１００℃以下のものが
このましい。水以外のバインダーの具体例としてはメタ
ノール、エタノール、プロパノール類、ブタノール類等
のアルコール、好ましくは炭素数１乃至４のアルコー
ル、エチルエーテル、ブチルエーテルまたはジオキサン
等のエーテル、酢酸エチル又は酢酸ブチル等のエステ
ル、アセトン又はメチルエチルケトン等のケトン等並び
にそれらの水溶液等が挙げられ、特にエタノールが好ま
しい。バインダーとしてエタノールを使用する場合、エ
タノール／水＝１０／０〜５／５（質量比）、好ましく
は１０／０〜７／３（質量比）が好ましい。これらバイ
ンダーの使用量は、スラリー乾燥体１００質量部に対し
て通常２〜６０質量部、好ましくは５〜２５質量部であ
る。The binder is not particularly limited as long as it is at least one selected from the group consisting of water and organic compounds having a boiling point of 150 ° C. or less under standard conditions (at 1 atm).
Taking into account drying after coating and the like, those having a boiling point of 100 ° C. or less are preferred. Specific examples of the binder other than water include alcohols such as methanol, ethanol, propanols and butanols, preferably alcohols having 1 to 4 carbon atoms, ethers such as ethyl ether, butyl ether or dioxane, and esters such as ethyl acetate or butyl acetate. , Acetone or ketones such as methyl ethyl ketone, and aqueous solutions thereof, and ethanol is particularly preferable. When ethanol is used as the binder, the ratio of ethanol / water is preferably 10/0 to 5/5 (mass ratio), and more preferably 10/0 to 7/3 (mass ratio). The amount of the binder to be used is generally 2 to 60 parts by mass, preferably 5 to 25 parts by mass, based on 100 parts by mass of the dried slurry.
【００１９】本発明において用いうる担体の具体例とし
ては、炭化珪素、アルミナ、シリカアルミナ、ムライ
ト、アランダム等の直径１〜１５ｍｍ、好ましくは２．
５〜１０ｍｍの球形担体等が挙げられる。これら担体は
通常は１０〜７０％の空孔率を有するものが用いられ
る。担体と被覆されるスラリー乾燥体の割合は通常、ス
ラリー乾燥体／（スラリー乾燥体＋担体）＝１０〜７５
質量％、好ましくは１５〜６０質量％となる量使用す
る。被覆されるスラリー乾燥体の割合が多い場合、被覆
触媒の反応活性は大きくなるが、機械的強度が小さくな
る（磨損度が大きくなる）傾向がある。逆に、被覆され
るスラリー乾燥体の割合が少ない場合、機械的強度は大
きい（磨損度は小さい）が、反応活性は小さくなる傾向
がある。Specific examples of the carrier that can be used in the present invention include silicon carbide, alumina, silica-alumina, mullite, alundum and the like having a diameter of 1 to 15 mm, preferably 2.
A spherical carrier having a size of 5 to 10 mm is exemplified. These carriers usually have a porosity of 10 to 70%. The ratio of the carrier and the dried slurry to be coated is usually the slurry dried product / (the dried slurry + the carrier) = 10 to 75.
%, Preferably 15 to 60% by weight. When the ratio of the dried slurry to be coated is large, the reaction activity of the coated catalyst increases, but the mechanical strength tends to decrease (the degree of friability increases). Conversely, when the ratio of the dried slurry to be coated is small, the mechanical strength is large (the friability is small), but the reaction activity tends to be small.
【００２０】本発明においては、スラリー乾燥体を担体
上に被覆する場合、更に必要によりシリカゲル、珪藻
土、アルミナ粉末等の成型助剤を用いてもよい。成型助
剤の使用量は、スラリー乾燥体１００質量部に対して通
常５〜６０質量部である。また、更に必要により触媒成
分に対して不活性な、セラミックス繊維、ウイスカー等
の無機繊維を強度向上材として用いる事は、触媒の機械
的強度の向上に有用である。しかし、チタン酸カリウム
ウイスカーや塩基性炭酸マグネシウムウイスカーの様な
触媒成分と反応する繊維は好ましくない。これら繊維の
使用量は、スラリー乾燥体１００質量部に対して通常１
〜３０質量部である。上記成型助剤及び強度向上材等の
添加剤は、通常被覆工程において、担体、スラリー乾燥
体、バインダー等と共に造粒機中に添加し、担体の被覆
に使用される。このようにしてスラリー乾燥体を担体に
被覆するが、この際得られる被覆品は通常直径が３〜１
５ｍｍ程度である。こうして得られた被覆触媒はそのま
ま触媒として気相接触酸化反応に供することができる
が、焼成（工程（ｄ））すると触媒活性が向上する場合
があり好ましい。この場合の焼成温度は通常１００〜４
２０℃、好ましくは２５０〜４００℃、焼成時間は１〜
２０時間である。In the present invention, when the dried slurry is coated on a carrier, a molding aid such as silica gel, diatomaceous earth, or alumina powder may be used as necessary. The amount of the molding aid used is usually 5 to 60 parts by mass based on 100 parts by mass of the dried slurry. Further, the use of inorganic fibers, such as ceramic fibers and whiskers, which are inert with respect to the catalyst component as necessary, is useful for improving the mechanical strength of the catalyst. However, fibers that react with catalyst components such as potassium titanate whiskers and basic magnesium carbonate whiskers are not preferred. The amount of these fibers is usually 1 to 100 parts by mass of the dried slurry.
３０30 parts by mass. The above-mentioned additives such as a molding aid and a strength improving material are usually added to a granulator together with a carrier, a dried slurry, a binder and the like in a coating step, and used for coating the carrier. The dried slurry is coated on a carrier in this manner, and the coated product obtained at this time usually has a diameter of 3 to 1 mm.
It is about 5 mm. The thus-obtained coated catalyst can be directly used as a catalyst in a gas-phase catalytic oxidation reaction, but calcining (step (d)) is preferable since the catalytic activity may be improved in some cases. The firing temperature in this case is usually 100 to 4
20 ° C, preferably 250 to 400 ° C, firing time is 1 to
20 hours.
【００２１】上記のようにして得られた本発明の触媒
は、メタクロレインを気相接触酸化してメタクリル酸を
製造する際に使用される。なお、本発明の触媒といった
場合、特に断らない限り、工程（ａ）〜（ｂ）、必要に
応じて更に（ｂ’）を経て得られたスラリー乾燥体、又
は更に工程（ｃ）（及び好ましくは工程（ｄ））を経て
得られた被覆触媒の両者を含む意味で使用する。The catalyst of the present invention obtained as described above is used for producing methacrylic acid by subjecting methacrolein to gas-phase catalytic oxidation. In the case of the catalyst of the present invention, unless otherwise specified, the dried slurry obtained through the steps (a) to (b) and, if necessary, further (b ′), or the step (c) (and preferably Is used to mean both of the coated catalyst obtained through the step (d)).
【００２２】気相接触酸化反応には分子状酸素又は分子
状酸素含有ガスが使用される。メタクロレインに対する
分子状酸素の使用割合はモル比で０．５〜２０の範囲が
好ましく、特に１〜１０の範囲が好ましい。反応を円滑
に進行させることを目的として、原料ガス中に水をメタ
クロレインに対しモル比で１〜２０の範囲で添加するこ
とが好ましい。原料ガスは酸素、必要により水（通常水
蒸気として含む）の他に窒素、炭酸ガス、飽和炭化水素
等の反応に不活性なガス等を含んでいてもよい。また、
メタクロレインはイソブチレン、第三級ブタノールを酸
化して得られたガスをそのまま供給してもよい。気相接
触酸化反応における反応温度は通常２００〜４００℃、
好ましくは２６０〜３６０℃、原料ガスの供給量は空間
速度（ＳＶ）にして、通常１００〜６０００ｈｒ−１、
好ましくは４００〜３０００ｈｒ−１である。本発明に
よる触媒を用いた場合、ＳＶを上げても反応成績には大
きな変化はなく、高空間速度にて反応を実施することが
可能である。また、接触酸化反応は加圧下または減圧下
でも可能であるが、一般的には大気圧付近の圧力が適し
ている。In the gas phase catalytic oxidation reaction, molecular oxygen or a gas containing molecular oxygen is used. The molar ratio of molecular oxygen to methacrolein is preferably in the range of 0.5 to 20, more preferably 1 to 10. For the purpose of allowing the reaction to proceed smoothly, it is preferable to add water to the raw material gas in a molar ratio of 1 to 20 with respect to methacrolein. The raw material gas may contain a gas inert to the reaction such as nitrogen, carbon dioxide gas, saturated hydrocarbon and the like, in addition to oxygen and, if necessary, water (normally included as water vapor). Also,
For methacrolein, a gas obtained by oxidizing isobutylene and tertiary butanol may be supplied as it is. The reaction temperature in the gas phase catalytic oxidation reaction is usually 200 to 400 ° C,
Preferably, the feed rate of the raw material gas is set to a space velocity (SV) of 260 to 360 ° C., usually 100 to 6000 hr −1 ,
Preferably it is 400-3000 hr < -1 >. When the catalyst according to the present invention is used, there is no significant change in the reaction result even when the SV is increased, and the reaction can be performed at a high space velocity. Further, the catalytic oxidation reaction can be performed under increased or reduced pressure, but generally, a pressure near the atmospheric pressure is suitable.
