JP6819699B2 - Methacrylic acid production catalyst, methacrylic acid production catalyst precursor, and their production methods, methacrylic acid production method, and methacrylic acid ester production method. - Google Patents
Methacrylic acid production catalyst, methacrylic acid production catalyst precursor, and their production methods, methacrylic acid production method, and methacrylic acid ester production method. Download PDFInfo
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- JP6819699B2 JP6819699B2 JP2018568053A JP2018568053A JP6819699B2 JP 6819699 B2 JP6819699 B2 JP 6819699B2 JP 2018568053 A JP2018568053 A JP 2018568053A JP 2018568053 A JP2018568053 A JP 2018568053A JP 6819699 B2 JP6819699 B2 JP 6819699B2
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- Prior art keywords
- methacrylic acid
- catalyst
- producing
- slurry
- catalyst precursor
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 129
- 239000003054 catalyst Substances 0.000 title claims description 99
- 239000012018 catalyst precursor Substances 0.000 title claims description 79
- 238000004519 manufacturing process Methods 0.000 title claims description 55
- 125000005397 methacrylic acid ester group Chemical group 0.000 title claims description 13
- 239000002002 slurry Substances 0.000 claims description 93
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000010955 niobium Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- 229910052750 molybdenum Inorganic materials 0.000 claims description 25
- 229910052758 niobium Inorganic materials 0.000 claims description 25
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 22
- 229910001882 dioxygen Inorganic materials 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 20
- 229910052720 vanadium Inorganic materials 0.000 claims description 20
- 239000012808 vapor phase Substances 0.000 claims description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 19
- 239000011733 molybdenum Substances 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052792 caesium Inorganic materials 0.000 claims description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052701 rubidium Inorganic materials 0.000 claims description 9
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 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 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 229910052732 germanium Inorganic materials 0.000 claims description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052714 tellurium Inorganic materials 0.000 claims description 8
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003868 ammonium compounds Chemical class 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 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 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000000243 solution Substances 0.000 description 28
- 238000010304 firing Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000011964 heteropoly acid Substances 0.000 description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000001099 ammonium carbonate Substances 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 5
- 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 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- ZFYIQPIHXRFFCZ-QMMMGPOBSA-N (2s)-2-(cyclohexylamino)butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NC1CCCCC1 ZFYIQPIHXRFFCZ-QMMMGPOBSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 description 4
- 239000011736 potassium bicarbonate Substances 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 229910052716 thallium Inorganic materials 0.000 description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 3
- AXIFGFAGYFPNFC-UHFFFAOYSA-I 2-hydroxy-2-oxoacetate;niobium(5+) Chemical compound [Nb+5].OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O AXIFGFAGYFPNFC-UHFFFAOYSA-I 0.000 description 2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000007696 Kjeldahl method Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007865 diluting Methods 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
- 238000002036 drum drying Methods 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
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- 230000008020 evaporation Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
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- 230000003068 static effect Effects 0.000 description 2
- SERHNBYDRHYCNM-UHFFFAOYSA-N tetraazanium oxalate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O SERHNBYDRHYCNM-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 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
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 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
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- CPWJKGIJFGMVPL-UHFFFAOYSA-K tricesium;phosphate Chemical compound [Cs+].[Cs+].[Cs+].[O-]P([O-])([O-])=O CPWJKGIJFGMVPL-UHFFFAOYSA-K 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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Description
本発明は、メタクリル酸製造用触媒、メタクリル酸製造用触媒前駆体、およびそれらの製造方法、メタクリル酸の製造方法、並びにメタクリル酸エステルの製造方法に関する。 The present invention relates to a catalyst for producing methacrylic acid, a catalyst precursor for producing methacrylic acid, a method for producing them, a method for producing methacrylic acid, and a method for producing a methacrylic acid ester.
メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する際に用いられるメタクリル酸製造用触媒（以下、単に「触媒」とも記す）としては、例えばモリブデン元素およびリン元素を含むヘテロポリ酸系触媒が挙げられる。該ヘテロポリ酸系触媒としては、カウンターカチオンがプロトンであるプロトン型ヘテロポリ酸と、そのプロトンの一部をプロトン以外のカチオンで置換したヘテロポリ酸塩が挙げられる（以下、これらを単に「ヘテロポリ酸」および「ヘテロポリ酸塩」とも言う。また両者を併せて「ヘテロポリ酸（塩）」とも言う）。 As a catalyst for producing methacrylic acid (hereinafter, also simply referred to as “catalyst”) used when methacrolein is vapor-phase contact oxidized with molecular oxygen to produce methacrylic acid, for example, a heteropolyacid containing an element of molybdenum and an element of phosphorus is used. A system catalyst can be mentioned. Examples of the heteropolyacid-based catalyst include a proton-type heteropolyacid in which the counter cation is a proton and a heteropolyate in which a part of the proton is replaced with a cation other than the proton (hereinafter, these are simply "heteropoly acid" and the like. It is also called "heteropolyate", and both are also collectively called "heteropoly acid (salt)").
ヘテロポリ酸（塩）の構造に関して、非特許文献１には、ヘテロポリ酸（塩）はその中心に異種元素（以下中心元素という）を有し、また酸素を共有して縮合酸基が縮合して形成される単核または複核の錯イオンを有していること、縮合形態は数種類知られていること、リン、ヒ素、ケイ素、ゲルマニウム、チタン等が中心元素になり得ることが記載されている。 Regarding the structure of the heteropolyacid (salt), Non-Patent Document 1 states that the heteropolyacid (salt) has a different element (hereinafter referred to as a central element) at the center thereof, and the condensed acid group is condensed by sharing oxygen. It is described that it has mononuclear or dinuclear complex ions to be formed, that several types of condensation forms are known, and that phosphorus, arsenic, silicon, germanium, titanium, etc. can be central elements.
また、非特許文献２には、ヘテロポリ酸（塩）の構造としては、ケギン、欠損型ケギン、ドーソン、欠損型ドーソンなど種々の構造が存在し、調製過程のｐＨを制御することでこれらの構造を作り分けることができること、ケギン型ヘテロポリ酸（塩）は調製過程のｐＨを６以下とすることで調製できることが記載されている。 Further, in Non-Patent Document 2, various structures such as kegin, defective kegin, doson, and defective doson exist as the structure of the heteropolyacid (salt), and these structures are controlled by controlling the pH in the preparation process. It is described that the kegin-type heteropolyacid (salt) can be prepared by setting the pH of the preparation process to 6 or less.
ヘテロポリ酸系触媒を用いてメタクロレインからメタクリル酸を製造する際に、メタクリル酸の選択率が高い触媒として、特許文献１には下記式（Ｉ）で表される触媒が開示されている。 Patent Document 1 discloses a catalyst represented by the following formula (I) as a catalyst having a high selectivity of methacrylic acid when methacrolein is produced from methacrolein using a heteropolyacid-based catalyst.
ＭｏａＰｂＶｃＣｕｄＳｂｅＮｂｆＸｇＹｈＺｉＯｊ （Ｉ）
（式（Ｉ）中、Ｍｏ、Ｐ、Ｖ、Ｃｕ、Ｓｂ、Ｎｂ及びＯはそれぞれモリブデン、リン、バナジウム、銅、アンチモン、ニオブ及び酸素を表し、Ｘは鉄、コバルト、ニッケル及び亜鉛からなる群より選ばれた少なくとも１種の元素、Ｙはマグネシウム、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、スズ、鉛、ヒ素、ビスマス、インジウム、イオウ、セレン、テルル、ランタン及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、Ｚはナトリウム、カリウム、ルビジウム、セシウム及びタリウムからなる群より選ばれた少なくとも１種の元素を表す。ただし、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ及びｉは各元素の原子比を表し、ａ＝１２のとき、０．１≦ｂ≦３、０．０１≦ｃ≦３、０．０１≦ｄ≦２、０．０１≦ｅ≦３、０．０１≦ｆ≦３、０．０１≦ｇ≦３、０≦ｈ≦３、０．０１≦ｉ≦３であり、ｊ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。） Mo a P b V c Cu d Sb e Nb f X g Y h Z i O j (I)
(In formula (I), Mo, P, V, Cu, Sb, Nb and O represent molybdenum, phosphorus, vanadium, copper, antimony, niobium and oxygen, respectively, and X is a group consisting of iron, cobalt, nickel and zinc. At least one element selected from, Y is magnesium, calcium, strontium, barium, titanium, chromium, tungsten, manganese, silver, boron, silicon, tin, lead, arsenic, bismuth, indium, sulfur, selenium, tellurium, At least one element selected from the group consisting of lanthanum and cerium, Z represents at least one element selected from the group consisting of sodium, potassium, rubidium, cesium and tarium, however, a, b, c,. d, e, f, g, h and i represent the atomic ratio of each element, and when a = 12, 0.1 ≦ b ≦ 3, 0.01 ≦ c ≦ 3, 0.01 ≦ d ≦ 2, 0.01 ≦ e ≦ 3, 0.01 ≦ f ≦ 3, 0.01 ≦ g ≦ 3, 0 ≦ h ≦ 3, 0.01 ≦ i ≦ 3, and j satisfies the atomic ratio of each component. The atomic ratio of oxygen required to do this.)
