JP4895265B2 - Process for producing methacrolein and / or methacrylic acid synthesis catalyst - Google Patents
Process for producing methacrolein and / or methacrylic acid synthesis catalyst Download PDFInfo
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- JP4895265B2 JP4895265B2 JP2005377635A JP2005377635A JP4895265B2 JP 4895265 B2 JP4895265 B2 JP 4895265B2 JP 2005377635 A JP2005377635 A JP 2005377635A JP 2005377635 A JP2005377635 A JP 2005377635A JP 4895265 B2 JP4895265 B2 JP 4895265B2
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- 239000003054 catalyst Substances 0.000 title claims description 70
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims description 45
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 41
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 238000003786 synthesis reaction Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 title description 20
- 239000002002 slurry Substances 0.000 claims description 132
- 239000002994 raw material Substances 0.000 claims description 128
- 238000001035 drying Methods 0.000 claims description 79
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims description 25
- 239000011733 molybdenum Substances 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 230000005484 gravity Effects 0.000 claims description 16
- 230000002194 synthesizing effect Effects 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000011133 lead Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 239000011669 selenium Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052716 thallium Inorganic materials 0.000 claims description 5
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 37
- 239000007789 gas Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000007254 oxidation reaction Methods 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000012071 phase Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000011964 heteropoly acid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000003839 salts Chemical group 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000001879 Curdlan Substances 0.000 description 1
- 229920002558 Curdlan Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229940078035 curdlan Drugs 0.000 description 1
- 235000019316 curdlan Nutrition 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
本発明はメタクロレインおよび／またはメタクリル酸合成用触媒、その製造方法、およびその触媒を用いるメタクロレインおよび／またはメタクリル酸を製造する方法に関する。 The present invention relates to a catalyst for synthesizing methacrolein and / or methacrylic acid, a method for producing the same, and a method for producing methacrolein and / or methacrylic acid using the catalyst.
イソブチレン、第三級ブチルアルコール（以下、ＴＢＡという。）、メチル第三級ブチルエーテル（以下、ＭＴＢＥという。）を分子状酸素により気相接触酸化してメタクロレインおよび／またはメタクリル酸を製造する際に使用される触媒としてモリブデンと、ビスマスと、鉄とを含有する酸化物触媒が知られている。このような酸化物触媒を製造する方法としては、モリブデンと、ビスマスと、鉄とを少なくとも含有する原料液を調製した後、原料液から溶媒を除去し、乾燥、焼成などの工程を適宜実施する方法が一般的である。例えば特許文献１には、モリブデンと、ビスマスと、鉄とを少なくとも含有する原料液の調製方法として、予めモリブデンを含有する水溶液または分散液を調製し、これに三酸化ビスマスを加えてから超音波処理し、次いで、これと鉄を含有する水溶液または分散液とを混合するメタクロレインおよび／またはメタクリル酸合成用触媒の製造方法が開示されている。 When producing methacrolein and / or methacrylic acid by vapor-phase catalytic oxidation of isobutylene, tertiary butyl alcohol (hereinafter referred to as TBA) and methyl tertiary butyl ether (hereinafter referred to as MTBE) with molecular oxygen. As a catalyst to be used, an oxide catalyst containing molybdenum, bismuth and iron is known. As a method for producing such an oxide catalyst, after preparing a raw material liquid containing at least molybdenum, bismuth, and iron, the solvent is removed from the raw material liquid, and steps such as drying and firing are appropriately performed. The method is common. For example, in Patent Document 1, as a method for preparing a raw material liquid containing at least molybdenum, bismuth, and iron, an aqueous solution or dispersion containing molybdenum is prepared in advance, and bismuth trioxide is added thereto, followed by ultrasonic waves. A method for producing a catalyst for synthesizing methacrolein and / or methacrylic acid, which is treated and then mixed with an aqueous solution or dispersion containing iron is disclosed.
また、メタクロレインを気相接触酸化してメタクリル酸を合成するメタクリル酸合成用触媒としてモリブデンおよびリンを含むヘテロポリ酸系触媒が有効であることは公知である。例えば、特許文献２には、リン、モリブデンおよびバナジウムを触媒成分元素として含有するヘテロポリ酸系触媒を製造する方法として、触媒成分元素を含有する化合物を混合したスラリーを濃縮または乾燥して、濃縮物または乾燥物中の水分含有量を５〜２０質量％に調節した後、１００〜２５０℃で熱処理するメタクリル酸合成用触媒の製造方法が開示されている。
しかし、特許文献１および２に記載の方法で製造した触媒を用いた気相接触酸化反応はメタクロレインおよび／またはメタクリル酸の収率が工業触媒としては不十分であり、更なる収率の向上が望まれている。 However, the gas-phase catalytic oxidation reaction using the catalyst produced by the methods described in Patent Documents 1 and 2 has insufficient yield of methacrolein and / or methacrylic acid as an industrial catalyst, and further increases the yield. Is desired.
本発明は、メタクロレインおよび／またはメタクリル酸を高い収率で製造できる触媒、その触媒の製造方法、並びにメタクロレインおよび／またはメタクリル酸を高い収率で製造する方法を提供することを目的とする。 An object of the present invention is to provide a catalyst capable of producing methacrolein and / or methacrylic acid in high yield, a method for producing the catalyst, and a method for producing methacrolein and / or methacrylic acid in high yield. .
本発明の第１は、少なくともモリブデンを含む原料スラリーを乾燥装置へ供給し、該乾燥装置内で前記原料スラリーを乾燥して乾燥粉を得る工程を有する、少なくともモリブデンを含むメタクリル酸合成用触媒の製造方法において、前記乾燥の開始時から終了時までの間、原料スラリーの粘度（単位：ｋｇ／（ｍ・ｓ））を原料スラリーの比重（単位：ｋｇ／ｍ３）で除した値である原料スラリーの比粘度（ｍ２／ｓ）が、下記式（Ｉ）を満足することを特徴とするメタクロレインおよび／またはメタクリル酸合成用触媒の製造方法である。
０．９５Ｘ０≦Ｘ≦１．０５Ｘ０ （Ｉ）
Ｘ：原料スラリーの比粘度（ｍ２／ｓ）
Ｘ０：乾燥開始時の原料スラリーの比粘度（ｍ２／ｓ）
A first aspect of the present invention is a catalyst for synthesizing methacrylic acid containing at least molybdenum, comprising a step of supplying a raw material slurry containing at least molybdenum to a drying device and drying the raw material slurry in the drying device to obtain a dry powder. In the production method, it is a value obtained by dividing the viscosity (unit: kg / (m · s)) of the raw material slurry by the specific gravity (unit: kg / m 3 ) of the raw material slurry from the start to the end of the drying. It is a method for producing methacrolein and / or methacrylic acid synthesis catalyst, characterized in that the specific viscosity (m 2 / s) of the raw material slurry satisfies the following formula (I).
0.95X 0 ≦ X ≦ 1.05X 0 (I)
X: Specific viscosity of raw material slurry (m 2 / s)
X 0 : Specific viscosity of raw material slurry at the start of drying (m 2 / s)
本発明の第２は、第１発明における乾燥開始時の原料スラリーの比粘度が、２．５×１０−４〜７．０×１０−４ｍ２／ｓであるメタクロレインおよび／またはメタクリル酸合成用触媒の製造方法である。 The second aspect of the present invention is methacrolein and / or methacrylic acid in which the specific viscosity of the raw material slurry at the start of drying in the first aspect of the invention is 2.5 × 10 −4 to 7.0 × 10 −4 m 2 / s. This is a method for producing a synthesis catalyst.
本発明の第３は、第１または２発明の方法で製造された、少なくともモリブデンを含有する触媒が前記式（１）で表される組成を有するメタクロレインおよび／またはメタクリル酸合成用触媒である。 A third aspect of the present invention is a catalyst for synthesizing methacrolein and / or methacrylic acid, wherein the catalyst containing at least molybdenum produced by the method of the first or second aspect of the invention has a composition represented by the formula (1). .
本発明の第４は、第１または２発明の方法で製造された、少なくともモリブデンを含有する触媒が前記式（２）で表される組成を有するメタクリル酸合成用触媒である。 A fourth aspect of the present invention is a catalyst for synthesizing methacrylic acid produced by the method of the first or second aspect, wherein the catalyst containing at least molybdenum has a composition represented by the formula (2).
本発明の第５は、第３発明のメタクロレインおよび／またはメタクリル酸合成用触媒を用いて、イソブチレン、ＴＢＡ、ＭＴＢＥからなる群より選ばれる少なくとも１種を分子状酸素により気相接触酸化するメタクロレインおよび／またはメタクリル酸の製造方法である。 According to a fifth aspect of the present invention, there is provided a methacrochromic reaction in which at least one selected from the group consisting of isobutylene, TBA, and MTBE is vapor-phase catalytically oxidized with molecular oxygen using the methacrolein and / or methacrylic acid synthesis catalyst of the third invention. A method for producing rain and / or methacrylic acid.
本発明の第６は、第４発明のメタクリル酸合成用触媒を用いて、メタクロレインを分子状酸素により気相接触酸化するメタクリル酸の製造方法である。 A sixth aspect of the present invention is a method for producing methacrylic acid in which methacrolein is vapor-phase contact oxidized with molecular oxygen using the catalyst for synthesizing methacrylic acid according to the fourth aspect of the invention.
本発明によれば、メタクロレインおよび／またはメタクリル酸を高い収率で製造できるメタクロレインおよび／またはメタクリル酸合成用触媒を製造することができ、本発明によるメタクロレインおよび／またはメタクリル酸合成用触媒を用いると、メタクロレインおよび／またはメタクリル酸を高い収率で製造できる。 According to the present invention, a catalyst for synthesizing methacrolein and / or methacrylic acid capable of producing methacrolein and / or methacrylic acid in high yield can be produced, and a catalyst for synthesizing methacrolein and / or methacrylic acid according to the present invention. Can be used to produce methacrolein and / or methacrylic acid in high yield.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の製造方法で製造されるメタクロレインおよび／またはメタクリル酸合成用触媒は、イソブチレン、ＴＢＡ、ＭＴＢＥからなる群より選ばれる少なくとも１種を分子状酸素により気相接触酸化して、メタクロレインおよび／またはメタクリル酸を製造する際に使用されるものであって、少なくともモリブデン、ビスマスおよび鉄を含有する複合酸化物である。本発明の製造方法で製造される酸化物触媒は、モリブデンと、ビスマスと、鉄とを含むものであれば特に限定されないが、触媒性能が良好であることから、下記式（１）で表される組成のものが好ましい。 The catalyst for synthesizing methacrolein and / or methacrylic acid produced by the production method of the present invention is obtained by subjecting at least one selected from the group consisting of isobutylene, TBA, and MTBE to gas phase catalytic oxidation with molecular oxygen, and methacrolein and It is used when producing methacrylic acid, and is a composite oxide containing at least molybdenum, bismuth and iron. The oxide catalyst produced by the production method of the present invention is not particularly limited as long as it contains molybdenum, bismuth, and iron, but is represented by the following formula (1) because the catalyst performance is good. Are preferred.