【００２３】[0023]
【実施例】以下に本発明を実施例により更に具体的に説
明する。尚、実施例中の触媒活性成分組成はいずれも仕
込み原料からの比率である。また式において酸素は省略
して表示した。EXAMPLES The present invention will be described more specifically with reference to the following examples. In addition, the composition of the catalytically active components in the examples is a ratio from the charged raw materials. In the formula, oxygen is omitted.
【００２４】実施例Ａ１ １）触媒の調整 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム１１．３７ｇ、酸化第二銅３．３１ｇ、酢酸
第二銅・一水和物８．３２ｇ、８５％正リン酸２８．８
２ｇ、６０％ヒ酸２４．６４ｇを分散あるいは溶解さ
せ、これを撹拌しつつ９５℃〜１００℃で約６時間加熱
還流して赤褐色の透明溶液を得た。そこに三酸化アンチ
モン１．５２ｇを添加して、さらに９５℃〜１００℃で
約３時間加熱還流して濃紺色の溶液を得た。続いて、こ
の溶液を噴霧乾燥機により乾燥して触媒顆粒を得た。次
に、回転するドラム中に球状多孔質アルミナ担体３００
ｇを仕込み、９０％エタノール水溶液を滴下しながら、
先に得た触媒顆粒３１９ｇをセラミック繊維４４．７ｇ
と均一に混合した粉末を徐々に担体上にふりかけ、球状
担体を触媒顆粒で被覆成型した。この間の粉末の損失は
ほとんど認められなかった。得られた成型物を空気流通
下で３１０℃で５時間焼成して被覆触媒を得た。得られ
た被覆触媒の活性成分組成はＭｏ10Ｖ0.6Ｐ1.2Ｃｕ0.4
Ａｓ0.5Ｓｂ0.05であった。 ２）メタクロレインの触媒酸化反応 得られた反応用触媒１０ｍｌを内径１８．４ｍｍのステ
ンレス反応管に充填し、原料ガス組成（モル比） メタ
クロレイン：酸素：水蒸気：窒素＝１：２．８：５．
０：２１．０、空間速度（ＳＶ）１０００ｈｒ−１、反
応温度３１０℃の条件で、メタクロレインの酸化反応を
行ったところ、メタクロレインの転化率は８５．９％で
あり、メタクリル酸の選択率は８４．８％であった。Example A1 1) Preparation of catalyst 300 g of molybdenum trioxide, 11.37 g of vanadium pentoxide, 3.31 g of cupric oxide, 8.32 g of cupric acetate monohydrate, 85% in 1900 ml of pure water Orthophosphoric acid 28.8
2 g and 24.64 g of 60% arsenic acid were dispersed or dissolved, and the mixture was heated and refluxed at 95 ° C. to 100 ° C. for about 6 hours with stirring to obtain a red-brown transparent solution. 1.52 g of antimony trioxide was added thereto, and the mixture was further heated under reflux at 95 ° C. to 100 ° C. for about 3 hours to obtain a dark blue solution. Subsequently, this solution was dried by a spray dryer to obtain catalyst granules. Next, a spherical porous alumina carrier 300 is placed in a rotating drum.
g, and dropping a 90% aqueous ethanol solution.
319 g of the catalyst granules obtained above were mixed with 44.7 g of ceramic fiber.
The powder uniformly mixed with the mixture was gradually sprinkled on the carrier, and the spherical carrier was coated with the catalyst granules and molded. During this time, almost no powder loss was observed. The obtained molded product was calcined at 310 ° C. for 5 hours under air flow to obtain a coated catalyst. The active component composition of the obtained coated catalyst was Mo 10 V 0.6 P 1.2 Cu 0.4
As 0.5 Sb 0.05 . 2) Catalytic oxidation reaction of methacrolein 10 ml of the obtained catalyst for reaction was filled in a stainless steel reaction tube having an inner diameter of 18.4 mm, and the raw material gas composition (molar ratio) methacrolein: oxygen: steam: nitrogen = 1: 2.8: 5.
When the oxidation reaction of methacrolein was carried out under the conditions of 0: 21.0, space velocity (SV) 1000 hr -1 and reaction temperature 310 ° C., the conversion of methacrolein was 85.9%, and the selection of methacrylic acid was carried out. The rate was 84.8%.
【００２５】比較例１ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム１１．３７ｇ、酸化第二銅６．６３ｇ、およ
び８５％正リン酸２８．８２ｇ、６０％ヒ酸２４．６４
ｇを分散あるいは溶解させ、これを撹拌しつつ９５〜１
００℃で６時間加熱還流して赤褐色の透明溶液を得た。
そこに三酸化アンチモン１．５２ｇを添加して、さらに
９５〜１００℃で ３時間加熱還流して濃紺色の溶液を
得た。続いて、この溶液を噴霧乾燥機により乾燥して触
媒顆粒を得た。以下は実施例Ａ１と同様の操作で被覆触
媒を得た。得られた被覆触媒の活性成分組成は実施例Ａ
１と同じでＭｏ10Ｖ0.6Ｐ1.2Ｃｕ 0.4Ａｓ0.5Ｓｂ0.05で
あった。続いて、得られた被覆触媒を用いて実施例Ａ１
と同様に反応を行った。メタクロレインの転化率は７
９．９％であり、メタクリル酸の選択率は８７．８％で
あった。Comparative Example 1 300 g of molybdenum trioxide and 1900 ml of pure water
11.37 g of vanadium, 6.63 g of cupric oxide, and
And 85% orthophosphoric acid 28.82 g, 60% arsenic acid 24.64
g is dispersed or dissolved.
The mixture was heated under reflux at 00 ° C. for 6 hours to obtain a reddish brown transparent solution.
1.52 g of antimony trioxide was added thereto, and further
Heat to reflux at 95-100 ° C for 3 hours to form a dark blue solution
Obtained. Subsequently, the solution is dried by a spray drier and touched.
Medium granules were obtained. The following is the same procedure as in Example A1 for covering.
A medium was obtained. The active ingredient composition of the resulting coated catalyst was determined in Example A.
Mo same as 1TenV0.6P1.2Cu 0.4As0.5Sb0.05so
there were. Subsequently, Example A1 was performed using the obtained coated catalyst.
The reaction was carried out in the same manner as described above. Conversion of methacrolein is 7
9.9%, and the selectivity of methacrylic acid was 87.8%.
there were.
【００２６】実施例Ａ２ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２４．６４ｇ、酢酸第二銅・一水和物８．３
２ｇ、および８５％正リン酸２６．４２ｇ、硝酸ルビジ
ウム ９．２２ｇを分散あるいは溶解させ、これを撹拌
しつつ９５〜１００℃で９時間加熱還流して赤褐色の透
明溶液を得た。続いて、この溶液を噴霧乾燥機により乾
燥して触媒顆粒を得た。以下は実施例Ａ１と同様の操作
で被覆触媒を得た。得られた被覆触媒の活性成分組成は
Ｍｏ10Ｖ1.3Ｐ1.1Ｃｕ0.2Ｒｂ0.3であった。続いて、得
られた被覆触媒を用いて実施例Ａ１と同様に反応を行っ
た。メタクロレインの転化率は７４．２％であり、メタ
クリル酸の選択率は７９．０％であった。Example A2 300 g of molybdenum trioxide, 24.64 g of vanadium pentoxide, 8.3 cupric acetate monohydrate in 1900 ml of pure water
2 g, 26.42 g of 85% orthophosphoric acid, and 9.22 g of rubidium nitrate were dispersed or dissolved, and heated and refluxed at 95 to 100 ° C. for 9 hours while stirring to obtain a reddish brown transparent solution. Subsequently, this solution was dried by a spray dryer to obtain catalyst granules. The following procedure was the same as in Example A1 to obtain a coated catalyst. The active component composition of the obtained coated catalyst was Mo 10 V 1.3 P 1.1 Cu 0.2 Rb 0.3 . Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. The conversion of methacrolein was 74.2% and the selectivity for methacrylic acid was 79.0%.
【００２７】比較例２ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２４．６４ｇ、酸化第二銅３．３１ｇ、およ
び８５％正リン酸２６．４２ｇ、硝酸ルビジウム９．２
２ｇを分散あるいは溶解させ、これを撹拌しつつ９５〜
１００℃で９時間加熱還流して赤褐色の透明溶液を得
た。続いて、この溶液を噴霧乾燥機により乾燥して触媒
顆粒を得た。以下は実施例Ａ１と同様の操作で被覆触媒
を得た。得られた反応用触媒の活性成分組成は実施例Ａ
２と同じでＭｏ10Ｖ1.3Ｐ1.1Ｃｕ0.2Ｒｂ0.3であった。
続いて、得られた反応用触媒を実施例Ａ１と同様に反応
を行った。メタクロレインの転化率は７１．７％であ
り、メタクリル酸の選択率は７９．７％であった。Comparative Example 2 300 g of molybdenum trioxide, 24.64 g of vanadium pentoxide, 3.31 g of cupric oxide, 26.42 g of 85% orthophosphoric acid, 9.2 g of rubidium nitrate in 1900 ml of pure water.
Disperse or dissolve 2 g, and stir it with 95-
The mixture was heated under reflux at 100 ° C. for 9 hours to obtain a reddish brown transparent solution. Subsequently, this solution was dried by a spray dryer to obtain catalyst granules. The following procedure was the same as in Example A1 to obtain a coated catalyst. The active component composition of the obtained reaction catalyst was determined in Example A.
It was Mo 10 V 1.3 P 1.1 Cu 0.2 Rb 0.3 same as 2.
Subsequently, the obtained reaction catalyst was reacted in the same manner as in Example A1. The conversion of methacrolein was 71.7% and the selectivity for methacrylic acid was 79.7%.