しかしながら、前記触媒を用いてメタクリル酸の製造を行ってもメタクリル酸の選択率の点でまだ不十分であり、工業的見地から更なる改良が望まれている。 However, even if methacrylic acid is produced using the catalyst, the selectivity of methacrylic acid is still insufficient, and further improvement is desired from an industrial point of view.
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選択率で製造できる触媒、触媒前駆体、およびそれらの製造方法、該触媒を用いたメタクリル酸の製造方法、並びにメタクリル酸エステルの製造方法を提供することを目的とする。 The present invention relates to a catalyst capable of producing methacrylic acid with high selectivity by vapor-phase catalytic oxidation of methacrolein, a catalyst precursor, and a method for producing them, a method for producing methacrylic acid using the catalyst, and a methacrylic acid ester. It is an object of the present invention to provide a manufacturing method.
本発明は、以下の［１］〜［１１］である。 The present invention is the following [1] to [11].
［１］メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する際に用いられる、下記式（１）で表される組成を有するメタクリル酸製造用触媒。 [1] A catalyst for producing methacrylic acid having a composition represented by the following formula (1), which is used when methacrolein is vapor-phase catalytically oxidized with molecular oxygen to produce methacrylic acid.
ＰａＭｏｂＶｃＮｂｄＣｕｅＡｆＥｇＧｈ（ＮＨ４）ｉＯｊ （１）
（式（１）中、Ｐ、Ｍｏ、Ｖ、Ｎｂ、Ｃｕ、ＮＨ４およびＯは、それぞれ、リン、モリブデン、バナジウム、ニオブ、銅、アンモニウム根および酸素を表す。Ａはケイ素、ゲルマニウム、ヒ素およびアンチモンからなる群から選択される少なくとも１種の元素を表す。Ｅはビスマス、ジルコニウム、テルル、銀、セレン、タングステン、ホウ素、鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、インジウム、硫黄、パラジウム、ガリウム、セリウムおよびランタンからなる群から選択される少なくとも１種の元素を示す。Ｇ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から選択される少なくとも１種の元素を表す。ａ〜ｊは、各成分のモル比率を表し、ｂ＝１２の時、０．５≦ａ＋ｆ≦２．１、０．０１≦ｃ＋ｄ≦３、０．５≦ａ、０≦ｃ、０．０１≦ｄ≦３、０．００５≦ｅ≦３、０≦ｆ、０≦ｇ≦３、０．０１≦ｈ≦３、０≦ｉ≦５を満たし、ｊは前記各成分の価数を満足するのに必要な酸素のモル比率である。）。P a Mo b V c Nb d Cu e A f E g G h (NH 4 ) i O j (1)
(In formula (1), P, Mo, V, Nb, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, niobium, copper, ammonium root and oxygen, respectively. A represents silicon, germanium, arsenic and Represents at least one element selected from the group consisting of antimony. E represents bismuth, zirconium, tellurium, silver, selenium, tungsten, boron, iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, Indicates at least one element selected from the group consisting of manganese, barium, titanium, tin, lead, indium, sulfur, palladium, gallium, cerium and lanthanum. G is from lithium, sodium, potassium, rubidium, cesium and tarium. Represents at least one element selected from the group. A to j represent the molar ratio of each component, and when b = 12, 0.5 ≦ a + f ≦ 2.1 and 0.01 ≦ c + d ≦ 3. , 0.5 ≦ a, 0 ≦ c, 0.01 ≦ d ≦ 3, 0.005 ≦ e ≦ 3, 0 ≦ f, 0 ≦ g ≦ 3, 0.01 ≦ h ≦ 3, 0 ≦ i ≦ 5 Is satisfied, and j is the molar ratio of oxygen required to satisfy the valence of each component.).