Ｍｏａ１Ｂｉｂ１Ｆｅｃ１Ｍｄ１Ｘｅ１Ｙｆ１Ｚｇ１Ｓｉｈ１Ｏｉ１ （１）
式（１）中、Ｍｏ、Ｂｉ、Ｆｅ、ＳｉおよびＯはそれぞれモリブデン、ビスマス、鉄、ケイ素および酸素を示し、Ｍはコバルトおよびニッケルからなる群より選ばれた少なくとも１種の元素を示し、Ｘはクロム、鉛、マンガン、カルシウム、マグネシウム、ニオブ、銀、バリウム、スズ、タンタルおよび亜鉛からなる群より選ばれた少なくとも１種の元素を示し、Ｙはリン、ホウ素、硫黄、セレン、テルル、セリウム、タングステン、アンチモンおよびチタンからなる群より選ばれた少なくとも１種の元素を示し、Ｚはリチウム、ナトリウム、カリウム、ルビジウム、セシウムおよびタリウムからなる群より選ばれた少なくとも１種の元素を示す。
Mo a1 Bi b1 Fe c1 M d1 X e1 Y f1 Z g1 Si h1 O i1 (1)
In the formula (1), Mo, Bi, Fe, Si and O each represent molybdenum, bismuth, iron, silicon and oxygen, M represents at least one element selected from the group consisting of cobalt and nickel, and X Represents at least one element selected from the group consisting of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc, and Y represents phosphorus, boron, sulfur, selenium, tellurium, cerium , Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and thallium.
また式（１）中、ａ１、ｂ１、ｃ１、ｄ１、ｅ１、ｆ１、ｇ１、ｈ１およびｉ１は各元素の原子比を表し、ａ１＝１２のとき０．０１≦ｂ１≦３、０．０１≦ｃ１≦５、１≦ｄ１≦１２、０≦ｅ１≦８、０≦ｆ１≦５、０．００１≦ｇ１≦２、０≦ｈ１≦２０であり、ｉ１は前記各成分の原子価を満足するのに必要な酸素の原子比である。 In the formula (1), a1, b1, c1, d1, e1, f1, g1, h1, and i1 represent atomic ratios of the respective elements. When a1 = 12, 0.01 ≦ b1 ≦ 3, 0.01 ≦ c1 ≦ 5, 1 ≦ d1 ≦ 12, 0 ≦ e1 ≦ 8, 0 ≦ f1 ≦ 5, 0.001 ≦ g1 ≦ 2, 0 ≦ h1 ≦ 20, and i1 satisfies the valence of each component. Is the atomic ratio of oxygen required for
一方、本発明の方法で製造するメタクリル酸合成用触媒は、少なくともモリブデンおよびリンを含有する複合酸化物である。この複合酸化物にはヘテロポリ酸および／またはヘテロポリ酸塩の構造が含まれていることが好ましい。触媒が複合酸化物であること、およびヘテロポリ酸および／またはその塩の構造が含まれていることはＸＲＤにより確認できる。 On the other hand, the catalyst for synthesizing methacrylic acid produced by the method of the present invention is a composite oxide containing at least molybdenum and phosphorus. This composite oxide preferably contains a heteropolyacid and / or heteropolyacid salt structure. It can be confirmed by XRD that the catalyst is a complex oxide and contains a heteropolyacid and / or a salt thereof.
また触媒は、モリブデンおよびリン以外に、カリウム、ルビジウム、セシウム、タリウム等のアルカリ金属を含んでいることが好ましく、さらにこれ以外に、銅、バナジウム、鉄、コバルト、ニッケル、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、クロム、タングステン、マンガン、銀、ホウ素、ケイ素、アルミニウム、ガリウム、ゲルマニウム、スズ、鉛、ヒ素、アンチモン、ビスマス、ニオブ、タンタル、ジルコニウム、インジウム、イオウ、セレン、テルル、ランタン、セリウム等を含んでいてもよい。特に、次の式（２）の組成式で表される複合酸化物が好ましい。 In addition to molybdenum and phosphorus, the catalyst preferably contains an alkali metal such as potassium, rubidium, cesium, thallium, etc. In addition, copper, vanadium, iron, cobalt, nickel, zinc, magnesium, calcium, Strontium, barium, titanium, chromium, tungsten, manganese, silver, boron, silicon, aluminum, gallium, germanium, tin, lead, arsenic, antimony, bismuth, niobium, tantalum, zirconium, indium, sulfur, selenium, tellurium, lanthanum, Cerium etc. may be included. In particular, a composite oxide represented by the following composition formula (2) is preferable.
Ｍｏａ２Ｐｂ２Ｃｕｃ２Ｖｄ２Ｘｅ２Ｙｆ２Ｏｇ２ （２）
式（２）中、Ｍｏ、Ｐ、Ｃｕ、ＶおよびＯはそれぞれモリブデン、リン、銅、バナジウムおよび酸素を表し、Ｘはカリウム、ルビジウム、セシウムおよびタリウムからなる群より選ばれた少なくとも１種の元素を表し、Ｙは鉄、コバルト、ニッケル、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、クロム、タングステン、マンガン、銀、ホウ素、ケイ素、アルミニウム、ガリウム、ゲルマニウム、スズ、鉛、ヒ素、アンチモン、ビスマス、ニオブ、タンタル、ジルコニウム、インジウム、イオウ、セレン、テルル、ランタンおよびセリウムからなる群より選ばれた少なくとも１種の元素を表す。
Mo a2 P b2 Cu c2 V d2 X e2 Y f2 O g2 (2)
In formula (2), Mo, P, Cu, V and O each represent molybdenum, phosphorus, copper, vanadium and oxygen, and X is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium Y represents iron, cobalt, nickel, zinc, magnesium, calcium, strontium, barium, titanium, chromium, tungsten, manganese, silver, boron, silicon, aluminum, gallium, germanium, tin, lead, arsenic, antimony, bismuth And at least one element selected from the group consisting of niobium, tantalum, zirconium, indium, sulfur, selenium, tellurium, lanthanum and cerium.
また式（２）中、ａ２、ｂ２、ｃ２、ｄ２、ｅ２、ｆ２およびｇ２は各元素の原子比を表し、ａ２＝１２のとき、０．１≦ｂ２≦３、０．０１≦ｃ２≦３、０．０１≦ｄ２≦３、０．０１≦ｅ２≦３、０≦ｆ２≦３であり、ｇ２は前記各成分の原子比を満足するのに必要な酸素の原子比である。 In formula (2), a2, b2, c2, d2, e2, f2, and g2 represent atomic ratios of each element. When a2 = 12, 0.1 ≦ b2 ≦ 3, 0.01 ≦ c2 ≦ 3 0.01 ≦ d2 ≦ 3, 0.01 ≦ e2 ≦ 3, and 0 ≦ f2 ≦ 3, and g2 is an atomic ratio of oxygen necessary to satisfy the atomic ratio of each component.
本発明において、上記の少なくともモリブデンを含有する原料スラリー（以下、原料スラリーという。）は、触媒の各構成元素の原料（以下、触媒原料という。）を用いて、例えば、従来の共沈法、酸化物混合法等により調製することができる。原料スラリーの調製に用いる原料は特に限定されず、触媒の各構成元素の、硝酸塩、炭酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物等を適宜組み合わせて使用することができる。モリブデン原料としては、例えば、パラモリブデン酸アンモニウム、三酸化モリブデン、モリブデン酸、塩化モリブデン等が使用でき、ビスマス原料としては、例えば、硝酸ビスマス、酸化ビスマス等が使用でき、鉄原料としては、例えば、硝酸第二鉄、水酸化鉄、三酸化鉄等が使用でき、リン原料としては、例えば、リン酸、五酸化リン、リン酸アンモニウム等が使用できる。溶媒としては、例えば、水、エチルアルコール、アセトン等が挙げられるが、水を用いることが好ましい。 In the present invention, the raw material slurry containing at least molybdenum described above (hereinafter referred to as raw material slurry) is prepared by using, for example, a conventional coprecipitation method using raw materials of constituent elements of the catalyst (hereinafter referred to as catalyst raw material). It can be prepared by an oxide mixing method or the like. The raw materials used for preparing the raw slurry are not particularly limited, and nitrates, carbonates, acetates, ammonium salts, oxides, halides, and the like of the respective constituent elements of the catalyst can be used in appropriate combinations. As the molybdenum raw material, for example, ammonium paramolybdate, molybdenum trioxide, molybdic acid, molybdenum chloride, and the like can be used.As the bismuth raw material, for example, bismuth nitrate, bismuth oxide, and the like can be used. Ferric nitrate, iron hydroxide, iron trioxide, and the like can be used, and examples of the phosphor raw material include phosphoric acid, phosphorus pentoxide, and ammonium phosphate. Examples of the solvent include water, ethyl alcohol, acetone and the like, but it is preferable to use water.
本発明において、原料スラリーを製造するための装置は、流体を入れる容器（攪拌槽）と流体をかき混ぜる可動部（攪拌翼）から構成される装置であることが好ましく、その形式は特に限定されず、例えば攪拌槽は円筒皿底、オートクレーブなど、攪拌翼はパドル翼（多段翼を含む）、大型翼など一般的に用いられる公知の装置を用いることができる。 In the present invention, the apparatus for producing the raw slurry is preferably an apparatus composed of a container (stirring tank) for containing a fluid and a movable part (stirring blade) for stirring the fluid, and its type is not particularly limited. For example, a well-known apparatus such as a cylindrical dish bottom or an autoclave may be used as the stirring tank, and a paddle blade (including multistage blades) or a large blade may be used as the stirring blade.