【００２８】実施例Ａ３ 実施例Ａ１の三酸化アンチモンの代わりに酸化セリウム
３．５９ｇを使用した以外は実施例Ａ１と同じようにし
て被覆触媒を調製した。得られた被覆触媒の活性成分組
成はＭｏ10Ｖ0.6Ｐ1.2Ｃｕ0.4Ａｓ0.5Ｃｅ0.1であっ
た。続いて、得られた被覆触媒を用いて実施例Ａ１と同
様に反応を行った。メタクロレインの転化率は８５．２
％であり、メタクリル酸の選択率は８４．０％であっ
た。Example A3 A coated catalyst was prepared in the same manner as in Example A1, except that 3.59 g of cerium oxide was used instead of antimony trioxide of Example A1. The active component composition of the obtained coated catalyst was Mo 10 V 0.6 P 1.2 Cu 0.4 As 0.5 Ce 0.1 . Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. Conversion of methacrolein is 85.2
%, And the selectivity for methacrylic acid was 84.0%.
【００２９】実施例Ａ４ 実施例Ａ１の酢酸第二銅・一水和物８．３２ｇを１６．
６４ｇ、酸化第二銅３．３１ｇを０ｇ、三酸化アンチモ
ンの代わりに酸化第二鉄１．６６ｇを使用した以外は実
施例Ａ１と同じようにして被覆触媒を調製した。得られ
た被覆触媒の活性成分組成はＭｏ10Ｖ0.6Ｐ1.2Ｃｕ0.4
Ａｓ0.5Ｆｅ0.1であった。続いて、得られた被覆触媒を
用いて実施例Ａ１と同様に反応を行った。メタクロレイ
ンの転化率は８６．０％であり、メタクリル酸の選択率
は８５．０％であった。Example A4 8.32 g of cupric acetate monohydrate of Example A1
A coated catalyst was prepared in the same manner as in Example A1 except that 0 g of 64 g, 3.31 g of cupric oxide was used, and 1.66 g of ferric oxide was used instead of antimony trioxide. The active component composition of the obtained coated catalyst was Mo 10 V 0.6 P 1.2 Cu 0.4
As 0.5 Fe 0.1 . Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. The conversion of methacrolein was 86.0% and the selectivity for methacrylic acid was 85.0%.
【００３０】実施例Ａ５ 実施例Ａ１の酢酸第二銅・一水和物８．３２ｇを１２．
４８ｇ、酸化第二銅３．３１ｇを１．６６ｇ、８５％正
リン酸２８．８２ｇを２７．６２ｇ、三酸化アンチモン
の代わりに１２タングストリン酸５．６２ｇを使用した
以外は実施例Ａ１と同じようにして被覆触媒を調製し
た。得られた被覆触媒の活性成分組成はＭｏ10Ｖ0.6Ｐ
1.2Ｃｕ0.4Ａｓ0.5Ｗ0.1であった。続いて、得られた被
覆触媒を用いて実施例Ａ１と同様に反応を行った。メタ
クロレインの転化率は８５．０％であり、メタクリル酸
の選択率は８４．５％であった。Example A5 8.32 g of cupric acetate monohydrate of Example A1
Same as Example A1 except for using 48 g, 1.31 g of 3.31 g of cupric oxide, 27.62 g of 28.82 g of 85% orthophosphoric acid, and 5.62 g of 12-tungstophosphoric acid instead of antimony trioxide. Thus, a coated catalyst was prepared. The active component composition of the resulting coated catalyst was Mo 10 V 0.6 P
It was 1.2 Cu 0.4 As 0.5 W 0.1 . Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. The conversion of methacrolein was 85.0% and the selectivity for methacrylic acid was 84.5%.
【００３１】実施例Ａ６ 実施例Ａ１の６０％ヒ酸２４．６４ｇを１９．７１ｇ、
三酸化アンチモンの代わりに硝酸カリ２．１１ｇ使用し
た以外は実施例Ａ１と同じようにして被覆触媒を調製し
た。得られた被覆触媒の活性成分組成はＭｏ10Ｖ0.6Ｐ
1.2Ｃｕ0.4Ａｓ0.4Ｋ0.1であった。続いて、得られた被
覆触媒を用いて実施例Ａ１と同様に反応を行った。メタ
クロレインの転化率は８２．３％であり、メタクリル酸
の選択率は８４．５％であった。Example A6 19.71 g of 24.64 g of the 60% arsenic acid of Example A1,
A coated catalyst was prepared in the same manner as in Example A1, except that 2.11 g of potassium nitrate was used instead of antimony trioxide. The active component composition of the resulting coated catalyst was Mo 10 V 0.6 P
1.2 Cu 0.4 As 0.4 K 0.1 . Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. The conversion of methacrolein was 82.3% and the selectivity for methacrylic acid was 84.5%.
【００３２】実施例Ａ７ 実施例Ａ１の６０％ヒ酸２４．６４ｇを１９．７１ｇ、
三酸化アンチモンの代わりに酸化錫３．１４ｇ、硝酸セ
シウム４．０６ｇを使用した以外は実施例Ａ１と同じよ
うにして被覆触媒を調製した。得られた被覆触媒の活性
成分組成はＭｏ10Ｖ0.6Ｐ1.2Ｃｕ0.4Ａｓ0.4Ｓｎ0.1Ｃ
ｓ0.1であった。続いて、得られた被覆触媒を用いて実
施例Ａ１と同様に反応を行った。メタクロレインの転化
率は８２．４％であり、メタクリル酸の選択率は８５．
７％であった。Example A7 19.71 g of 24.64 g of the 60% arsenic acid of Example A1,
A coated catalyst was prepared in the same manner as in Example A1, except that 3.14 g of tin oxide and 4.06 g of cesium nitrate were used instead of antimony trioxide. The active component composition of the obtained coated catalyst was Mo 10 V 0.6 P 1.2 Cu 0.4 As 0.4 Sn 0.1 C
s 0.1 . Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. The conversion of methacrolein is 82.4% and the selectivity of methacrylic acid is 85.
7%.
【００３３】実施例Ａ８ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２４．６４ｇ、酢酸第二銅・一水和物８．３
２ｇ、および８５％正リン酸２４．０２ｇ、硝酸セシウ
ム１２．１８ｇを分散あるいは溶解させ、これを撹拌し
つつ９５〜１００℃で９時間加熱還流して赤褐色の透明
溶液を得た。続いて、この溶液を噴霧乾燥機により乾燥
して触媒顆粒を得た。以下は実施例Ａ１と同様の操作で
被覆触媒を得た。得られた被覆触媒の活性成分組成はＭ
ｏ10Ｖ1.3Ｐ1.0Ｃｕ0.4Ｃｓ0.3であった。続いて、得ら
れた被覆触媒を用いて実施例Ａ１と同様に反応を行っ
た。メタクロレインの転化率は７５．３％であり、メタ
クリル酸の選択率は７９．０％であった。Example A8 300 g of molybdenum trioxide, 24.64 g of vanadium pentoxide, 8.3 cupric acetate monohydrate in 1900 ml of pure water
2 g, 24.02 g of 85% orthophosphoric acid, and 12.18 g of cesium nitrate were dispersed or dissolved, and heated and refluxed at 95 to 100 ° C. for 9 hours while stirring to obtain a reddish brown transparent solution. Subsequently, this solution was dried by a spray dryer to obtain catalyst granules. The following procedure was the same as in Example A1 to obtain a coated catalyst. The active component composition of the obtained coated catalyst is M
o 10 V 1.3 P 1.0 Cu 0.4 Cs 0.3 Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. The conversion of methacrolein was 75.3% and the selectivity for methacrylic acid was 79.0%.
【００３４】実施例Ａ９ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２２．７４ｇ、酢酸第二銅・一水和物８．３
２ｇ、８５％正リン酸２６．４２ｇを分散あるいは溶解
させ、これを撹拌しつつ９５〜１００℃で約６時間加熱
還流して赤褐色の透明溶液を得た。そこに酸化ゲルマニ
ウム１．０９ｇを添加して、さらに９５〜１００℃で約
３時間加熱還流して赤褐色の溶液を得た。続いて、この
溶液を噴霧乾燥機により乾燥して触媒顆粒を得た。次
に、回転するドラム中に球状多孔質アルミナ担体３００
ｇを仕込み、７０％エタノール水溶液を滴下しながら、
先に得た触媒顆粒３１９ｇをセラミック繊維４４．７ｇ
と均一に混合した粉末を徐々に担体上にふりかけ、球状
担体を触媒顆粒で被覆成型した。得られた成型物を空気
流通下で３１０℃で５時間焼成して被覆触媒を得た。得
られた被覆触媒の活性成分組成はＭｏ10Ｖ1.2Ｐ1.1Ｃｕ
0.2Ｇｅ0.05であった。得られた被覆触媒を用いて実施
例Ａ１と同様に反応を行った。メタクロレインの転化率
は７３．２％であり、メタクリル酸の選択率は７７．８
％であった。Example A9 300 g of molybdenum trioxide, 22.74 g of vanadium pentoxide, 8.3 cupric acetate monohydrate in 1900 ml of pure water
2 g and 26.42 g of 85% orthophosphoric acid were dispersed or dissolved, and the mixture was heated and refluxed at 95 to 100 ° C. for about 6 hours with stirring to obtain a reddish brown transparent solution. Thereto was added 1.09 g of germanium oxide, and the mixture was further heated under reflux at 95 to 100 ° C. for about 3 hours to obtain a reddish brown solution. Subsequently, this solution was dried by a spray dryer to obtain catalyst granules. Next, a spherical porous alumina carrier 300 is placed in a rotating drum.
g, and a 70% aqueous ethanol solution is added dropwise.