［２］メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する際に用いられる触媒の、前駆体であって、ケギン型構造を有し、下記式（２）で表される組成を有するメタクリル酸製造用触媒前駆体。 [2] A precursor of a catalyst used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen, which has a kegin-type structure and is represented by the following formula (2). A catalyst precursor for producing methacrylic acid having a composition.
ＰａＭｏｂＶｃＮｂｄＣｕｅＡｆＥｇＧｈ（ＮＨ４）ｉＯｊ （２）
（式（２）中、Ｐ、Ｍｏ、Ｖ、Ｎｂ、Ｃｕ、ＮＨ４およびＯは、それぞれ、リン、モリブデン、バナジウム、ニオブ、銅、アンモニウム根および酸素を表す。Ａはケイ素、ゲルマニウム、ヒ素およびアンチモンからなる群から選択される少なくとも１種の元素を表す。Ｅはビスマス、ジルコニウム、テルル、銀、セレン、タングステン、ホウ素、鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、インジウム、硫黄、パラジウム、ガリウム、セリウムおよびランタンからなる群から選択される少なくとも１種の元素を示す。Ｇ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から選択される少なくとも１種の元素を表す。ａ〜ｊは、各成分のモル比率を表し、ｂ＝１２の時、０．５≦ａ＋ｆ≦２．４、０．０１≦ｃ＋ｄ≦３、０．５≦ａ、０≦ｃ、０．０１≦ｄ≦３、０．００５≦ｅ≦３、０≦ｆ、０≦ｇ≦３、０．０１≦ｈ≦３、０．１≦ｉ≦２０を満たし、ｊは前記各成分の価数を満足するのに必要な酸素のモル比率である。）。P a Mo b V c Nb d Cu e A f E g G h (NH 4 ) i O j (2)
(In formula (2), P, Mo, V, Nb, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, niobium, copper, ammonium root and oxygen, respectively. A represents silicon, germanium, arsenic and Represents at least one element selected from the group consisting of antimony. E represents bismuth, zirconium, tellurium, silver, selenium, tungsten, boron, iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, Indicates at least one element selected from the group consisting of manganese, barium, titanium, tin, lead, indium, sulfur, palladium, gallium, cerium and lanthanum. G is from lithium, sodium, potassium, rubidium, cesium and tarium. Represents at least one element selected from the group. A to j represent the molar ratio of each component, and when b = 12, 0.5 ≦ a + f ≦ 2.4 and 0.01 ≦ c + d ≦ 3. , 0.5 ≦ a, 0 ≦ c, 0.01 ≦ d ≦ 3, 0.005 ≦ e ≦ 3, 0 ≦ f, 0 ≦ g ≦ 3, 0.01 ≦ h ≦ 3, 0.1 ≦ i ≤20 is satisfied, and j is the molar ratio of oxygen required to satisfy the valence of each component.)
［３］前記式（１）において、０．３５≦ｄ／（ｃ＋ｄ）≦１を満たす［１］に記載のメタクリル酸製造用触媒。 [3] The catalyst for producing methacrylic acid according to [1], which satisfies 0.35 ≦ d / (c + d) ≦ 1 in the above formula (1).
［４］前記式（２）において、０．３５≦ｄ／（ｃ＋ｄ）≦１を満たす［２］に記載のメタクリル酸製造用触媒前駆体。 [4] The catalyst precursor for methacrylic acid production according to [2], which satisfies 0.35 ≦ d / (c + d) ≦ 1 in the above formula (2).