本発明において、触媒を製造する好ましい手順としては、例えば、モリブデン酸化物やパラモリブデン酸アンモニウム等のモリブデン原料を水に溶解または懸濁させた後にその他の触媒原料と混合し、得られた原料スラリーを乾燥させ、熱処理する方法が挙げられる。原料スラリー調製時に混合する、その他の触媒原料は、そのまままたは水等の液体媒体に適宜溶解または懸濁させたものが使用できる。また、触媒原料の混合途中または混合後にアンモニア水等を添加してもよい。 In the present invention, as a preferred procedure for producing a catalyst, for example, a molybdenum raw material such as molybdenum oxide or ammonium paramolybdate is dissolved or suspended in water and then mixed with other catalyst raw materials, and the raw material slurry obtained The method of drying and heat-treating is mentioned. As the other catalyst raw materials to be mixed at the time of preparing the raw slurry, those that are dissolved or suspended as appropriate in a liquid medium such as water can be used. Further, ammonia water or the like may be added during or after the mixing of the catalyst raw materials.
本発明において、上記の原料スラリーは、より低い比粘度のスラリーを調製し、そのスラリーを加熱して濃縮することにより調製することが好ましい。濃縮とは、スラリーを加熱し、スラリー中の溶媒等を揮発させる操作のことである。濃縮は、原料混合時と同じ攪拌槽を使用してもよいし、別の反応槽等に移し変えてもよい。濃縮は、スラリーの入った反応槽等の容器を電気ヒーターや蒸気等の熱源を用いて加熱することで行える。濃縮時のスラリーの温度は特に限定されないが、５０℃〜１２０℃が好ましく、９０℃〜１１０℃がより好ましい。濃縮中は適宜粘度および比重を測定し、比粘度が２．５×１０−４〜７．０×１０−４ｍ２／ｓの範囲で濃縮を終了することが好ましく、より好ましくは３．０×１０−４〜６．５×１０−４ｍ２／ｓの範囲である。比粘度とは、粘度（単位：ｋｇ／（ｍ・ｓ））を比重（単位：ｋｇ／ｍ３）で除した値である。粘度は反応槽または原料スラリー循環ラインにおいてインラインで測定してもよいし、原料スラリーの一部をサンプリングして測定してもよい。粘度計は、振動式、Ｂ型粘度計等を用いて測定することができる。粘度の測定は原料スラリーを十分に混合した後に行うことが好ましい。比重は原料スラリーの一部をサンプリングし、体積と質量を測定し、質量を体積で除して算出することができる。濃縮期間の粘度および比重の測定は、連続または間欠のどちらでもよいが、５分以内毎に間欠的に測定することが好ましい。また、上記の特定の比粘度になることが予め分かっている条件で濃縮する場合には、粘度および比重は特に測定しなくてもよい。 In the present invention, the raw material slurry is preferably prepared by preparing a slurry having a lower specific viscosity, and heating and concentrating the slurry. Concentration is an operation of heating the slurry and volatilizing the solvent and the like in the slurry. Concentration may use the same agitation tank used when mixing the raw materials, or may be transferred to another reaction tank or the like. Concentration can be performed by heating a container such as a reaction tank containing the slurry using a heat source such as an electric heater or steam. Although the temperature of the slurry at the time of concentration is not specifically limited, 50 to 120 degreeC is preferable and 90 to 110 degreeC is more preferable. During the concentration, the viscosity and the specific gravity are appropriately measured, and the concentration is preferably finished when the specific viscosity is in the range of 2.5 × 10 −4 to 7.0 × 10 −4 m 2 / s, more preferably 3.0. in the range of × 10 -4 ~6.5 × 10 -4 m 2 / s. The specific viscosity is a value obtained by dividing the viscosity (unit: kg / (m · s)) by the specific gravity (unit: kg / m 3 ). The viscosity may be measured in-line in a reaction vessel or a raw material slurry circulation line, or may be measured by sampling a part of the raw material slurry. The viscometer can be measured using a vibration type, a B-type viscometer or the like. The viscosity is preferably measured after the raw material slurry is sufficiently mixed. The specific gravity can be calculated by sampling a part of the raw slurry, measuring the volume and mass, and dividing the mass by the volume. The measurement of the viscosity and specific gravity during the concentration period may be continuous or intermittent, but it is preferable to measure intermittently every 5 minutes or less. Moreover, when it concentrates on the conditions known beforehand that it becomes said specific specific viscosity, a viscosity and specific gravity do not need to measure in particular.
本発明において、原料スラリーは乾燥装置で乾燥される。本発明において、乾燥とは、原料スラリー中の水分を蒸発させて粉体を得ることを指し、乾燥後の粉体に含まれる水分は５質量％以下が好ましい。乾燥開始までの原料スラリーの保持は、原料混合時や、濃縮を行った場合の濃縮時と同じ槽を使用してもよいし、別の槽に移し変えてもよい。別の槽に移し変える場合には、濃縮時に使用した槽から原料スラリーを全量移し変えた後、濃縮時に使用した槽を触媒調製時に使用した溶媒を用いて洗浄することが好ましく、この洗浄後のスラリーを含む溶媒は、乾燥に適する原料スラリーの比粘度が下記範囲であれば、原料スラリーを移し変えた槽にそのまま投入してもよい。一方、洗浄後のスラリーを含む溶媒を原料スラリーを移し変えた槽に投入することにより、乾燥に適する原料スラリーの比粘度が下記範囲より小さくなる場合は、洗浄後のスラリーを含む溶媒を加熱操作により溶媒量を減じた後に、原料スラリーを移し変えた槽に投入すればよい。 In the present invention, the raw slurry is dried with a drying apparatus. In the present invention, drying refers to obtaining a powder by evaporating moisture in the raw slurry, and the moisture contained in the dried powder is preferably 5% by mass or less. The holding of the raw material slurry until the start of drying may be performed using the same tank at the time of raw material mixing or at the time of concentration when concentration is performed, or may be transferred to another tank. When transferring to another tank, it is preferable to transfer the entire amount of the raw slurry from the tank used at the time of concentration, and then wash the tank used at the time of concentration with the solvent used at the time of catalyst preparation. If the specific viscosity of the raw material slurry suitable for drying is in the following range, the solvent containing the slurry may be directly added to the tank where the raw material slurry has been transferred. On the other hand, when the specific viscosity of the raw material slurry suitable for drying is smaller than the following range by introducing the solvent containing the washed slurry into the tank where the raw material slurry has been transferred, the solvent containing the washed slurry is heated. After reducing the amount of the solvent, the raw material slurry may be transferred to the transferred tank.
本発明においては、乾燥開始までの期間において、原料スラリーの比粘度を２．５×１０−４〜７．０×１０−４ｍ２／ｓの範囲に保持して、乾燥開始時の原料スラリーの比粘度がこの範囲となるようにすることが好ましい。より好ましくは３．０×１０−４〜６．５×１０−４ｍ２／ｓの範囲である。原料スラリーの調製後、乾燥開始までの期間は特に制限されないが、原料スラリーの物性等が変化しない期間での保持が好ましい。具体的には、０〜３０日間が好ましく、０〜５日間がより好ましい。この原料スラリーの調製後、乾燥開始までの期間においては、原料スラリーの比粘度を安定に保持するために、原料スラリーを保持した槽の攪拌を行うことが好ましい。また、原料スラリーを保持した槽から一旦スラリーを抜出し、槽外の配管を通して、再び原料スラリーを保持した槽へ戻すスラリーの循環を行うことが好ましい。槽外の配管としては、原料を保持した槽と乾燥装置へのスラリー供給配管を含むことが好ましい。このような循環を行うことで、スラリーの比粘度を安定に保持できるばかりでなく、配管内の詰りも防止することができる。このスラリーの循環は、定量ポンプ等を用いて行うことができる。 In the present invention, during the period until the start of drying, the specific viscosity of the raw material slurry is maintained in the range of 2.5 × 10 −4 to 7.0 × 10 −4 m 2 / s, and the raw material slurry at the start of drying It is preferable that the specific viscosity is in this range. More preferably in the range of 3.0 × 10 -4 ~6.5 × 10 -4 m 2 / s. The period from the preparation of the raw slurry to the start of drying is not particularly limited, but it is preferable to hold it during a period in which the physical properties of the raw slurry do not change. Specifically, 0 to 30 days is preferable, and 0 to 5 days is more preferable. In the period from the preparation of the raw slurry to the start of drying, it is preferable to stir the tank holding the raw slurry in order to stably maintain the specific viscosity of the raw slurry. In addition, it is preferable to circulate the slurry once withdrawn from the tank holding the raw slurry and returning to the tank holding the raw slurry again through a pipe outside the tank. The piping outside the tank preferably includes a tank holding the raw material and a slurry supply pipe to the drying apparatus. By performing such a circulation, not only can the specific viscosity of the slurry be stably maintained, but also clogging in the piping can be prevented. The slurry can be circulated using a metering pump or the like.
本発明において、原料スラリーを保持する槽から乾燥装置へ原料スラリーを供給し、乾燥装置内で原料スラリーを乾燥して乾燥粉を得る。原料スラリーの乾燥装置への供給は連続でも不連続でもよいが、連続が好ましい。特に不連続の場合は、上記の循環を行うことが好ましい。 In the present invention, the raw material slurry is supplied from the tank holding the raw material slurry to the drying device, and the raw material slurry is dried in the drying device to obtain a dry powder. Supply of the raw material slurry to the drying apparatus may be continuous or discontinuous, but continuous is preferable. In particular, in the case of discontinuity, it is preferable to perform the above circulation.
本発明においては、乾燥装置における乾燥の開始時から終了時までの間、下記式（Ｉ）を満足することが重要である。 In the present invention, it is important to satisfy the following formula (I) from the start to the end of drying in the drying apparatus.