319 g of the catalyst granules obtained above were mixed with 44.7 g of ceramic fiber.
The powder uniformly mixed with the mixture was gradually sprinkled on the carrier, and the spherical carrier was coated with the catalyst granules and molded. The obtained molded product was calcined at 310 ° C. for 5 hours under air flow to obtain a coated catalyst. The active component composition of the obtained coated catalyst was Mo 10 V 1.2 P 1.1 Cu
0.2 Ge was 0.05 . Using the obtained coated catalyst, a reaction was carried out in the same manner as in Example A1. The conversion of methacrolein is 73.2% and the selectivity of methacrylic acid is 77.8.
%Met.
【００３５】実施例Ａ１０ 実施例Ａ９の酸化ゲルマニウムの代わりに酸化ガリウム
１．９５ｇを使用した以外は実施例Ａ９と同じようにし
て被覆触媒を調製した。得られた被覆触媒の活性成分組
成はＭｏ10Ｖ1.2Ｐ1.1Ｃｕ0.2Ｇａ0.1であった。続い
て、得られた被覆触媒を用いて実施例Ａ１と同様に反応
を行った。メタクロレインの転化率は７５．９％であ
り、メタクリル酸の選択率は７４．９％であった。Example A10 A coated catalyst was prepared in the same manner as in Example A9 except that 1.95 g of gallium oxide was used instead of germanium oxide of Example A9. The active component composition of the resulting coated catalyst was Mo 10 V 1.2 P 1.1 Cu 0.2 Ga 0.1 . Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. The conversion of methacrolein was 75.9% and the selectivity for methacrylic acid was 74.9%.
【００３６】実施例Ａ１１ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２４．６４ｇ、酢酸第二銅・一水和物１６．
６４ｇ、酸化第二銅３．３１ｇ、８５％正リン酸３６．
０３ｇを分散あるいは溶解させ、これを撹拌しつつ９５
〜１００℃で約６時間加熱還流して赤褐色の透明溶液を
得た。そこに三酸化二硼素２．５８ｇを添加して、さら
に９５〜１００℃で約３時間加熱還流して赤褐色の溶液
を得た。続いて、この溶液を噴霧乾燥機により乾燥して
触媒顆粒を得た。次に、回転するドラム中に球状多孔質
アルミナ担体３００ｇを仕込み、９０％エタノール水溶
液を滴下しながら、先に得た触媒顆粒３１９ｇをセラミ
ック繊維４４．７ｇと均一に混合した粉末を徐々に担体
上にふりかけ、球状担体を触媒顆粒で被覆成型した。得
られた成型物を空気流通下で３１０℃で５時間焼成して
被覆触媒を得た。得られた被覆触媒の活性成分組成はＭ
ｏ10Ｖ1.3Ｐ1.5Ｃｕ0.6Ｂ0.2であった。続いて、得られ
た被覆触媒を用いて実施例Ａ１と同様に反応を行った。
メタクロレインの転化率は８１．２％であり、メタクリ
ル酸の選択率は７８．０％であった。Example A11 300 g of molybdenum trioxide, 24.64 g of vanadium pentoxide, cupric acetate monohydrate in 1900 ml of pure water
64 g, cupric oxide 3.31 g, 85% orthophosphoric acid
03g is dispersed or dissolved, and the mixture is stirred for 95%.
The mixture was heated under reflux at 100 ° C. for about 6 hours to obtain a reddish brown transparent solution. Thereto was added 2.58 g of diboron trioxide, and the mixture was further heated under reflux at 95 to 100 ° C. for about 3 hours to obtain a reddish brown solution. Subsequently, this solution was dried by a spray dryer to obtain catalyst granules. Next, 300 g of a spherical porous alumina carrier was charged into a rotating drum, and a powder obtained by uniformly mixing 319 g of the catalyst granules obtained above with 44.7 g of ceramic fibers was gradually added onto the carrier while a 90% aqueous ethanol solution was dropped. And the spherical carrier was coated with the catalyst granules and molded. The obtained molded product was calcined at 310 ° C. for 5 hours under air flow to obtain a coated catalyst. The active component composition of the obtained coated catalyst is M
o 10 V 1.3 P 1.5 Cu 0.6 B 0.2 Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst.
The conversion of methacrolein was 81.2% and the selectivity for methacrylic acid was 78.0%.
【００３７】実施例Ａ１２ 実施例Ａ１１の三酸化二硼素２．５８ｇの代わりに硝酸
ビスマス1０．１１ｇを使用した以外は実施例Ａ１１と
同じようにして被覆触媒を調製した。得られた被覆触媒
の活性成分組成はＭｏ10Ｖ1.3Ｐ1.5Ｃｕ0.6Ｂｉ0.1であ
った。続いて、得られた被覆触媒を用いて実施例Ａ１と
同様に反応を行った。メタクロレインの転化率は７９．
３％であり、メタクリル酸の選択率は７８．５％であっ
た。Example A12 A coated catalyst was prepared in the same manner as in Example A11 except that 10.11 g of bismuth nitrate was used instead of 2.58 g of diboron trioxide of Example A11. The active component composition of the obtained coated catalyst was Mo 10 V 1.3 P 1.5 Cu 0.6 Bi 0.1 . Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. The conversion of methacrolein is 79.
The selectivity for methacrylic acid was 78.5%.
【００３８】実施例Ａ１３ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２４．６４ｇ、酢酸第二銅・一水和物１２．
４８ｇ、酸化第二銅１．１６ｇ、８５％正リン酸３１．
２２ｇを分散あるいは溶解させ、これを撹拌しつつ９５
〜１００℃で約６時間加熱還流して赤褐色の透明溶液を
得た。そこに酸化第二鉄０．３３ｇ、三酸化アンチモン
０．６１ｇ、酸化セリウム０．７２ｇ、硝酸セシウム
２．０３ｇを添加して、さらに９５〜１００℃で約５時
間加熱還流して濃紺色の溶液を得た。続いて、この溶液
を噴霧乾燥機により乾燥して触媒顆粒を得た。次に、回
転するドラム中に球状多孔質アルミナ担体３００ｇを仕
込み、９０％エタノール水溶液を滴下しながら、先に得
た触媒顆粒３１９ｇをセラミック繊維４４．７ｇと均一
に混合した粉末を徐々に担体上にふりかけ、球状担体を
触媒顆粒で被覆成型した。得られた成型物を空気流通下
で３１０℃で５時間焼成して被覆触媒を得た。得られた
被覆触媒の活性成分組成はＭｏ10Ｖ1.3Ｐ1.3Ｃｕ0.4Ｆ
ｅ0.02Ｓｂ0.02Ｃｅ0.02Ｃｓ0.05であった。続いて、得
られた被覆触媒を用いて実施例Ａ１と同様に反応を行っ
た。メタクロレインの転化率は８０．３％であり、メタ
クリル酸の選択率は７９．２％であった。Example A13 300 g of molybdenum trioxide, 24.64 g of vanadium pentoxide, cupric acetate monohydrate in 1900 ml of pure water
48 g, cupric oxide 1.16 g, 85% orthophosphoric acid
Disperse or dissolve 22 g and mix with stirring
The mixture was heated under reflux at 100 ° C. for about 6 hours to obtain a reddish brown transparent solution. 0.33 g of ferric oxide, 0.61 g of antimony trioxide, 0.72 g of cerium oxide and 2.03 g of cesium nitrate were added thereto, and the mixture was further heated at 95-100 ° C. for about 5 hours under reflux to give a dark blue solution. I got Subsequently, this solution was dried by a spray dryer to obtain catalyst granules. Next, 300 g of a spherical porous alumina carrier was charged into a rotating drum, and a powder obtained by uniformly mixing 319 g of the catalyst granules obtained above with 44.7 g of ceramic fibers was gradually added onto the carrier while a 90% aqueous ethanol solution was dropped. And the spherical carrier was coated with the catalyst granules and molded. The obtained molded product was calcined at 310 ° C. for 5 hours under air flow to obtain a coated catalyst. The active component composition of the obtained coated catalyst was Mo 10 V 1.3 P 1.3 Cu 0.4 F
e 0.02 Sb 0.02 Ce 0.02 Cs 0.05 . Subsequently, a reaction was carried out in the same manner as in Example A1 using the obtained coated catalyst. The conversion of methacrolein was 80.3% and the selectivity for methacrylic acid was 79.2%.
【００３９】実施例Ａ１４ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２４．６４ｇ、酢酸第二銅・一水和物１６．
６４ｇ、酸化第二銅３．３１ｇ、８５％正リン酸３６．
０３ｇを分散あるいは溶解させ、これを撹拌しつつ９５
〜１００℃で約６時間加熱還流して赤褐色の透明溶液を
得た。そこに三酸化アンチモン３９．１１ｇ、硝酸セシ
ウム２０．３０ｇを添加して、さらに９５〜１００℃で
約５時間加熱還流して濃紺色の溶液を得た。続いて、こ
の溶液を噴霧乾燥機により乾燥して触媒顆粒を得た。次
に、回転するドラム中に球状多孔質アルミナ担体３００
ｇを仕込み、９０％エタノール水溶液を滴下しながら、
先に得た触媒顆粒３１９ｇをセラミック繊維４４．７ｇ
と均一に混合した粉末を徐々に担体上にふりかけ、球状
担体を触媒顆粒で被覆成型した。得られた成型物を空気
流通下で３１０℃で５時間焼成して被覆触媒を得た。得
られた被覆触媒の活性成分組成はＭｏ10Ｖ1.3Ｐ1.5Ｃｕ
0.6Ｓｂ0.3Ｃｓ0.5であった。続いて、得られた被覆触
媒を用いて実施例Ａ１で反応温度を３２０℃に変更した
以外は同様に反応を行った。メタクロレインの転化率は
８０．６％であり、メタクリル酸の選択率は７８．８％
であった。Example A14 300 g of molybdenum trioxide, 24.64 g of vanadium pentoxide, cupric acetate monohydrate in 1900 ml of pure water
64 g, cupric oxide 3.31 g, 85% orthophosphoric acid
03g is dispersed or dissolved, and the mixture is stirred for 95%.