［５］［２］または［４］に記載のメタクリル酸製造用触媒前駆体の製造方法であって、
（ｉ）少なくともモリブデンの原料を含むスラリー（Ｉ）または溶液（Ｉ）を調製する工程と、
（ｉｉ）前記スラリー（Ｉ）または前記溶液（Ｉ）にアンモニウム化合物を添加して、アンモニウム塩を含むスラリー（ＩＩ）を調製する工程と、
（ｉｉｉ）前記スラリー（ＩＩ）を乾燥し、前記ケギン型構造を有するメタクリル酸製造用触媒前駆体を得る工程と、
を含み、
前記工程（ｉ）および（ｉｉ）において、前記スラリー（Ｉ）、前記溶液（Ｉ）、および前記スラリー（ＩＩ）のｐＨを０．１〜６．５の範囲内に維持するメタクリル酸製造用触媒前駆体の製造方法。[5] The method for producing a catalyst precursor for producing methacrylic acid according to [2] or [4].
(I) A step of preparing a slurry (I) or a solution (I) containing at least a molybdenum raw material, and
(Ii) A step of adding an ammonium compound to the slurry (I) or the solution (I) to prepare a slurry (II) containing an ammonium salt.
(Iii) A step of drying the slurry (II) to obtain a catalyst precursor for producing methacrylic acid having the kegin-type structure.
Including
A catalyst for producing methacrylic acid that maintains the pH of the slurry (I), the solution (I), and the slurry (II) in the range of 0.1 to 6.5 in the steps (i) and (ii). Method for producing a precursor.
［６］［５］に記載の方法により製造したメタクリル酸製造用触媒前駆体を焼成する工程を含むメタクリル酸製造用触媒の製造方法。 [6] A method for producing a catalyst for producing methacrylic acid, which comprises a step of calcining a catalyst precursor for producing methacrylic acid produced by the method according to [5].
［７］［１］または［３］に記載のメタクリル酸製造用触媒を用いて、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造するメタクリル酸の製造方法。 [7] A method for producing methacrylic acid, which produces methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen using the catalyst for producing methacrylic acid according to [1] or [3].
［８］［６］に記載の方法によりメタクリル酸製造用触媒を製造し、該メタクリル酸製造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してメタクリル酸を製造するメタクリル酸の製造方法。 [8] A catalyst for producing methacrylic acid is produced by the method according to [6], and methacrolein is vapor-phase contact-oxidized with molecular oxygen using the catalyst for producing methacrylic acid to produce methacrylic acid. Production method.
［９］［６］に記載の方法により製造されたメタクリル酸製造用触媒を用いて、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造するメタクリル酸の製造方法。 [9] A method for producing methacrylic acid, which produces methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen using the methacrylic acid production catalyst produced by the method according to [6].
［１０］［７］から［９］のいずれかに記載の方法により製造されたメタクリル酸をエステル化するメタクリル酸エステルの製造方法。 [10] A method for producing a methacrylic acid ester that esterifies methacrylic acid produced by the method according to any one of [7] to [9].
［１１］［７］から［９］のいずれかに記載の方法によりメタクリル酸を製造し、該メタクリル酸をエステル化するメタクリル酸エステルの製造方法。 [11] A method for producing a methacrylic acid ester, which comprises producing methacrylic acid by the method according to any one of [7] to [9] and esterifying the methacrylic acid.
本発明によれば、メタクロレインを気相接触酸化してメタクリル酸を高選択率で製造できる触媒、触媒前駆体、およびそれらの製造方法、該触媒を用いたメタクリル酸の製造方法、並びにメタクリル酸エステルの製造方法を提供することができる。 According to the present invention, a catalyst capable of producing methacrylic acid with high selectivity by vapor-phase catalytic oxidation of methacrolein, a catalyst precursor, and a method for producing them, a method for producing methacrylic acid using the catalyst, and methacrylic acid. A method for producing an ester can be provided.