０．９５Ｘ０≦Ｘ≦１．０５Ｘ０ （Ｉ）
Ｘ：原料スラリーの比粘度（ｍ２／ｓ）
Ｘ０：乾燥開始時の原料スラリーの比粘度（ｍ２／ｓ）
式（Ｉ）の最左辺は０．９７Ｘ０であることが好ましく、式（Ｉ）の最左辺は１．０３Ｘ０であることが好ましい。
0.95X 0 ≦ X ≦ 1.05X 0 (I)
X: Specific viscosity of raw material slurry (m 2 / s)
X 0 : Specific viscosity of raw material slurry at the start of drying (m 2 / s)
Preferably the outermost left-hand side of formula (I) is 0.97X 0, it is preferable top left side of the formula (I) is 1.03X 0.
乾燥の開始時から終了時までの間、原料スラリーの比粘度を上記範囲に保つことにより、安定した物性の乾燥粉を調製することができ、結果としてメタクロレインおよび／またはメタクリル酸収率に優れた性能を示す触媒を調製することができる。原料スラリーの比粘度が、乾燥開始時の原料スラリーの比粘度±５％の範囲を超えると、得られる乾燥粉体の粒径が変化し、所定の性能を持つ触媒を得ることができない。具体的には、乾燥開始時の原料スラリーの比粘度＋５％を超えると、乾燥粉体の粒径が大きくなり活性が下がる。乾燥開始時の原料スラリーの比粘度−５％より下がると、乾燥粉体の粒径が小さくなり、物質拡散が悪くなって選択性が低下する影響がある。 By maintaining the specific viscosity of the raw material slurry in the above range from the start to the end of drying, it is possible to prepare a dry powder with stable physical properties, resulting in excellent yields of methacrolein and / or methacrylic acid. Catalysts exhibiting excellent performance can be prepared. When the specific viscosity of the raw material slurry exceeds the range of the specific viscosity ± 5% of the raw material slurry at the start of drying, the particle size of the obtained dry powder changes and a catalyst having a predetermined performance cannot be obtained. Specifically, when the specific viscosity of the raw material slurry at the start of drying exceeds 5%, the particle size of the dry powder increases and the activity decreases. When the specific viscosity of the raw material slurry at the start of drying is lower than -5%, the particle size of the dry powder becomes small, and the material diffusion becomes worse and the selectivity is lowered.
本発明においては、原料スラリーの比粘度を所定範囲に保つ方法としては、原料スラリーを保持する装置に蓋をする、その装置内で攪拌をする、原料スラリーの温度を一定に保つなどの手段を適宜組み合わせて行うことができる。 In the present invention, as a method for maintaining the specific viscosity of the raw material slurry within a predetermined range, means such as covering the raw material slurry holding device, stirring in the device, keeping the raw material slurry temperature constant, etc. It can carry out in combination as appropriate.
特に本発明においては、乾燥開始時から終了時までの間、原料スラリーの比粘度のほか、原料スラリーの温度をできるだけ一定に保つことが好ましい。保持温度には特に制限はなく、乾燥に適した温度で保持すればよいが、５０〜９０℃が好ましい。原料スラリーの温度は、乾燥開始時の温度に対して±３℃の範囲に保つことが好ましい。 In particular, in the present invention, it is preferable to keep the temperature of the raw material slurry as constant as possible in addition to the specific viscosity of the raw material slurry from the start to the end of drying. There is no restriction | limiting in particular in holding temperature, What is necessary is just to hold | maintain at the temperature suitable for drying, but 50-90 degreeC is preferable. The temperature of the raw material slurry is preferably maintained in a range of ± 3 ° C. with respect to the temperature at the start of drying.
本発明で使用する乾燥装置としては、通常の乾燥装置が挙げられる。連続的に乾燥する装置としては、噴霧乾燥法、気流乾燥法、ドラム乾燥法などの各装置が挙げられ、一方、不連続的に乾燥する装置としては、必要量だけ別の容器に移液する箱型乾燥法、蒸発乾固法などが挙げられる。乾燥温度は特に限定されないが、１００℃〜５００℃が好ましく、１１０℃〜４００℃がより好ましい。乾燥時間は特に限定されないが、０．１〜４８時間が好ましく、０．３〜２４時間がより好ましい。 Examples of the drying apparatus used in the present invention include a normal drying apparatus. Examples of the continuous drying device include spray drying method, air flow drying method, drum drying method, and the like. On the other hand, as the device for discontinuous drying, only a necessary amount is transferred to another container. Examples include a box-type drying method and an evaporation to dryness method. Although drying temperature is not specifically limited, 100 to 500 degreeC is preferable and 110 to 400 degreeC is more preferable. Although drying time is not specifically limited, 0.1 to 48 hours are preferable and 0.3 to 24 hours are more preferable.
本発明において、原料スラリーの乾燥装置への供給方法は、ポンプで送ってもよいし、乾燥装置より原料スラリーを保持している装置内の圧力を高くして圧力差により供給してもよいが、一定量を供給できる定量ポンプ等を利用するのが好ましい。 In the present invention, the method of supplying the raw material slurry to the drying device may be sent by a pump, or the pressure in the device holding the raw material slurry may be higher than the drying device and supplied by a pressure difference. It is preferable to use a metering pump that can supply a constant amount.
得られた乾燥物の平均粒径は、１〜１０００μｍであることが好ましい。なお、平均粒径とは、レーザー式粒度分布測定装置で測定される粒径分布から読み取ったメジアン径を言う。 The average particle size of the obtained dried product is preferably 1 to 1000 μm. The average particle diameter means a median diameter read from a particle diameter distribution measured with a laser particle size distribution measuring apparatus.
次いで、得られた乾燥物は３００〜５００℃、好ましくは３００〜４５０℃で焼成する。焼成は、空気等の酸素含有ガス流通下および／または不活性ガス流通下で行うことが好ましい。焼成時間は０．５時間以上が好ましく、より好ましくは１〜４０時間である。成形触媒を製造する場合は、乾燥物をそのまま焼成し、得られた焼成物を成形してもよいが、乾燥物を予め成形し、得られた成形物を焼成することが好ましい。乾燥物または焼成物の成形方法は特に限定されないが、例えば、打錠成形、押出成形、造粒等の各種の成形法を用いることができる。成形に際しては、比表面積、細孔容積および細孔分布の揃った成形物を再現性良く製造する、成形物の機械的強度を高める等の目的で、例えば、硫酸バリウム、硫酸アンモニウム等の無機塩類、グラファイト等の滑剤、セルロース類、でんぷん、ポリビニルアルコール、ステアリン酸等の有機物、シリカゾル、アルミナゾル等の水酸化物ゾル、ウィスカー、ガラス繊維、炭素繊維等の無機質繊維等の添加剤や添加物を適宜添加してもよい。成形物の形状は特に限定されず、例えば、球状、円柱状、リング状、板状等が挙げられる。 Next, the obtained dried product is fired at 300 to 500 ° C, preferably 300 to 450 ° C. Firing is preferably performed under a flow of oxygen-containing gas such as air and / or under a flow of inert gas. The firing time is preferably 0.5 hours or more, more preferably 1 to 40 hours. When producing a molded catalyst, the dried product may be calcined as it is, and the obtained calcined product may be molded. However, it is preferable to mold the dried product in advance and calcine the obtained molded product. There are no particular limitations on the method of molding the dried or fired product, and various molding methods such as tableting, extrusion, and granulation can be used. In the molding, for example, inorganic salts such as barium sulfate, ammonium sulfate, etc. for the purpose of producing a molded product having a uniform specific surface area, pore volume and pore distribution with good reproducibility and increasing the mechanical strength of the molded product, Additives and additives such as lubricants such as graphite, organic substances such as celluloses, starch, polyvinyl alcohol and stearic acid, hydroxide sols such as silica sol and alumina sol, inorganic fibers such as whiskers, glass fibers and carbon fibers May be. The shape of the molded product is not particularly limited, and examples thereof include a spherical shape, a cylindrical shape, a ring shape, and a plate shape.
このよう方法によりメタクロレインおよび／またはメタクリル酸収率の高い触媒が製造できる理由は明らかではないが、乾燥時のスラリーの比粘度を前記の特定範囲にすることにより、安定した性状の乾燥粉を得ることができ、結果として気相接触酸化反応に有利に働く成形体が形成されると推測している。 The reason why a catalyst with a high yield of methacrolein and / or methacrylic acid can be produced by such a method is not clear, but by setting the specific viscosity of the slurry during drying to the above specific range, a dry powder having a stable property can be obtained. It can be obtained, and as a result, it is presumed that a molded body that favors the gas phase catalytic oxidation reaction is formed.
次に、このようにして得られた本発明の触媒を用いて、イソブチレン、ＴＢＡ、ＭＴＢＥからなる群より選ばれる少なくとも１種、あるいはメタクロレイン（以下、これらのまとめて反応原料という。）を気相接触酸化してメタクロレインおよび／またはメタクリル酸を製造する方法について説明する。 Next, using the catalyst of the present invention thus obtained, at least one selected from the group consisting of isobutylene, TBA, and MTBE, or methacrolein (hereinafter collectively referred to as reaction raw materials) is taken care of. A method for producing methacrolein and / or methacrylic acid by phase contact oxidation will be described.
気相接触酸化反応（以下、単に反応ともいう。）では、少なくとも反応原料と分子状酸素を含む原料ガスを触媒と接触させる。通常、反応は触媒を充填した管式反応器が使用される。工業的には多管式反応器が好ましく使用される。 In the gas phase catalytic oxidation reaction (hereinafter also simply referred to as reaction), a raw material gas containing at least a reaction raw material and molecular oxygen is brought into contact with a catalyst. Usually, a tubular reactor filled with a catalyst is used for the reaction. Industrially, a multitubular reactor is preferably used.
反応において、触媒は、必要に応じてシリカ、アルミナ、シリカ−アルミナ、マグネシア、チタニア、シリコンカーバイト等の不活性物質で希釈された状態で使用される。 In the reaction, the catalyst is used in a state diluted with an inert substance such as silica, alumina, silica-alumina, magnesia, titania, silicon carbide or the like as necessary.
本発明において、反応に用いる原料ガスの濃度は広い範囲で変えることができ、原料ガス中の反応原料の濃度は１〜２０容量％が好ましく、特に３〜１０容量％が好ましい。原料ガス中の反応原料と酸素とのモル比は、１：０．４〜１：４の範囲が好ましく、特に１：０．５〜１：３の範囲が好ましい。 In the present invention, the concentration of the raw material gas used for the reaction can be varied within a wide range, and the concentration of the reactive raw material in the raw material gas is preferably 1 to 20% by volume, particularly preferably 3 to 10% by volume. The molar ratio of the reaction raw material and oxygen in the raw material gas is preferably in the range of 1: 0.4 to 1: 4, particularly preferably in the range of 1: 0.5 to 1: 3.