The mixture was heated under reflux at 100 ° C. for about 6 hours to obtain a reddish brown transparent solution. 39.11 g of antimony trioxide and 20.30 g of cesium nitrate were added thereto, and the mixture was further heated under reflux at 95 to 100 ° C. for about 5 hours to obtain a dark blue solution. Subsequently, this solution was dried by a spray dryer to obtain catalyst granules. Next, a spherical porous alumina carrier 300 is placed in a rotating drum.
g, and dropping a 90% aqueous ethanol solution.
319 g of the catalyst granules obtained above were mixed with 44.7 g of ceramic fiber.
The powder uniformly mixed with the mixture was gradually sprinkled on the carrier, and the spherical carrier was coated with the catalyst granules and molded. The obtained molded product was calcined at 310 ° C. for 5 hours under air flow to obtain a coated catalyst. The active component composition of the obtained coated catalyst was Mo 10 V 1.3 P 1.5 Cu
0.6 Sb 0.3 Cs 0.5 . Subsequently, a reaction was carried out in the same manner as in Example A1 except that the reaction temperature was changed to 320 ° C. using the obtained coated catalyst. The conversion of methacrolein is 80.6% and the selectivity for methacrylic acid is 78.8%.
Met.
【００４０】実施例Ｂ１ １）触媒の調整 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム１１．３７ｇ、酸化第二銅３．３１ｇ及び８
５％正リン酸２８．８２ｇ、６０％ヒ酸２４．６４ｇを
分散あるいは溶解させ、これを撹拌しつつ９５〜１００
℃で約６時間加熱還流して赤褐色の透明溶液を得た。そ
こに三酸化アンチモン１．５２ｇを添加して、さらに９
５〜１００℃で約３時間加熱還流して濃紺色の溶液を得
た。続いて、この溶液を噴霧乾燥機により乾燥して得た
顆粒３１６ｇに、原子比でＭｏ10に対してＣｕ0.2にな
る量の固体酢酸第二銅・一水和物７．６４ｇ、セラミッ
クス繊維４４．７ｇを均一に添加混合し混合粉末を得
た。次に、回転するドラム中に球状多孔質アルミナ担体
３００ｇを仕込み、９０％エタノール水溶液を滴下しな
がら、上記混合粉末を徐々に担体上にふりかけ、球状担
体を触媒活性成分で被覆成型した。この間の粉末の損失
はほとんど認められなかった。得られた成型物を空気流
通下で３１０℃で５時間焼成して本発明の被覆触媒を得
た。得られた被覆触媒の活性成分組成はＭｏ10Ｖ0.6Ｐ
1.2Ｃｕ0.4Ａｓ0. 5Ｓｂ0.05であった。 ２）メタクロレインの触媒酸化反応 得られた被覆触媒１０ｍｌを内径１８．４ｍｍのステン
レス反応管に充填し、原料ガス組成（モル比） メタク
ロレイン：酸素：水蒸気：窒素＝１：２．８：５．０：
２１．０、空間速度（ＳＶ）１０００ｈｒ−１、反応温
度３１０℃の条件で、メタクロレインの酸化反応を行っ
たところ、メタクロレインの転化率は８８．８％であ
り、メタクリル酸の選択率は８４．５％であった。Example B1 1) Preparation of catalyst 300 g of molybdenum trioxide, 11.37 g of vanadium pentoxide, 3.31 g of cupric oxide and 1900 ml of pure water
28.82 g of 5% orthophosphoric acid and 24.64 g of 60% arsenic acid are dispersed or dissolved, and the mixture is stirred for 95 to 100%.
The mixture was heated and refluxed at about 6 hours to obtain a reddish brown transparent solution. 1.52 g of antimony trioxide was added thereto, and 9
The mixture was heated and refluxed at 5 to 100 ° C. for about 3 hours to obtain a dark blue solution. Subsequently, 7.64 g of solid cupric acetate monohydrate in an amount of Cu0.2 relative to Mo10 in atomic ratio was added to 316 g of granules obtained by drying the solution with a spray dryer, and ceramic fibers 44 0.7 g was uniformly added and mixed to obtain a mixed powder. Next, 300 g of a spherical porous alumina carrier was charged into a rotating drum, and while the 90% aqueous ethanol solution was dropped, the mixed powder was gradually sprinkled on the carrier to coat and mold the spherical carrier with a catalytically active component. During this time, almost no powder loss was observed. The obtained molded product was calcined at 310 ° C. for 5 hours under an air flow to obtain a coated catalyst of the present invention. The active component composition of the resulting coated catalyst was Mo 10 V 0.6 P
1.2 was Cu 0.4 As 0. 5 Sb 0.05. 2) Catalytic oxidation reaction of methacrolein 10 ml of the obtained coated catalyst was filled in a stainless steel reaction tube having an inner diameter of 18.4 mm, and the raw material gas composition (molar ratio) methacrolein: oxygen: steam: nitrogen = 1: 2.8: 5 .0:
When the oxidation reaction of methacrolein was performed under the conditions of 21.0, space velocity (SV) 1000 hr -1 and reaction temperature 310 ° C., the conversion of methacrolein was 88.8% and the selectivity of methacrylic acid was 84.5%.
【００４１】実施例Ｂ２ 実施例Ｂ１の五酸化バナジウム１１．３７ｇを１３．２
６ｇ、酸化第二銅３．３１ｇを４．９６ｇ、８５％正リ
ン酸２８．８２ｇを３１．２２ｇ、三酸化アンチモン
１．５２ｇを３．０４ｇに、固体酢酸第二銅・一水和物
７．６４ｇを３．７５ｇに変更した以外は実施例Ｂ１と
同じようにして本発明の被覆触媒を調製した。得られた
被覆触媒の活性成分組成はＭｏ10Ｖ0.７Ｐ1.3Ｃｕ0.4Ａ
ｓ0.5Ｓｂ 0.1であった。得られた被覆触媒を用いて、
実施例Ｂ１と同様に反応を行ったところ、 メタクロレ
インの転化率は８４．４％であり、メタクリル酸の選択
率は８６．７％であった。Example B2 11.37 g of vanadium pentoxide of Example B1 was added to 13.2 g.
6 g, 3.31 g of cupric oxide to 4.96 g, 28.82 g of 85% orthophosphoric acid to 31.22 g, 1.52 g of antimony trioxide to 3.04 g, solid cupric acetate monohydrate 7 A coated catalyst of the present invention was prepared in the same manner as in Example B1, except that 0.64 g was changed to 3.75 g. The active component composition of the obtained coated catalyst was Mo 10 V 0.7 P 1.3 Cu 0.4 A.
s 0.5 Sb 0.1 . Using the obtained coated catalyst,
When the reaction was carried out in the same manner as in Example B1, the conversion of methacrolein was 84.4% and the selectivity for methacrylic acid was 86.7%.
【００４２】実施例Ｂ３ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２４．６４ｇ、および８５％正リン酸４０．
８３ｇを分散あるいは溶解させ、これを撹拌しつつ９５
〜１００℃で６時間、更に硝酸カリウム８．４２ｇを添
加して３時間加熱還流して赤褐色の溶液を得た。続い
て、この溶液を噴霧乾燥機により乾燥して得た顆粒を乳
鉢で２４メッシュ以下に粉砕して粉末を得た。この粉末
３１０ｇに原子比でＭｏ10に対してＣｕ0.6になる量の
固体酢酸第二銅・一水和物２１．８７ｇ、セラミックス
繊維４４．７ｇを均一に添加混合し混合粉末を得た。次
に、回転するドラム中に球状多孔質アルミナ担体３００
ｇを仕込み、９０％エタノール水溶液を滴下しながら、
上記混合粉末を徐々に担体上にふりかけ、球状担体を触
媒活性成分組成物で被覆成型した。この間の粉末の損失
はほとんど認められなかった。得られた成型物を空気流
通下で３１０℃で５時間焼成して本発明の被覆触媒を得
た。得られた被覆触媒の活性成分組成はＭｏ10Ｖ1.3Ｐ
1.7Ｃｕ0.6Ｋ0.4であった。得られた被覆触媒を用い
て、実施例Ｂ１と同様に反応を行ったところ、メタクロ
レインの転化率は８５．９％であり、メタクリル酸の選
択率は７３．８％であった。Example B3 300 g of molybdenum trioxide, 24.64 g of vanadium pentoxide, and 85% orthophosphoric acid in 1900 ml of pure water
83 g is dispersed or dissolved, and this is stirred with 95 g
At -100 ° C for 6 hours, 8.42 g of potassium nitrate was further added, and the mixture was heated under reflux for 3 hours to obtain a reddish brown solution. Subsequently, the solution was dried by a spray dryer, and the granules obtained were pulverized in a mortar to 24 mesh or less to obtain a powder. To 310 g of this powder, 21.87 g of solid cupric acetate monohydrate and 44.7 g of ceramic fibers were uniformly added and mixed in an amount of Cu 0.6 with respect to Mo10 in an atomic ratio to obtain a mixed powder. Next, a spherical porous alumina carrier 300 is placed in a rotating drum.
g, and dropping a 90% aqueous ethanol solution.