［メタクリル酸製造用触媒］
本発明に係るメタクリル酸製造用触媒は、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する際に用いられ、下記式（１）で表される組成を有する。[Catalyst for methacrylic acid production]
The catalyst for producing methacrylic acid according to the present invention is used when methacrolein is vapor-phase catalytically oxidized with molecular oxygen to produce methacrylic acid, and has a composition represented by the following formula (1).
ＰａＭｏｂＶｃＮｂｄＣｕｅＡｆＥｇＧｈ（ＮＨ４）ｉＯｊ （１）
式（１）中、Ｐ、Ｍｏ、Ｖ、Ｎｂ、Ｃｕ、ＮＨ４およびＯは、それぞれ、リン、モリブデン、バナジウム、ニオブ、銅、アンモニウム根および酸素を表す。Ａはケイ素、ゲルマニウム、ヒ素およびアンチモンからなる群から選択される少なくとも１種の元素を表す。Ｅはビスマス、ジルコニウム、テルル、銀、セレン、タングステン、ホウ素、鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、インジウム、硫黄、パラジウム、ガリウム、セリウムおよびランタンからなる群から選択される少なくとも１種の元素を示す。Ｇ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から選択される少なくとも１種の元素を表す。ａ〜ｊは、各成分のモル比率を表し、ｂ＝１２の時、０．５≦ａ＋ｆ≦２．１、０．０１≦ｃ＋ｄ≦３、０．５≦ａ、０≦ｃ、０．０１≦ｄ≦３、０．００５≦ｅ≦３、０≦ｆ、０≦ｇ≦３、０．０１≦ｈ≦３、０≦ｉ≦５を満たし、ｊは前記各成分の価数を満足するのに必要な酸素のモル比率である。P a Mo b V c Nb d Cu e A f E g G h (NH 4 ) i O j (1)
In formula (1), P, Mo, V, Nb, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, niobium, copper, ammonium root and oxygen, respectively. A represents at least one element selected from the group consisting of silicon, germanium, arsenic and antimony. E is bismuth, zirconium, tellurium, silver, selenium, tungsten, boron, iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, lead, indium, sulfur, palladium, Indicates at least one element selected from the group consisting of gallium, cerium and lanthanum. G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. a to j represent the molar ratio of each component, and when b = 12, 0.5 ≦ a + f ≦ 2.1, 0.01 ≦ c + d ≦ 3, 0.5 ≦ a, 0 ≦ c, 0.01 ≦ d ≦ 3, 0.005 ≦ e ≦ 3, 0 ≦ f, 0 ≦ g ≦ 3, 0.01 ≦ h ≦ 3, 0 ≦ i ≦ 5, and j satisfies the valence of each component. It is the molar ratio of oxygen required for.
なお、本発明において「アンモニウム根」とは、アンモニウムイオン（ＮＨ４ ＋）になり得るアンモニア（ＮＨ３）、およびアンモニウム塩などのアンモニウム含有化合物に含まれるアンモニウムの総称である。Note that the "ammonium ions" in the present invention, ammonia (NH 3) can become an ammonium ion (NH 4 +), and ammonium salts is a general term of ammonium contained in the ammonium-containing compound such.
また、各元素のモル比率は、触媒または触媒前駆体をアンモニア水に溶解した成分をＩＣＰ発光分析法で分析することによって求めた値とする。またアンモニウム根のモル比率は、触媒または触媒前駆体をケルダール法で分析することによって求めた値とする。 The molar ratio of each element is a value obtained by analyzing a component in which a catalyst or a catalyst precursor is dissolved in aqueous ammonia by ICP emission spectrometry. The molar ratio of ammonium roots is a value obtained by analyzing the catalyst or catalyst precursor by the Kjeldahl method.
本発明によれば、前記式（１）で表される組成を有する触媒を用いることで、メタクリル酸の選択率が向上する。通常、メタクロレインが酸化されメタクリル酸となった後、さらに酸化反応が継続して一酸化炭素や二酸化炭素等が生成する逐次酸化反応が起こる。しかしながら、本発明に係る触媒はこの逐次酸化反応を抑制するため、メタクリル酸の選択率が向上すると考えられる。 According to the present invention, the selectivity of methacrylic acid is improved by using a catalyst having the composition represented by the formula (1). Usually, after methacrolein is oxidized to methacrylic acid, the oxidation reaction continues and a sequential oxidation reaction occurs in which carbon monoxide, carbon dioxide and the like are produced. However, since the catalyst according to the present invention suppresses this sequential oxidation reaction, it is considered that the selectivity of methacrylic acid is improved.