原料ガスの分子状酸素源には空気を用いるのが工業的に有利であるが、必要に応じて純酸素で富化した空気等も使用できる。また、原料ガスは、窒素、炭酸ガス等の不活性ガス、水蒸気等で希釈されていることが好ましい。 Although it is industrially advantageous to use air as the molecular oxygen source of the source gas, air or the like enriched with pure oxygen can also be used if necessary. The source gas is preferably diluted with an inert gas such as nitrogen or carbon dioxide, water vapor or the like.
原料のメタクロレインには、水、低級飽和アルデヒド等の実質的に反応に影響を与えない不純物が少量含まれている場合があるが、原料ガスにはこのようなメタクロレイン由来の不純物が含まれていてもよい。 The raw material methacrolein may contain a small amount of impurities that do not substantially affect the reaction, such as water, lower saturated aldehydes, etc., but the raw material gas contains such an impurity derived from methacrolein. It may be.
反応圧力は大気圧〜５気圧が好ましく、より好ましくは大気圧〜３気圧である。反応温度は２００〜４５０℃が好ましく、より好ましくは２５０〜４００℃である。原料ガスと触媒の接触時間は１．５〜１５秒が好ましく、より好ましくは２〜７秒である。 The reaction pressure is preferably from atmospheric pressure to 5 atmospheres, more preferably from atmospheric pressure to 3 atmospheres. 200-450 degreeC of reaction temperature is preferable, More preferably, it is 250-400 degreeC. The contact time between the raw material gas and the catalyst is preferably 1.5 to 15 seconds, more preferably 2 to 7 seconds.
以下に本発明を実施例および比較例を用いて説明する。ただし、実施例および比較例中の「部」は質量部を意味する。 The present invention will be described below with reference to examples and comparative examples. However, “parts” in Examples and Comparative Examples means parts by mass.
原料がイソブチレンの場合、原料であるイソブチレンの反応率、並びに生成物であるメタクロレインの選択率、メタクリル酸の選択率、メタクロレインおよびメタクリル酸の合計単流収率（以下、合計単流収率という。）はそれぞれ以下のように定義される。 When the raw material is isobutylene, the reaction rate of the raw material isobutylene, the selectivity of the product methacrolein, the selectivity of methacrylic acid, the total single stream yield of methacrolein and methacrylic acid (hereinafter, the total single stream yield) Are defined as follows.
イソブチレンの反応率（％）＝（Ｂ１／Ａ１）×１００
メタクロレインの選択率（％）＝（Ｃ１／Ｂ１）×１００
メタクリル酸の選択率（％）＝（Ｄ１／Ｂ１）×１００
合計単流収率（％）＝（Ｃ１＋Ｄ１）／Ａ１×１００
ここで、Ａ１は供給した原料イソブチレンのモル数、Ｂ１は反応した原料イソブチレンのモル数、Ｃ１は生成したメタクロレインのモル数、Ｄ１は生成したメタクリル酸のモル数である。
Reaction rate of isobutylene (%) = (B1 / A1) × 100
Selectivity of methacrolein (%) = (C1 / B1) × 100
Methacrylic acid selectivity (%) = (D1 / B1) × 100
Total single flow yield (%) = (C1 + D1) / A1 × 100
Here, A1 is the number of moles of raw material isobutylene supplied, B1 is the number of moles of reacted raw material isobutylene, C1 is the number of moles of produced methacrolein, and D1 is the number of moles of produced methacrylic acid.
また原料がメタクロレインの場合、原料であるメタクロレインの転化率、並びに生成物であるメタクリル酸の選択率および単流収率は、以下のように定義される。 When the raw material is methacrolein, the conversion rate of the raw material methacrolein, the selectivity of the product methacrylic acid, and the single stream yield are defined as follows.
メタクロレイン反応率（％）＝（Ｂ２／Ａ２）×１００
メタクリル酸選択率（％）＝（Ｃ２／Ｂ２）×１００
メタクリル酸単流収率（％）＝（Ｃ２／Ａ２）×１００
ここで、Ａ２は供給したメタクロレインのモル数、Ｂ２は反応したメタクロレインのモル数、Ｃ２は生成したメタクリル酸のモル数である。
Methacrolein reaction rate (%) = (B2 / A2) × 100
Methacrylic acid selectivity (%) = (C2 / B2) × 100
Methacrylic acid single stream yield (%) = (C2 / A2) × 100
Here, A2 is the number of moles of methacrolein supplied, B2 is the number of moles of reacted methacrolein, and C2 is the number of moles of methacrylic acid produced.
実施例および比較例において、原料ガスおよび生成物の定量はガスクロマトグラフィーで行った。原料スラリーの粘度（ｋｇ／（ｍ・ｓ））は、原料スラリーの一部をサンプリングし、固形分が分離しないように十分に攪拌を行った後にＢ型粘度計を用いて測定した。原料スラリーの比重（ｋｇ／ｍ３）は、原料スラリーの一部をサンプリングし、体積（ｍ３）と質量（ｋｇ）を測定し、質量を体積で除して算出した。濃縮中のこれらの測定は５分間隔で行った。比粘度（ｍ２／ｓ）は粘度（ｋｇ／（ｍ・ｓ））を比重（ｋｇ／ｍ３）で除して算出した。触媒が複合酸化物であること、およびヘテロポリ酸および／またはその塩の構造が含まれていることはＸＲＤにより確認した。 In Examples and Comparative Examples, the raw material gas and the product were quantified by gas chromatography. The viscosity (kg / (m · s)) of the raw material slurry was measured using a B-type viscometer after a part of the raw material slurry was sampled and sufficiently stirred so that the solid content was not separated. The specific gravity (kg / m 3 ) of the raw material slurry was calculated by sampling a part of the raw material slurry, measuring the volume (m 3 ) and mass (kg), and dividing the mass by the volume. These measurements during concentration were made at 5 minute intervals. The specific viscosity (m 2 / s) was calculated by dividing the viscosity (kg / (m · s)) by the specific gravity (kg / m 3 ). It was confirmed by XRD that the catalyst was a complex oxide and contained a heteropolyacid and / or a salt thereof.
[実施例１]
パドル翼（１段）付の攪拌槽（加熱、冷却用ジャケット付）に、純水１０００部に対して、パラモリブデン酸アンモニウム５００部、パラタングステン酸アンモニウム６．２部、硝酸セシウム２３．０部、三酸化アンチモン２４．０部および三酸化ビスマス３３．０部を順次加え（Ａ液）、加熱攪拌を開始した（以下、濃縮終了まで攪拌を継続した）。別にパドル翼（１段）付の攪拌槽に、純水１０００部に対して、硝酸第二鉄２０９．８部、硝酸ニッケル７５．５部、硝酸コバルト４５３．３部および硝酸鉛３１．３部を順次加え、溶解した（Ｂ液）。ついで、Ａ液にＢ液を加えて水性スラリーとして、このスラリーを１０１℃まで加熱し、濃縮を開始した。濃縮開始時のスラリーの粘度は０．０５ｋｇ／（ｍ・ｓ）、比重は１．２７×１０３ｋｇ／ｍ３で、比粘度は０．３９０×１０−４ｍ２／ｓであり、スラリーの粘度が０．８７ｋｇ／（ｍ・ｓ）、比重が１．４４×１０３ｋｇ／ｍ３で、比粘度が６．０４×１０−４ｍ２／ｓの時点で加熱を停止して濃縮を終了した。濃縮終了後、直ちに攪拌槽の原料投入口に蓋をして、濃縮後スラリーを攪拌しながら７０℃に降温した。
[Example 1]
500 parts of ammonium paramolybdate, 6.2 parts of ammonium paratungstate, 23.0 parts of cesium nitrate in 1000 parts of pure water in a stirring tank (with a heating and cooling jacket) with a paddle blade (one stage) Then, 24.0 parts of antimony trioxide and 33.0 parts of bismuth trioxide were sequentially added (liquid A), and heating and stirring were started (hereinafter, stirring was continued until the end of concentration). Separately, in a stirring tank with a paddle blade (one stage), ferric nitrate 209.8 parts, nickel nitrate 75.5 parts, cobalt nitrate 453.3 parts and lead nitrate 31.3 parts with respect to 1000 parts of pure water Were sequentially added and dissolved (solution B). Next, liquid B was added to liquid A to form an aqueous slurry, and this slurry was heated to 101 ° C. to start concentration. The viscosity of the slurry at the start of concentration is 0.05 kg / (m · s), the specific gravity is 1.27 × 10 3 kg / m 3 , and the specific viscosity is 0.390 × 10 −4 m 2 / s. When the viscosity is 0.87 kg / (m · s), the specific gravity is 1.44 × 10 3 kg / m 3 , and the specific viscosity is 6.04 × 10 −4 m 2 / s, the heating is stopped and the liquid is concentrated. Ended. Immediately after the completion of concentration, the raw material inlet of the stirring vessel was covered, and the temperature was lowered to 70 ° C. while stirring the slurry after concentration.
次にこの濃縮後スラリー（原料スラリー）を７０±１．５℃の範囲に設定した撹拌槽中で保持しながら噴霧乾燥機にて乾燥を行った。なお、乾燥は入口熱風温度；３００℃、出口温度；１２０〜１３０℃でロータリーアトマイザー回転数；１５，０００ｒｐｍの条件で行い、乾燥には１６時間を要した。この間、原料スラリーの比粘度は最大６．１４×１０−４ｍ２／ｓ、最小は５．９５×１０−４ｍ２／ｓであり、乾燥開始時に対してそれぞれ＋１．７％、−１．５％であった。なお、乾燥期間中（１６時間）に原料スラリーの温度は６０℃±１℃で保持されていた。得られた乾燥粉体をよく混合し、レーザー式粒度分布測定装置で粒径を測定したところ、５０％における平均粒径（メジアン径）は５５μｍであった。 Next, this concentrated slurry (raw material slurry) was dried in a spray dryer while being held in a stirring tank set in a range of 70 ± 1.5 ° C. In addition, drying was performed on condition of inlet hot air temperature; 300 degreeC, outlet temperature; 120-130 degreeC, rotary atomizer rotation speed; 15,000 rpm, and drying required 16 hours. During this period, the specific viscosity of the raw slurry is 6.14 × 10 −4 m 2 / s at the maximum and 5.95 × 10 −4 m 2 / s at the minimum, and + 1.7% and −1 with respect to the start of drying, respectively. .5%. During the drying period (16 hours), the temperature of the raw material slurry was maintained at 60 ° C. ± 1 ° C. The obtained dry powder was mixed well and the particle size was measured with a laser type particle size distribution analyzer. The average particle size (median diameter) at 50% was 55 μm.