The mixed powder was gradually sprinkled on the carrier, and the spherical carrier was coated with the catalytically active component composition and molded. During this time, almost no powder loss was observed. The obtained molded product was calcined at 310 ° C. for 5 hours under an air flow to obtain a coated catalyst of the present invention. The active component composition of the obtained coated catalyst was Mo 10 V 1.3 P
1.7 Cu 0.6 K 0.4 When a reaction was carried out in the same manner as in Example B1 using the obtained coated catalyst, the conversion of methacrolein was 85.9% and the selectivity of methacrylic acid was 73.8%.
【００４３】実施例Ｂ４ 実施例Ｂ１の三酸化アンチモンの代わりに酸化セリウム
３．３９ｇを使用し、固体酢酸第二銅・一水和物７．６
４ｇを７．５９ｇに変更した以外は実施例Ｂ１と同じよ
うにして本発明の被覆触媒を調製した。得られた被覆触
媒の活性成分組成はＭｏ10Ｖ0.6Ｐ1.2Ｃｕ0.4Ａｓ0.5Ｃ
ｅ0.1であった。得られた被覆触媒を用いて、反応温度
を３０５℃に変更した以外は実施例Ｂ１と同様に反応を
行ったところ、メタクロレインの転化率は８５．９％で
あり、メタクリル酸の選択率は８４．６％であった。Example B4 Instead of antimony trioxide of Example B1, 3.39 g of cerium oxide was used, and 7.6 cupric acetate monohydrate monohydrate was used.
A coated catalyst of the present invention was prepared in the same manner as in Example B1, except that 4 g was changed to 7.59 g. The active component composition of the obtained coated catalyst was Mo 10 V 0.6 P 1.2 Cu 0.4 As 0.5 C
e was 0.1 . Using the obtained coated catalyst, the reaction was carried out in the same manner as in Example B1 except that the reaction temperature was changed to 305 ° C., and the conversion of methacrolein was 85.9% and the selectivity of methacrylic acid was 84.6%.
【００４４】実施例Ｂ５ 実施例Ｂ１において三酸化アンチモンの代わりに酸化亜
鉛１．７０ｇを使用し、かつスラリー液調製時添加する
銅化合物として酸化第二銅３．３１ｇの代わりに酸化第
二銅１．６６ｇ及び固体酢酸第二銅・一水和物４．１６
ｇを使用した以外は実施例Ｂ１と同じようにして本発明
の被覆触媒を調製した。得られた被覆触媒の活性成分組
成はＭｏ10Ｖ0.6Ｐ1.2Ｃｕ0.4Ａｓ0.5Ｚｎ0.1であっ
た。得られた被覆触媒を用いて、反応温度を３０５℃に
した以外は実施例Ｂ１と同様に反応を行った。メタクロ
レインの転化率は８０．５％であり、メタクリル酸の選
択率は８５．０％であった。Example B5 In Example B1, 1.70 g of zinc oxide was used instead of antimony trioxide, and as a copper compound to be added at the time of preparing the slurry, cupric oxide was used instead of 3.31 g of cupric oxide. .66 g and solid cupric acetate monohydrate 4.16
A coated catalyst of the present invention was prepared in the same manner as in Example B1 except that g was used. The active component composition of the obtained coated catalyst was Mo 10 V 0.6 P 1.2 Cu 0.4 As 0.5 Zn 0.1 . Using the obtained coated catalyst, a reaction was carried out in the same manner as in Example B1, except that the reaction temperature was 305 ° C. The conversion of methacrolein was 80.5% and the selectivity for methacrylic acid was 85.0%.
【００４５】実施例Ｂ６ 実施例Ｂ１において三酸化アンチモンの代わりに硝酸コ
バルト５．９０ｇを使用し、五酸化バナジウム１１．３
７ｇを１３．２７ｇ、８５％正リン酸３１．２２ｇを２
６．４２ｇに変更した以外は実施例Ｂ１と同じようにし
て本発明の被覆触媒を調製した。得られた被覆触媒の活
性成分組成はＭｏ10Ｖ0.7Ｐ1.1Ｃｕ0.4Ａｓ0.5Ｃｏ0.1
であった。得られた被覆触媒を用いて、実施例Ｂ１と同
様に反応を行ったところ、メタクロレインの転化率は８
７．２％であり、メタクリル酸の選択率は８４．８％で
あった。Example B6 In Example B1, 5.90 g of cobalt nitrate was used in place of antimony trioxide, and 11.3 vanadium pentoxide was used.
7.27 g 13.27 g, 85% orthophosphoric acid 31.22 g 2
A coated catalyst of the present invention was prepared in the same manner as in Example B1, except that the amount was changed to 6.42 g. The active component composition of the obtained coated catalyst was Mo 10 V 0.7 P 1.1 Cu 0.4 As 0.5 Co 0.1
Met. When the reaction was carried out in the same manner as in Example B1 using the obtained coated catalyst, the conversion of methacrolein was 8%.
7.2%, and the selectivity for methacrylic acid was 84.8%.
【００４６】実施例Ｂ７ 実施例Ｂ６において硝酸コバルトの代わりにリン酸アル
ミニウム２．５４ｇを使用し、８５％正リン酸２６．４
２ｇを２４．０２ｇに変更した以外は実施例Ｂ６と同じ
ようにして本発明の被覆触媒を調製した。得られた被覆
触媒の活性成分組成はＭｏ10Ｖ0.7Ｐ1.1Ｃｕ0.4Ａｓ0.5
Ａｌ0.1であった。得られた被覆触媒を用いて、実施例
Ｂ１と同様に反応を行ったところ、メタクロレインの転
化率は８６．８％であり、メタクリル酸の選択率は８
５．２％であった。Example B7 In Example B6, 2.54 g of aluminum phosphate was used instead of cobalt nitrate, and 26.4% of 85% orthophosphoric acid was used.
A coated catalyst of the present invention was prepared in the same manner as in Example B6 except that 2 g was changed to 24.02 g. The active component composition of the obtained coated catalyst was Mo 10 V 0.7 P 1.1 Cu 0.4 As 0.5
Al 0.1 . When the reaction was carried out in the same manner as in Example B1 using the obtained coated catalyst, the conversion of methacrolein was 86.8%, and the selectivity of methacrylic acid was 8%.
It was 5.2%.
【００４７】実施例Ｂ８ 実施例Ｂ６において硝酸コバルトの代わりに硼酸７．７
３ｇ、１２タングストリン酸３５．７３ｇを使用し、８
５％リン酸２６．４２ｇを２５．２２ｇ、酸化第二銅
３．３１ｇを０ｇ、固体酢酸第二銅・一水和物７．６３
ｇを１４．０９ｇに変更した以外は実施例Ｂ６と同じよ
うにして本発明の被覆触媒を調製した。得られた被覆触
媒の活性成分組成はＭｏ10Ｖ0.7Ｐ1.1Ｃｕ0.4Ａｓ0.5Ｂ
0.6Ｗ0.6であった。得られた被覆触媒を用いて、実施例
Ｂ１と同様に反応を行ったところ、メタクロレインの転
化率は８７．３％であり、メタクリル酸の選択率は８
５．９％であった。Example B8 In Example B6, 7.7 of boric acid was used instead of cobalt nitrate.
Using 3g, 35.73g of 12 tungstophosphoric acid, 8
25.22 g of 26.42 g of 5% phosphoric acid, 0 g of 3.31 g of cupric oxide, and 7.63 of solid cupric acetate monohydrate
A coated catalyst of the present invention was prepared in the same manner as in Example B6 except that g was changed to 14.09 g. The active component composition of the obtained coated catalyst was Mo 10 V 0.7 P 1.1 Cu 0.4 As 0.5 B
0.6 W 0.6 . When the reaction was carried out in the same manner as in Example B1 using the obtained coated catalyst, the conversion of methacrolein was 87.3%, and the selectivity of methacrylic acid was 8%.
It was 5.9%.