前記メタクリル酸製造用触媒において、各成分のモル比率が前記式（１）で規定される範囲から外れると、目的生成物であるメタクリル酸の選択率が低下する。前記式（１）において、ｂ＝１２の時、リンとＡの合計量であるａ＋ｆは０．５≦ａ＋ｆ≦２．１を満たす。特に、２．１＜ａ＋ｆの場合はメタクリル酸の選択率が大幅に低下する。ａ＋ｆの下限は０．６以上が好ましく、０．８以上がより好ましく、０．９以上がさらに好ましく、１．３以上が最も好ましい。またａ＋ｆの上限は２．０以下が好ましく、１．９以下がより好ましく、１．８以下がさらに好ましい。ａは０．５≦ａを満たす。ａの下限は０．６以上が好ましく、０．７以上がより好ましい。ａの上限は１．９以下が好ましく、１．８以下がより好ましい。ｆは０≦ｆを満たす。ｆの下限は０．０１以上が好ましく、０．１以上がより好ましい。ｆの上限は１．０以下が好ましく、０．９以下がより好ましい。 In the catalyst for producing methacrylic acid, when the molar ratio of each component deviates from the range defined by the above formula (1), the selectivity of methacrylic acid, which is the target product, decreases. In the above formula (1), when b = 12, a + f, which is the total amount of phosphorus and A, satisfies 0.5 ≦ a + f ≦ 2.1. In particular, when 2.1 <a + f, the selectivity of methacrylic acid is significantly reduced. The lower limit of a + f is preferably 0.6 or more, more preferably 0.8 or more, further preferably 0.9 or more, and most preferably 1.3 or more. The upper limit of a + f is preferably 2.0 or less, more preferably 1.9 or less, and even more preferably 1.8 or less. a satisfies 0.5 ≦ a. The lower limit of a is preferably 0.6 or more, more preferably 0.7 or more. The upper limit of a is preferably 1.9 or less, and more preferably 1.8 or less. f satisfies 0 ≦ f. The lower limit of f is preferably 0.01 or more, more preferably 0.1 or more. The upper limit of f is preferably 1.0 or less, more preferably 0.9 or less.
また、ＶとＮｂの合計量であるｃ＋ｄは０．０１≦ｃ＋ｄ≦３を満たす。ただし、触媒はＮｂを少なくとも含み、０≦ｃ、０．０１≦ｄ≦３である。ｃ＋ｄの下限は０．１以上が好ましく、０．１５以上がより好ましく、０．２以上がさらに好ましい。またｃ＋ｄの上限は２．５以下が好ましく、２以下がより好ましく、１以下がさらに好ましい。ｄの下限は０．１以上が好ましく、０．１５以上がより好ましく、０．２以上がさらに好ましい。またｄの上限は２．５以下が好ましく、２以下がより好ましく、１以下がさらに好ましい。ｄ／（ｃ＋ｄ）は０．３５≦ｄ／（ｃ＋ｄ）≦１を満たすことが好ましい。これによりメタクリル酸の選択率がより向上する。ｄ／（ｃ＋ｄ）の下限は０．５以上がより好ましく、０．７５以上がさらに好ましく、０．９以上が特に好ましい。 Further, c + d, which is the total amount of V and Nb, satisfies 0.01 ≦ c + d ≦ 3. However, the catalyst contains at least Nb, and is 0 ≦ c and 0.01 ≦ d ≦ 3. The lower limit of c + d is preferably 0.1 or more, more preferably 0.15 or more, and even more preferably 0.2 or more. The upper limit of c + d is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1 or less. The lower limit of d is preferably 0.1 or more, more preferably 0.15 or more, and even more preferably 0.2 or more. The upper limit of d is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1 or less. It is preferable that d / (c + d) satisfies 0.35 ≦ d / (c + d) ≦ 1. This further improves the selectivity of methacrylic acid. The lower limit of d / (c + d) is more preferably 0.5 or more, further preferably 0.75 or more, and particularly preferably 0.9 or more.