このようにして得られた乾燥粉体５００部に対してヒドロキシプロピルメチルセルロース２０部およびカードラン５部を添加した後、よく乾式混合した。この混合物と純水１９０部を双腕式ニーダーに投入し、粘土状物質になるまで混練を行った。得られた粘土状物質を押出成形機により、外形５ｍｍ、内径２ｍｍ、平均長さ５ｍｍのリング状に成形した。得られた触媒成形体を空気流通下１１０℃熱風乾燥機を用いて乾燥を行い、その後、この触媒成形体を４００℃にて３時間焼成して、触媒成形体の最終焼成体を得た。 After adding 20 parts of hydroxypropylmethylcellulose and 5 parts of curdlan to 500 parts of the dry powder thus obtained, the mixture was thoroughly dry-mixed. This mixture and 190 parts of pure water were put into a double-arm kneader and kneaded until a clay-like substance was obtained. The obtained clay-like substance was formed into a ring shape having an outer diameter of 5 mm, an inner diameter of 2 mm, and an average length of 5 mm by an extrusion molding machine. The obtained catalyst molded body was dried using a 110 ° C. hot air dryer under air flow, and then the catalyst molded body was calcined at 400 ° C. for 3 hours to obtain a final fired body of the catalyst molded body.
得られた触媒の酸素以外の元素の組成は、Ｍｏ１２Ｗ０．１Ｂｉ０．６Ｆｅ２．２Ｓｂ０．７Ｎｉ１．１Ｃｏ６．６Ｐｂ０．４Ｃｓ０．６であった
この触媒を反応管に充填し、イソブチレン５％、酸素１２％、水蒸気１０％、窒素７３％（容量％）の混合ガスを、大気圧下、反応温度３４０℃、接触時間３．６秒で通じてイソブチレンの気相接触酸化反応を行った。この結果を表１に示した。
The composition of elements other than oxygen in the obtained catalyst was Mo 12 W 0.1 Bi 0.6 Fe 2.2 Sb 0.7 Ni 1.1 Co 6.6 Pb 0.4 Cs 0.6 . This catalyst is packed in a reaction tube, and a mixed gas of 5% isobutylene, 12% oxygen, 10% water vapor and 73% nitrogen (volume%) is passed under atmospheric pressure at a reaction temperature of 340 ° C. and a contact time of 3.6 seconds. Then, gas phase catalytic oxidation reaction of isobutylene was performed. The results are shown in Table 1.
［比較例１］
乾燥期間中の攪拌槽の原料投入口の蓋を閉めず、かつ撹拌槽Ａの温度のコントロールをせずに原料スラリーを保持した点以外は、実施例１と同様にして触媒を製造およびメタクロレインの気相接触酸化反応を行った。なお、乾燥期間中（１６時間）に原料スラリーの温度は７０℃から３５℃に低下した。乾燥期間中の原料スラリーの比粘度の最大値及び最小値、並びに気相接触酸化反応結果を表１に示した。
[Comparative Example 1]
The catalyst was produced and methacrolein in the same manner as in Example 1 except that the raw material slurry was held without closing the raw material inlet of the stirring tank during the drying period and without controlling the temperature of the stirring tank A. The gas phase catalytic oxidation reaction of was carried out. During the drying period (16 hours), the temperature of the raw material slurry decreased from 70 ° C. to 35 ° C. Table 1 shows the maximum value and the minimum value of the specific viscosity of the raw material slurry during the drying period, and the results of the gas phase catalytic oxidation reaction.
［実施例２］
パドル２段翼付の攪拌槽（加熱、冷却用ジャケット付）に純水４００部を投入し８０ｒｐｍで攪拌を開始した（以下、濃縮終了まで攪拌を継続した）。そこへ三酸化モリブデン１００部、８５質量％リン酸水溶液７．３部、五酸化バナジウム３．２部、酸化銅０．５部、酸化鉄０．２部、硝酸セリウム２．５部を加え、９５℃で５時間加熱攪拌を行った。この液を５０℃まで冷却した後、硝酸セシウム１１．３部を純水３０部に溶解した溶液を滴下し１５分間攪拌した。次いでこの液を７０℃に昇温し、２９質量％アンモニア水３７．４部を滴下し、５０℃で１５分間攪拌した。さらにこのスラリーを１０１℃まで加熱し、濃縮を開始した。濃縮開始時のスラリーの粘度は０．０３ｋｇ／（ｍ・ｓ）、比重は１．２５×１０３ｋｇ／ｍ３で、比粘度は０．２４０×１０−４ｍ２／ｓであり、スラリーの粘度が０．９５ｋｇ／（ｍ・ｓ）、比重が１．６０×１０３ｋｇ／ｍ３で、比粘度が５．９４×１０−４ｍ２／ｓの時点で加熱を停止して濃縮を終了した。濃縮終了後、直ちに攪拌槽Ａの原料投入口に蓋をして、濃縮後スラリーを攪拌しながら８０℃に降温した。
[Example 2]
400 parts of pure water was put into a stirring tank with a two-stage paddle blade (with a heating and cooling jacket), and stirring was started at 80 rpm (hereinafter, stirring was continued until concentration was completed). Thereto, 100 parts of molybdenum trioxide, 7.3 parts of 85 mass% phosphoric acid aqueous solution, 3.2 parts of vanadium pentoxide, 0.5 parts of copper oxide, 0.2 parts of iron oxide, 2.5 parts of cerium nitrate, Stirring was performed at 95 ° C. for 5 hours. After cooling this solution to 50 ° C., a solution prepared by dissolving 11.3 parts of cesium nitrate in 30 parts of pure water was added dropwise and stirred for 15 minutes. Subsequently, this liquid was heated up to 70 degreeC, 37.4 parts of 29 mass% ammonia water was dripped, and it stirred at 50 degreeC for 15 minutes. The slurry was further heated to 101 ° C. and concentration was started. The viscosity of the slurry at the start of concentration is 0.03 kg / (m · s), the specific gravity is 1.25 × 10 3 kg / m 3 , and the specific viscosity is 0.240 × 10 −4 m 2 / s. When the viscosity is 0.95 kg / (m · s), the specific gravity is 1.60 × 10 3 kg / m 3 , and the specific viscosity is 5.94 × 10 −4 m 2 / s, the heating is stopped and the solution is concentrated. Ended. Immediately after the completion of concentration, the raw material inlet of the stirring tank A was covered, and the temperature was lowered to 80 ° C. while stirring the slurry after concentration.
次にこの濃縮後スラリー（原料スラリー）を８０±１．０℃の範囲に設定した撹拌槽中で保持しながら噴霧乾燥機にて乾燥を行った。なお、乾燥は入口熱風温度；３００℃、出口温度；１１０〜１２０℃でロータリーアトマイザー回転数；１８，０００ｒｐｍの条件で行い、乾燥には１０時間を要した。この間、原料スラリーの比粘度は最大６．０１×１０−４ｍ２／ｓ、最小は５．８１×１０−４ｍ２／ｓであり、乾燥開始時に対してそれぞれ＋１．２％、−１．３％であった。なお、乾燥期間中（１０時間）に原料スラリーの温度は８０℃±１℃で保持されていた。得られた乾燥粉体をよく混合し、レーザー式粒度分布測定装置で粒径を測定したところ、５０％における平均粒径（メジアン径）は３５μｍであった。 Next, this concentrated slurry (raw material slurry) was dried in a spray drier while being held in a stirring tank set in a range of 80 ± 1.0 ° C. The drying was performed under conditions of inlet hot air temperature: 300 ° C., outlet temperature: 110-120 ° C., rotary atomizer rotation speed: 18,000 rpm, and drying took 10 hours. During this period, the specific viscosity of the raw slurry is a maximum of 6.01 × 10 −4 m 2 / s and a minimum of 5.81 × 10 −4 m 2 / s, and + 1.2% and −1, respectively, at the start of drying. 3%. During the drying period (10 hours), the temperature of the raw material slurry was maintained at 80 ° C. ± 1 ° C. When the obtained dry powder was mixed well and the particle size was measured with a laser type particle size distribution analyzer, the average particle size (median diameter) at 50% was 35 μm.
このようにして得られた乾燥粉体１００部に対してヒドロキシプロピルセルロース３部およびエチルアルコール３０部を添加した後、双腕式ニーダーで混練を行った。得られた粘土状物質を押出成形機により、外形５ｍｍ、長さ５ｍｍの円柱状に成形した。得られた成形品を空気流通下、３７０℃にて１２時間焼成して、Ｐ１．１Ｍｏ１２Ｖ０．６Ｃｕ０．１Ｆｅ０．０５Ｃｅ０．１Ｃｓ１．０なる組成（酸素およびその原子比は省略、以下同じ）のヘテロポリ酸およびその塩の構造を含む複合酸化物触媒を得た。 After adding 3 parts of hydroxypropyl cellulose and 30 parts of ethyl alcohol to 100 parts of the dry powder thus obtained, the mixture was kneaded with a double-arm kneader. The obtained clay-like substance was molded into a cylindrical shape having an outer shape of 5 mm and a length of 5 mm by an extruder. The obtained molded product was fired at 370 ° C. for 12 hours under air flow, and a composition (oxygen) of P 1.1 Mo 12 V 0.6 Cu 0.1 Fe 0.05 Ce 0.1 Cs 1.0 In addition, a composite oxide catalyst including a heteropolyacid and a salt thereof was omitted.