【００４８】実施例Ｂ９ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２２．７４ｇ、酸化第二銅３．３１ｇ及び８
５％正リン酸２８．６３ｇを分散あるいは溶解させ、こ
れを撹拌しつつ９５〜１００℃で約６時間加熱還流して
赤褐色の透明溶液を得た。そこに１２タングストリン酸
５．６２ｇを添加して、さらに９５〜１００℃で約３時
間加熱還流した。続いて、この溶液を噴霧乾燥機により
乾燥して得た顆粒３１６ｇに、原子比でＭｏ10に対して
Ｃｕ0.2になる量の固体酢酸第二銅・一水和物７．５４
ｇ、セラミックス繊維４４．７ｇを均一に添加混合し混
合粉末を得た。次に、回転するドラム中に球状多孔質ア
ルミナ担体３００ｇを仕込み、９０％エタノール水溶液
を滴下しながら、上記混合粉末を徐々に担体上にふりか
け、球状担体を触媒活性成分組成物で被覆成型した。こ
の間の粉末の損失はほとんど認められなかった。得られ
た成型物を空気流通下で３１０℃で５時間焼成して本発
明の被覆触媒を得た。得られた被覆触媒の活性成分組成
はＭｏ10Ｖ1.2Ｐ1.2Ｃｕ0.4Ｗ0.1であった。得られた被
覆触媒を用いて、実施例Ｂ１と同様に反応を行ったとこ
ろ、 メタクロレインの転化率は８０．３％であり、メ
タクリル酸の選択率は７９．１％であった。Example B9 300 g of molybdenum trioxide, 22.74 g of vanadium pentoxide, 3.31 g of cupric oxide, and 8 g in 1900 ml of pure water
28.63 g of 5% orthophosphoric acid was dispersed or dissolved, and the mixture was heated and refluxed at 95 to 100 ° C. for about 6 hours with stirring to obtain a reddish brown transparent solution. Thereto, 5.52 g of 12 tungstophosphoric acid was added, and the mixture was further heated and refluxed at 95 to 100 ° C. for about 3 hours. Subsequently, 316 g of granules obtained by drying this solution with a spray drier was added to solid cupric acetate monohydrate 7.54 in an amount of Cu0.2 in atomic ratio to Mo10.
g and 44.7 g of ceramic fiber were uniformly added and mixed to obtain a mixed powder. Next, 300 g of a spherical porous alumina carrier was charged into a rotating drum, and while the 90% aqueous ethanol solution was dropped, the mixed powder was gradually sprinkled on the carrier to coat and mold the spherical carrier with the catalytically active component composition. During this time, almost no powder loss was observed. The obtained molded product was calcined at 310 ° C. for 5 hours under an air flow to obtain a coated catalyst of the present invention. The active component composition of the obtained coated catalyst was Mo 10 V 1.2 P 1.2 Cu 0.4 W 0.1 . When a reaction was carried out in the same manner as in Example B1 using the obtained coated catalyst, the conversion of methacrolein was 80.3% and the selectivity of methacrylic acid was 79.1%.
【００４９】実施例Ｂ１０ 実施例Ｂ９において１２タングストリン酸の代わりに酸
化ゲルマニウム２．１８ｇを使用し、五酸化バナジウム
２２．７４ｇを２４．６４ｇ、酸化第二銅３．３１ｇを
０ｇ、８５％正リン酸２８．６３ｇを２８．８２ｇ、固
体酢酸第二銅・一水和物７．５４ｇを１１．５２ｇに変
更した以外は実施例Ｂ９と同様にして本発明の被覆触媒
を調製した。得られた被覆触媒の活性成分組成はＭｏ10
Ｖ1.3Ｐ1.2Ｃｕ0.3Ｇｅ0.１であった。得られた被覆触
媒を用いて、実施例Ｂ１と同様に反応を行ったところ、
メタクロレインの転化率は８１．９％であり、メタクリ
ル酸の選択率は８３．１％であった。Example B10 In Example B9, 2.18 g of germanium oxide was used in place of 12 tungstophosphoric acid, 24.64 g of 22.74 g of vanadium pentoxide, 0 g of 3.31 g of cupric oxide, and 85% positive. A coated catalyst of the present invention was prepared in the same manner as in Example B9, except that 28.63 g of phosphoric acid was changed to 28.82 g, and 7.54 g of solid cupric acetate monohydrate was changed to 11.52 g. The active component composition of the obtained coated catalyst was Mo 10
V 1.3 P 1.2 Cu 0.3 Ge 0.1 . When a reaction was carried out in the same manner as in Example B1 using the obtained coated catalyst,
The conversion of methacrolein was 81.9% and the selectivity for methacrylic acid was 83.1%.
【００５０】実施例Ｂ１１ 純水１９００ｍｌに三酸化モリブデン３００ｇ、五酸化
バナジウム２４．６４ｇ、および８５％正リン酸４０．
８３ｇ、酸化セリウム６．７８ｇ、三酸化アンチモン
６．０８ｇを分散あるいは溶解させ、これを撹拌しつつ
９５〜１００℃で６時間、更に硝酸セシウム１２．１８
ｇを添加して３時間加熱還流して濃紺色の溶液を得た。
続いて、この溶液を噴霧乾燥機により乾燥して得た顆粒
を乳鉢で２４メッシュ以下に粉砕して粉末を得た。この
粉末３１０ｇに原子比でＭｏ10に対してＣｕ0.6になる
量の固体酢酸第二銅・一水和物２０．８１ｇ、セラミッ
クス繊維４４．７ｇを均一に添加混合し混合粉体を得
た。次に、回転するドラム中に球状多孔質アルミナ担体
３００ｇを仕込み、９０％エタノール水溶液を滴下しな
がら、上記混合粉末を徐々に担体上にふりかけ、球状担
体を触媒活性成分で被覆成型した。この間の粉末の損失
はほとんど認められなかった。得られた成型物を空気流
通下で３１０℃で５時間焼成して本発明の被覆触媒を得
た。得られた被覆触媒の活性成分組成はＭｏ10Ｖ1.3Ｐ
1.7Ｃｕ0.6Ｃｅ0.2Ｓｂ0.2Ｃｓ0.3であった。得られた
被覆触媒を用いて、実施例Ｂ１と同様に反応を行ったと
ころ、メタクロレインの転化率は８３．８％であり、メ
タクリル酸の選択率は８０．２％であった。Example B11 300 g of molybdenum trioxide, 24.64 g of vanadium pentoxide, and 40% of 85% orthophosphoric acid in 1900 ml of pure water
83 g, 6.78 g of cerium oxide, and 6.08 g of antimony trioxide are dispersed or dissolved, and the mixture is stirred at 95 to 100 ° C. for 6 hours, and further with cesium nitrate 12.18.
g was added and the mixture was heated under reflux for 3 hours to obtain a dark blue solution.
Subsequently, the solution was dried by a spray dryer, and the granules obtained were pulverized in a mortar to 24 mesh or less to obtain a powder. To 310 g of this powder, 20.81 g of solid cupric acetate monohydrate and 44.7 g of ceramic fibers were uniformly added and mixed in an amount of Cu 0.6 with respect to Mo10 in an atomic ratio to obtain a mixed powder. Next, 300 g of a spherical porous alumina carrier was charged into a rotating drum, and while the 90% aqueous ethanol solution was dropped, the mixed powder was gradually sprinkled on the carrier to coat and mold the spherical carrier with a catalytically active component. During this time, almost no powder loss was observed. The obtained molded product was calcined at 310 ° C. for 5 hours under an air flow to obtain a coated catalyst of the present invention. The active component composition of the obtained coated catalyst was Mo 10 V 1.3 P
1.7 Cu 0.6 Ce 0.2 Sb 0.2 Cs 0.3 . When a reaction was carried out in the same manner as in Example B1 using the obtained coated catalyst, the conversion of methacrolein was 83.8% and the selectivity of methacrylic acid was 80.2%.
【００５１】[0051]
【発明の効果】本発明の触媒は高収率、高選択的にメタ
クリル酸を製造することができ、更に高負荷条件の反応
に使用することができるため工業的価値が極めて大き
い。Industrial Applicability The catalyst of the present invention can produce methacrylic acid with high yield and high selectivity, and can be used for a reaction under a high load condition, and therefore has a very large industrial value.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ Ｆターム(参考） 4G069 AA02 AA08 BA01A BA01B BA03A BA13A BA13B BA21C BB01C BB04C BB07A BB07B BB15A BC03A BC03B BC05A BC05B BC06A BC06B BC10A BC16A BC16B BC17B BC21A BC22A BC22B BC23A BC23B BC25A BC25B BC26A BC26B BC27A BC27B BC31A BC31B BC31C BC32A BC35A BC35B BC43A BC43B BC46A BC50A BC51A BC54A BC54B BC58A BC59A BC59B BC60A BC60B BC64A BC66A BC66B BC67A BC67B BC68A BD01C BD02C BD03A BD03B BD05A BD07A BD07B BE06C BE07C BE08C BE09C BE10C CB17 EA02Y EA04Y EB18Y EC27 ED03 EE01 FA01 FA03 FB06 FB07 FB09 FB15 FB16 FB30 FB62 FB71 FC02 FC05 FC08 4H006 AA02 AC46 BA02 BA05 BA07 BA08 BA09 BA11 BA12 BA13 BA14 BA19 BA20 BA30 BA35 BA55 BA60 BA81 BB61 BB62 BC10 BC18 BS10 4H039 CA65 CC30 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (reference) // C07B 61/00 300 C07B 61/00 300 F term (reference) 4G069 AA02 AA08 BA01A BA01B BA03A BA13A BA13B BA21C BB01C BB04C BB07A BB07B BB15A BC03A BC03B BC05A BC05B BC06A BC06B BC10A BC16A BC16B BC17B BC21A BC22A BC22B BC23A BC23B BC25A BC25B BC26A BC26B BC27A BC27B BC31A BC31B BC31C BC32A BC35A BC35B BC43A BC43B BC46A BC50A BC51A BC54A BC54B BC58A BC59A BC59B BC60A BC60B BC64A BC66A BC66B BC67A BC67B BC68A BD01C BD02C BD03A BD03B BD05A BD07A BD07B BE06C BE07C BE08C BE09C BE10C CB17 EA02Y EA04Y EB18Y EC27 ED03 EE01 FA01 FA03 FB06 FB07 FB09 FB15 FB16 FB30 FB61 FB71 BB61 BB62 BC10 BC18 BS10 4H039 CA65 C C30
Claims (16)
する触媒において、該触媒の調製用Ｃｕ原料として、そ
の必要量の全部又は一部に酢酸銅を使用したものである
ことを特徴とするメタクロレインの気相接触酸化による
メタクリル酸製造用触媒。1. A catalyst containing Mo, V, P and Cu as essential active components, wherein copper acetate is used as a Cu raw material for preparing the catalyst, in whole or in part of a required amount thereof. A catalyst for producing methacrylic acid by gas phase catalytic oxidation of methacrolein.
する触媒において、酢酸銅の全部又は一部が、水性溶液
とされることなく、固体のまま配合されたものであるこ
とを特徴とする請求項１記載の触媒。2. A catalyst containing Mo, V, P and Cu as essential active components, wherein all or a part of copper acetate is compounded as a solid without being converted into an aqueous solution. The catalyst according to claim 1, characterized in that:
スラリー乾燥体とを混合したものであることを特徴とす
る請求項２記載の触媒。3. The catalyst according to claim 2, wherein the mixture is a mixture of solid copper acetate and a dried slurry containing Mo, V and P.
請求項１ないし３のいずれか一項に記載の触媒。4. The catalyst according to claim 1, wherein the catalyst further contains As as an active ingredient.
ブデン、バナジウム、リン、銅、ヒ素及び酸素を表し、
ＸはＡｇ、Ｍｇ、Ｚｎ、Ａｌ、Ｂ、Ｇｅ、Ｓｎ、Ｐｂ、
Ｔｉ、Ｚｒ、Ｓｂ、Ｃｒ、Ｒｅ、Ｂｉ、Ｗ、Ｆｅ、Ｃ
ｏ、Ｎｉ、Ｃｅ及びＴｈからなる群から選ばれる少なく
とも一種の元素を表し、ＹはＫ、Ｒｂ及びＣｓからなる
群より選ばれた少なくとも一種の元素を表す。ａ、ｂ、
ｃ、ｄ、ｅ、ｆ及びｇは各元素の原子比を表し、ａは
０．１≦ａ≦６、ｂは０．５≦ｂ≦６、ｃは０＜ｃ≦
３、ｄは０≦ｄ≦３、ｅは０≦ｅ≦３、ｆは０≦ｆ≦
１、ｇは他の元素の原子価ならびに原子比により定まる
値である。）で表される請求項１ないし３のいずれか一
項に記載の触媒。5. The composition of catalytically active component is represented by the following formula (1) Mo 10 V a P b Cu c As d X e Y f O g (1) ( wherein, Mo, V, P, Cu , As, O Represents molybdenum, vanadium, phosphorus, copper, arsenic and oxygen, respectively.
X is Ag, Mg, Zn, Al, B, Ge, Sn, Pb,
Ti, Zr, Sb, Cr, Re, Bi, W, Fe, C
Y represents at least one element selected from the group consisting of o, Ni, Ce and Th, and Y represents at least one element selected from the group consisting of K, Rb and Cs. a, b,
c, d, e, f and g represent the atomic ratio of each element, a is 0.1 ≦ a ≦ 6, b is 0.5 ≦ b ≦ 6, and c is 0 <c ≦
3, d is 0 ≦ d ≦ 3, e is 0 ≦ e ≦ 3, f is 0 ≦ f ≦
1, g is a value determined by the valence and atomic ratio of another element. The catalyst according to any one of claims 1 to 3, which is represented by:
記載の触媒。6. The catalyst according to claim 5, comprising As as an active ingredient.
む化合物及び酢酸銅を、水と混合し、これらの化合物の
水溶液又は水分散体（以下、両者を含めてスラリー液と
いう）を調製する工程、（ｂ）工程（ａ）で得られたス
ラリー液を乾燥してスラリー乾燥体を得る工程、（ｃ）
工程（ｂ）で得られたスラリー乾燥体を、バインダーを
用いて担体に被覆する工程、（ｄ）工程（ｃ）で得られ
た被覆成型物を焼成する工程、からなる被覆触媒の製法
であって、前記バインダーとして、水及び１気圧下での
沸点が１５０℃以下である有機化合物からなる群から選
ばれる少なくとも１種を用いることを特徴とするメタク
ロレインの気相接触酸化によるメタクリル酸製造用被覆
触媒の製法。7. (a) A compound containing each or a plurality of Mo, V and P and copper acetate are mixed with water, and an aqueous solution or an aqueous dispersion of these compounds (hereinafter referred to as a slurry liquid including both) is added. Preparing, (b) drying the slurry liquid obtained in step (a) to obtain a dried slurry, (c)
A method of producing a coated catalyst, comprising: a step of coating a dried slurry obtained in step (b) on a carrier with a binder; and a step of (d) firing the coated molded article obtained in step (c). For producing methacrylic acid by gas phase catalytic oxidation of methacrolein, wherein at least one selected from the group consisting of water and an organic compound having a boiling point at 150 ° C. or less at 1 atm is used as the binder. Manufacturing method of coated catalyst.
む化合物を水と混合し、これら化合物の水溶液又は水分
散体（以下、両者を含めてスラリー液という）を調製す
る工程、（ｂ）工程（ａ）で得られたスラリー液を乾燥
してスラリー乾燥体を得る工程、（ｂ’）工程（ｂ）で
得られたスラリー乾燥体に固体酢酸銅を混合する工程、
（ｃ）工程（ｂ’）で得られた混合物を、バインダーを
用いて担体に被覆する工程、（ｄ）工程（ｃ）で得られ
た被覆成型物を焼成する工程、からなる被覆触媒の製法
であって、前記バインダーとして、水及び１気圧下での
沸点が１５０℃以下である有機化合物からなる群から選
ばれる少なくとも１種を用いることを特徴とするメタク
ロレインの気相接触酸化によるメタクリル酸製造用被覆
触媒の製法。8. (a) a step of mixing a compound containing each or a plurality of Mo, V, and P with water to prepare an aqueous solution or an aqueous dispersion of these compounds (hereinafter, referred to as a slurry liquid including both); b) drying the slurry liquid obtained in step (a) to obtain a dried slurry, (b ′) mixing solid copper acetate with the dried slurry obtained in step (b),
(C) a step of coating the mixture obtained in step (b ′) on a carrier using a binder, and (d) a step of firing the coated molded article obtained in step (c). Methacrylic acid obtained by gas phase catalytic oxidation of methacrolein, wherein the binder is at least one selected from the group consisting of water and an organic compound having a boiling point of 150 ° C. or less at 1 atm. Method of producing coated catalyst for production.
て更にＡｓ含有化合物を用いる請求項７又は８に記載の
被覆触媒の製法。9. The process for producing a coated catalyst according to claim 7, wherein an As-containing compound is further used as a raw material of the slurry liquid in the step (a).
して、更に酸化銅を用いる請求項７又は８に記載の被覆
触媒の製法。10. The method for producing a coated catalyst according to claim 7, wherein copper oxide is further used as a raw material of the slurry liquid in the step (a).
して、更にＡｓ含有化合物及び酸化銅を用いる請求項７
又は８に記載の被覆触媒の製法。11. The method according to claim 7, wherein in step (a), an As-containing compound and copper oxide are further used as raw materials for the slurry liquid.
Or a method for producing a coated catalyst according to item 8.
求項７ないし１１のいずれか一項に記載の被覆触媒の製
法。12. The method for producing a coated catalyst according to claim 7, wherein ethanol is used as a binder.
〜５／５（質量比）である請求項１２に記載の被覆触媒
の製法。13. The binder is ethanol / water = 10/0.
The method for producing a coated catalyst according to claim 12, wherein the mass ratio is about 5/5.
載の製法により得られるとするメタクロレインの気相接
触酸化によるメタクリル酸製造用被覆触媒。14. A coated catalyst for the production of methacrylic acid by gas phase catalytic oxidation of methacrolein obtained by the process according to claim 7. Description:
の活性成分とする触媒を被覆した被覆触媒であって、該
触媒を調製する際のＣｕ原料の全部又は一部に酢酸銅を
使用したものであることを特徴とするメタクロレインの
気相接触酸化によるメタクリル酸製造用被覆触媒。15. A coated catalyst comprising a carrier coated with a catalyst containing Mo, V, P and Cu as essential active components, wherein all or part of a Cu raw material used in preparing the catalyst is copper acetate. A coated catalyst for the production of methacrylic acid by gas phase catalytic oxidation of methacrolein, characterized in that the catalyst is used.
いるものである請求項１５に記載の被覆触媒。16. The coated catalyst according to claim 15, wherein the catalyst has a heteropolyacid (salt) structure.
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| JP2000286326 | 2000-09-21 | ||
| JP2000-286326 | 2000-09-21 | ||
| JP2000373761 | 2000-12-08 | ||
| JP2000-373761 | 2000-12-08 | ||
| JP2001281720A JP4671320B2 (en) | 2000-09-21 | 2001-09-17 | Production of coated catalyst for methacrylic acid production |
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| JP2002233760A true JP2002233760A (en) | 2002-08-20 |
| JP4671320B2 JP4671320B2 (en) | 2011-04-13 |
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| WO2004073857A1 (en) * | 2003-02-20 | 2004-09-02 | Nippon Kayaku Kabushiki Kaisha | Catalyst for methacrylic acid production and process for producing the same |
| WO2004105941A1 (en) * | 2003-05-30 | 2004-12-09 | Nippon Kayaku Kabushiki Kaisha | Process for producing catalyst for methacrylic acid production |
| JP2006513033A (en) * | 2004-01-09 | 2006-04-20 | エルジー・ケム・リミテッド | Novel heteropolyacid catalyst and production method thereof |
| JPWO2006001360A1 (en) * | 2004-06-28 | 2008-04-17 | 三菱レイヨン株式会社 | Method for producing catalyst for synthesis of methacrylic acid |
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| JP2008542468A (en) * | 2005-05-25 | 2008-11-27 | セラニーズ・インターナショナル・コーポレーション | Layered composition and method for preparing and using the same |
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