この触媒を反応管に充填し、メタクロレイン５％、酸素１０％、水蒸気３０％、窒素５５％（容量％）の混合ガスを、大気圧下、反応温度２８５℃、接触時間３．６秒で通じてメタクロレインの気相接触酸化反応を行った。この結果を表２に示した。 The catalyst was charged into a reaction tube, and a mixed gas of 5% methacrolein, 10% oxygen, 30% water vapor, and 55% nitrogen (volume%) was applied at atmospheric pressure, reaction temperature of 285 ° C., and contact time of 3.6 seconds. A gas phase catalytic oxidation reaction of methacrolein was performed. The results are shown in Table 2.
［実施例３］
乾燥期間中の攪拌槽の原料投入口の蓋を閉めずに原料スラリーを保持した点以外は、実施例２と同様にして触媒を製造およびメタクロレインの気相接触酸化反応を行った。なお、乾燥期間中（１０時間）に原料スラリーの温度は８０℃から７４℃に低下した。乾燥期間中の原料スラリーの比粘度の最大値及び最小値、並びに気相接触酸化反応結果を表２に示した。
[Example 3]
A catalyst was prepared and a gas phase catalytic oxidation reaction of methacrolein was carried out in the same manner as in Example 2 except that the raw material slurry was retained without closing the raw material inlet opening lid of the stirring tank during the drying period. During the drying period (10 hours), the temperature of the raw slurry decreased from 80 ° C. to 74 ° C. Table 2 shows the maximum value and the minimum value of the specific viscosity of the raw material slurry during the drying period, and the results of the gas phase catalytic oxidation reaction.
［比較例２］
乾燥期間中の攪拌槽の原料投入口の蓋を閉めず、かつ撹拌槽Ａの温度のコントロールをせずに原料スラリーを保持した点以外は、実施例２と同様にして触媒を製造およびメタクロレインの気相接触酸化反応を行った。なお、乾燥期間中（１０時間）に原料スラリーの温度は８０℃から５５℃に低下した。乾燥期間中の原料スラリーの比粘度の最大値及び最小値、並びに気相接触酸化反応結果を表２に示した。
[Comparative Example 2]
The catalyst was produced and methacrolein in the same manner as in Example 2 except that the raw material slurry was held without closing the raw material inlet of the stirring tank during the drying period and without controlling the temperature of the stirring tank A. The gas phase catalytic oxidation reaction of was carried out. During the drying period (10 hours), the temperature of the raw material slurry decreased from 80 ° C. to 55 ° C. Table 2 shows the maximum value and the minimum value of the specific viscosity of the raw material slurry during the drying period, and the results of the gas phase catalytic oxidation reaction.
［比較例３］
乾燥期間中の攪拌槽の原料投入口の蓋を閉めず、かつ撹拌槽の温度のコントロールをせずに原料スラリーを保持し、かつ乾燥機への原料スラリー供給を２時間経過後に一旦止め、２時間放置後、乾燥を再開する操作を繰り返した点以外は、実施例２と同様にして触媒を製造およびメタクロレインの気相接触酸化反応を行った。乾燥期間は１８時間を要し、原料スラリーの温度は８０℃から３５℃に低下した。乾燥期間中の原料スラリーの比粘度の最大値及び最小値、並びに気相接触酸化反応結果を表２に示した。
[Comparative Example 3]
The raw material slurry is held without closing the raw material inlet port of the stirring tank during the drying period, and the temperature of the stirring tank is not controlled, and the supply of the raw material slurry to the dryer is temporarily stopped after 2 hours. The catalyst was produced and the gas phase catalytic oxidation reaction of methacrolein was carried out in the same manner as in Example 2 except that the operation of restarting drying was repeated after standing for a period of time. The drying period required 18 hours, and the temperature of the raw material slurry decreased from 80 ° C to 35 ° C. Table 2 shows the maximum value and the minimum value of the specific viscosity of the raw material slurry during the drying period, and the results of the gas phase catalytic oxidation reaction.
［実施例４］
パドル１段翼付の原料混合槽（加熱、冷却用ジャケット付）に純水２００部を投入し９０ｒｐｍで攪拌を開始した（以下、濃縮終了まで攪拌を継続した）。そこへパラモリブデン酸アンモニウム１００部を溶解し、さらにメタバナジン酸アンモニウム３．４部、８５質量％リン酸水溶液６．６部を純水３０部に溶解した溶液を加え、１０分間攪拌を続けた。ここに、三酸化アンチモン２．１部、硝酸銅１．１部を純水３０部に溶解した溶液および６０％砒酸水溶液２．２部を純水１０部に溶解した溶液を順次加え、これを攪拌しながら９０℃まで加熱し、液温を９０℃に保ちつつ５時間過熱攪拌した後に、硝酸セシウム９．２部を純水１００部に溶解した溶液をこれに加え１５分間攪拌してスラリーを得た。このスラリーを１０１℃まで加熱し、攪拌しながら濃縮を開始した。濃縮開始時のスラリーの粘度は０．０２ｋｇ／（ｍ・ｓ）、比重は１．２２×１０３ｋｇ／ｍ３で、比粘度は０．１６×１０−４ｍ２／ｓであった。濃縮中は温度を１０１℃に保ち、スラリーの粘度が０．６５ｋｇ／（ｍ・ｓ）、比重が１．６１×１０３ｋｇ／ｍ３で、比粘度が４．０４×１０−４ｍ２／ｓの時点で加熱を停止して濃縮を終了した。
[Example 4]
200 parts of pure water was put into a raw material mixing tank (with a heating and cooling jacket) with a paddle one-stage blade, and stirring was started at 90 rpm (hereinafter, stirring was continued until concentration was completed). Thereto, 100 parts of ammonium paramolybdate was dissolved, and a solution prepared by dissolving 3.4 parts of ammonium metavanadate and 6.6 parts of 85 mass% phosphoric acid aqueous solution in 30 parts of pure water was added, and stirring was continued for 10 minutes. A solution prepared by dissolving 2.1 parts of antimony trioxide, 1.1 parts of copper nitrate in 30 parts of pure water and a solution of 2.2 parts of a 60% aqueous arsenic acid solution in 10 parts of pure water were sequentially added thereto. The mixture was heated to 90 ° C. with stirring, and heated and stirred for 5 hours while maintaining the liquid temperature at 90 ° C. Then, a solution prepared by dissolving 9.2 parts of cesium nitrate in 100 parts of pure water was added thereto and stirred for 15 minutes. Obtained. The slurry was heated to 101 ° C. and concentration was started while stirring. The viscosity of the slurry at the start of concentration was 0.02 kg / (m · s), the specific gravity was 1.22 × 10 3 kg / m 3 , and the specific viscosity was 0.16 × 10 −4 m 2 / s. During concentration, the temperature is maintained at 101 ° C., the viscosity of the slurry is 0.65 kg / (m · s), the specific gravity is 1.61 × 10 3 kg / m 3 , and the specific viscosity is 4.04 × 10 −4 m 2. At the time of / s, the heating was stopped and the concentration was completed.
濃縮終了後、直ちに原料混合槽から攪拌槽Ａ（電気ヒーター付）に濃縮後スラリー（原料スラリー）を移液し、攪拌槽Ａの原料投入口に蓋をして、原料スラリーを攪拌しながら８５℃に調整した。 Immediately after the concentration, the concentrated slurry (raw material slurry) is transferred from the raw material mixing tank to the stirring tank A (with electric heater), and the raw material charging port of the stirring tank A is covered, and the raw material slurry is stirred. Adjusted to ° C.
次にこの原料スラリーを８５±１℃の範囲に設定した撹拌槽Ａ中で保持しながら、ドラムドライヤーで乾燥した。原料スラリーの供給はロータリーポンプで連続でおこなった。乾燥には８時間を要した。この間、原料スラリーの比粘度は最大４．１４×１０−４ｍ２／ｓ、最小は３．９７×１０−４ｍ２／ｓであり、乾燥開始時に対してそれぞれ＋２．４％、−１．８％であった。なお、乾燥期間中（８時間）に原料スラリーの温度は８５℃±１℃で保持されていた。得られた乾燥粉体をよく混合し、レーザー式粒度分布測定装置で粒径を測定したところ、５０％における平均粒径（メジアン径）は４３μｍであった。 Next, this raw material slurry was dried with a drum dryer while being held in a stirring tank A set in a range of 85 ± 1 ° C. The raw material slurry was continuously supplied with a rotary pump. The drying took 8 hours. During this period, the specific viscosity of the raw slurry is 4.14 × 10 −4 m 2 / s at the maximum and 3.97 × 10 −4 m 2 / s at the minimum, and + 2.4% and −1, respectively, relative to the start of drying. 8%. During the drying period (8 hours), the temperature of the raw slurry was maintained at 85 ° C. ± 1 ° C. The obtained dry powder was mixed well, and the particle size was measured with a laser type particle size distribution analyzer. The average particle size (median diameter) at 50% was 43 μm.
このようにして得られた乾燥粉体１００部に対してグラファイト２部を添加した後、打錠成形機により、外形５ｍｍ、内径２ｍｍ、長さ５ｍｍのリング状に成型した。得られた成形品は空気流通下、３８０℃にて６時間焼成して、Ｐ１．２Ｍｏ１２Ｖ０．６Ｃｕ０．１Ｓｂ０．３Ａｓ０．２Ｃｓ１なる組成のヘテロポリ酸およびその塩の構造を含む複合酸化物触媒を得た。 After adding 2 parts of graphite to 100 parts of the dry powder thus obtained, it was molded into a ring shape having an outer diameter of 5 mm, an inner diameter of 2 mm, and a length of 5 mm by a tableting machine. The obtained molded product was fired at 380 ° C. for 6 hours under air flow, and a heteropolyacid having a composition of P 1.2 Mo 12 V 0.6 Cu 0.1 Sb 0.3 As 0.2 Cs 1 and A composite oxide catalyst containing the salt structure was obtained.
この触媒を反応管に充填し、反応温度を２９５℃にした点以外は、実施例２と同様にしてメタクロレインの気相接触酸化反応を行った。この結果を表２に示した。 A gas phase catalytic oxidation reaction of methacrolein was carried out in the same manner as in Example 2 except that this catalyst was filled in a reaction tube and the reaction temperature was 295 ° C. The results are shown in Table 2.
［比較例４］
実施例４において、乾燥期間中の攪拌槽Ａの原料投入口の蓋を閉めず、かつ温度のコントロールをせずに原料スラリーを保持した点以外は、実施例４と同様にして触媒を製造およびメタクロレインの気相接触酸化反応を行った。なお、乾燥期間中（８時間）に原料スラリーの温度は８５℃から６０℃に低下した。乾燥期間中の原料スラリーの比粘度の最大値及び最小値、並びに気相接触酸化反応結果を表２に示した。
In Example 4, the catalyst was produced in the same manner as in Example 4 except that the raw material slurry was retained without closing the raw material inlet port of the stirring tank A during the drying period and without controlling the temperature. A gas phase catalytic oxidation reaction of methacrolein was performed. During the drying period (8 hours), the temperature of the raw slurry decreased from 85 ° C. to 60 ° C. Table 2 shows the maximum value and the minimum value of the specific viscosity of the raw material slurry during the drying period, and the results of the gas phase catalytic oxidation reaction.
Claims (2)
０．９５Ｘ０≦Ｘ≦１．０５Ｘ０ （Ｉ）
Ｘ：原料スラリーの比粘度（ｍ２／ｓ）
Ｘ０：乾燥開始時の原料スラリーの比粘度（ｍ２／ｓ）
Ｍｏ ａ１ Ｂｉ ｂ１ Ｆｅ ｃ１ Ｍ ｄ１ Ｘ ｅ１ Ｙ ｆ１ Ｚ ｇ１ Ｓｉ ｈ１ Ｏ ｉ１ （１）
式（１）中、Ｍｏ、Ｂｉ、Ｆｅ、ＳｉおよびＯはそれぞれモリブデン、ビスマス、鉄、ケイ素および酸素を示し、Ｍはコバルトおよびニッケルからなる群より選ばれた少なくとも１種の元素を示し、Ｘはクロム、鉛、マンガン、カルシウム、マグネシウム、ニオブ、銀、バリウム、スズ、タンタルおよび亜鉛からなる群より選ばれた少なくとも１種の元素を示し、Ｙはリン、ホウ素、硫黄、セレン、テルル、セリウム、タングステン、アンチモンおよびチタンからなる群より選ばれた少なくとも１種の元素を示し、Ｚはリチウム、ナトリウム、カリウム、ルビジウム、セシウムおよびタリウムからなる群より選ばれた少なくとも１種の元素を示す。ａ１、ｂ１、ｃ１、ｄ１、ｅ１、ｆ１、ｇ１、ｈ１およびｉ１は各元素の原子比を表し、ａ１＝１２のとき０．０１≦ｂ１≦３、０．０１≦ｃ１≦５、１≦ｄ１≦１２、０≦ｅ１≦８、０≦ｆ１≦５、０．００１≦ｇ１≦２、０≦ｈ１≦２０であり、ｉ１は前記各成分の原子価を満足するのに必要な酸素の原子比である。 A method for producing a catalyst for synthesizing methacrolein and / or methacrylic acid containing at least molybdenum, comprising a step of supplying a raw material slurry containing at least molybdenum to a drying device and drying the raw material slurry in the drying device to obtain a dry powder. The raw material slurry having a value obtained by dividing the viscosity (unit: kg / (m · s)) of the raw material slurry by the specific gravity (unit: kg / m 3 ) of the raw material slurry from the start to the end of the drying Specific viscosity (m 2 / s) satisfies the following formula (I) , and the specific viscosity X 0 of the raw material slurry at the start of drying is 2.5 × 10 −4 to 7.0 × 10 −4. A method for producing methacrolein and / or a catalyst for synthesizing methacrylic acid represented by the following formula (1), wherein m 2 / s.
0.95X 0 ≦ X ≦ 1.05X 0 (I)
X: Specific viscosity of raw material slurry (m 2 / s)
X 0 : Specific viscosity of raw material slurry at the start of drying (m 2 / s)
Mo a1 Bi b1 Fe c1 M d1 X e1 Y f1 Z g1 Si h1 O i1 (1)
In the formula (1), Mo, Bi, Fe, Si and O each represent molybdenum, bismuth, iron, silicon and oxygen, M represents at least one element selected from the group consisting of cobalt and nickel, and X Represents at least one element selected from the group consisting of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc, and Y represents phosphorus, boron, sulfur, selenium, tellurium, cerium , Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and thallium. a1, b1, c1, d1, e1, f1, g1, h1, and i1 represent the atomic ratio of each element. When a1 = 12, 0.01 ≦ b1 ≦ 3, 0.01 ≦ c1 ≦ 5, 1 ≦ d1 ≦ 12, 0 ≦ e1 ≦ 8, 0 ≦ f1 ≦ 5, 0.001 ≦ g1 ≦ 2, 0 ≦ h1 ≦ 20, i1 is the atomic ratio of oxygen necessary to satisfy the valence of each component It is.
０．９５Ｘ０≦Ｘ≦１．０５Ｘ０ （Ｉ）
Ｘ：原料スラリーの比粘度（ｍ２／ｓ）
Ｘ０：乾燥開始時の原料スラリーの比粘度（ｍ２／ｓ）
Ｍｏ ａ２ Ｐ ｂ２ Ｃｕ ｃ２ Ｖ ｄ２ Ｘ ｅ２ Ｙ ｆ２ Ｏ ｇ２ （２）
式（２）中、Ｍｏ、Ｐ、Ｃｕ、ＶおよびＯはそれぞれモリブデン、リン、銅、バナジウムおよび酸素を表し、Ｘはカリウム、ルビジウム、セシウムおよびタリウムからなる群より選ばれた少なくとも１種の元素を表し、Ｙは鉄、コバルト、ニッケル、亜鉛、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、クロム、タングステン、マンガン、銀、ホウ素、ケイ素、アルミニウム、ガリウム、ゲルマニウム、スズ、鉛、ヒ素、アンチモン、ビスマス、ニオブ、タンタル、ジルコニウム、インジウム、イオウ、セレン、テルル、ランタンおよびセリウムからなる群より選ばれた少なくとも１種の元素を表す。ａ２、ｂ２、ｃ２、ｄ２、ｅ２、ｆ２およびｇ２は各元素の原子比を表し、ａ２＝１２のとき、０．１≦ｂ２≦３、０．０１≦ｃ２≦３、０．０１≦ｄ２≦３、０．０１≦ｅ２≦３、０≦ｆ２≦３であり、ｇ２は前記各成分の原子比を満足するのに必要な酸素の原子比である。 In the method for producing a catalyst for synthesizing methacrylic acid containing at least molybdenum, the raw material slurry containing at least molybdenum is supplied to a drying device, and the raw material slurry is dried in the drying device to obtain a dry powder. From the start to the end, the viscosity of the raw material slurry (m: s) divided by the specific gravity of the raw material slurry (unit: kg / m 3 ) is the specific viscosity of the raw material slurry (m 2 / s) satisfies the following formula (I) , and the specific viscosity X 0 of the raw material slurry at the start of drying is 2.5 × 10 −4 to 7.0 × 10 −4 m 2 / s. A method for producing a methacrylic acid synthesis catalyst represented by the following formula (2):
0.95X 0 ≦ X ≦ 1.05X 0 (I)
X: Specific viscosity of raw material slurry (m 2 / s)
X 0 : Specific viscosity of raw material slurry at the start of drying (m 2 / s)
Mo a2 P b2 Cu c2 V d2 X e2 Y f2 O g2 (2)
In formula (2), Mo, P, Cu, V and O each represent molybdenum, phosphorus, copper, vanadium and oxygen, and X is at least one element selected from the group consisting of potassium, rubidium, cesium and thallium Y represents iron, cobalt, nickel, zinc, magnesium, calcium, strontium, barium, titanium, chromium, tungsten, manganese, silver, boron, silicon, aluminum, gallium, germanium, tin, lead, arsenic, antimony, bismuth And at least one element selected from the group consisting of niobium, tantalum, zirconium, indium, sulfur, selenium, tellurium, lanthanum and cerium. a2, b2, c2, d2, e2, f2, and g2 represent atomic ratios of the respective elements. When a2 = 12, 0.1 ≦ b2 ≦ 3, 0.01 ≦ c2 ≦ 3, 0.01 ≦ d2 ≦ 3, 0.01 ≦ e2 ≦ 3, 0 ≦ f2 ≦ 3, and g2 is an atomic ratio of oxygen necessary to satisfy the atomic ratio of each component.
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| JP2009090200A (en) * | 2007-10-05 | 2009-04-30 | Mitsubishi Rayon Co Ltd | Method for manufacturing catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid |
| JP5626583B2 (en) * | 2010-01-28 | 2014-11-19 | 三菱レイヨン株式会社 | Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid |
| US9643171B2 (en) | 2010-02-25 | 2017-05-09 | Saudi Basic Industries Corporation | Method of making heteropoly acid compound catalysts |
| JP5462300B2 (en) * | 2012-02-23 | 2014-04-02 | 三菱レイヨン株式会社 | Process for producing catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid |
| JP7418252B2 (en) | 2019-03-25 | 2024-01-19 | 日本化薬株式会社 | Catalyst precursor, catalyst using the same, and manufacturing method thereof |
| JP2020179312A (en) | 2019-04-23 | 2020-11-05 | 日本化薬株式会社 | Catalyst, and production method thereof |
| JP7306491B2 (en) * | 2020-01-08 | 2023-07-11 | 三菱ケミカル株式会社 | Method for producing catalyst for producing methacrylic acid, method for producing methacrylic acid, method for producing methacrylic acid ester, and apparatus for producing catalyst for producing methacrylic acid |
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| JP3391532B2 (en) * | 1993-12-27 | 2003-03-31 | 住友化学工業株式会社 | Method for producing catalyst for producing methacrylic acid |
| JP4947753B2 (en) * | 2001-06-21 | 2012-06-06 | 三菱レイヨン株式会社 | Catalyst for methacrylic acid synthesis and method for producing methacrylic acid |
| JP4280797B2 (en) * | 2001-11-21 | 2009-06-17 | 三菱化学株式会社 | Method for producing composite oxide catalyst |
| JP4242597B2 (en) * | 2002-02-28 | 2009-03-25 | 株式会社日本触媒 | Unsaturated aldehyde synthesis catalyst, production method thereof, and production method of unsaturated aldehyde using the catalyst |
| JP2005186064A (en) * | 2003-12-04 | 2005-07-14 | Mitsubishi Chemicals Corp | Production method for catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid |
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