ｅは０．００５≦ｅ≦３を満たす。特に、ｅ＜０．００５の場合はメタクロレインの反応率が低下する。ｅの下限は０．０１以上が好ましく、０．０３以上がより好ましく、０．０５以上がさらに好ましい。またｅの上限は２以下が好ましく、１以下がより好ましく、０．５以下がさらに好ましい。 e satisfies 0.005 ≦ e ≦ 3. In particular, when e <0.005, the reaction rate of methacrolein decreases. The lower limit of e is preferably 0.01 or more, more preferably 0.03 or more, and even more preferably 0.05 or more. The upper limit of e is preferably 2 or less, more preferably 1 or less, and even more preferably 0.5 or less.
ｇは０≦ｇ≦３を満たす。ｈは０．０１≦ｈ≦３を満たす。ｈの下限は０．１以上が好ましく、０．３以上がより好ましく、０．５以上がさらに好ましい。またｈの上限は２．５以下が好ましく、２以下がより好ましく、１．５以下がさらに好ましい。ｉは０≦ｉ≦５を満たす。ｉの上限は３以下が好ましく、２以下がより好ましい。 g satisfies 0 ≦ g ≦ 3. h satisfies 0.01 ≦ h ≦ 3. The lower limit of h is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. The upper limit of h is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1.5 or less. i satisfies 0 ≦ i ≦ 5. The upper limit of i is preferably 3 or less, and more preferably 2 or less.
［メタクリル酸製造用触媒前駆体］
また本発明に係るメタクリル酸製造用触媒前駆体（以下、触媒前駆体とも言う）は、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する際に用いられる触媒の、前駆体であって、ケギン型構造を有し、下記式（２）で表される組成を有する。[Catalyst precursor for methacrylic acid production]
The catalyst precursor for methacrylic acid production according to the present invention (hereinafter, also referred to as catalyst precursor) is a precursor of a catalyst used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen. It has a kegin-type structure and has a composition represented by the following formula (2).
ＰａＭｏｂＶｃＮｂｄＣｕｅＡｆＥｇＧｈ（ＮＨ４）ｉＯｊ （２）
式（２）中、Ｐ、Ｍｏ、Ｖ、Ｎｂ、Ｃｕ、ＮＨ４およびＯは、それぞれ、リン、モリブデン、バナジウム、ニオブ、銅、アンモニウム根および酸素を表す。Ａはケイ素、ゲルマニウム、ヒ素およびアンチモンからなる群から選択される少なくとも１種の元素を表す。Ｅはビスマス、ジルコニウム、テルル、銀、セレン、タングステン、ホウ素、鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、インジウム、硫黄、パラジウム、ガリウム、セリウムおよびランタンからなる群から選択される少なくとも１種の元素を示す。Ｇ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から選択される少なくとも１種の元素を表す。ａ〜ｊは、各成分のモル比率を表し、ｂ＝１２の時、０．５≦ａ＋ｆ≦２．４、０．０１≦ｃ＋ｄ≦３、０．５≦ａ、０≦ｃ、０．０１≦ｄ≦３、０．００５≦ｅ≦３、０≦ｆ、０≦ｇ≦３、０．０１≦ｈ≦３、０．１≦ｉ≦２０を満たし、ｊは前記各成分の価数を満足するのに必要な酸素のモル比率である。P a Mo b V c Nb d Cu e A f E g G h (NH 4 ) i O j (2)
In formula (2), P, Mo, V, Nb, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, niobium, copper, ammonium root and oxygen, respectively. A represents at least one element selected from the group consisting of silicon, germanium, arsenic and antimony. E is bismuth, zirconium, tellurium, silver, selenium, tungsten, boron, iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, manganese, barium, titanium, tin, lead, indium, sulfur, palladium, Indicates at least one element selected from the group consisting of gallium, cerium and lanthanum. G represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. a to j represent the molar ratio of each component, and when b = 12, 0.5 ≦ a + f ≦ 2.4, 0.01 ≦ c + d ≦ 3, 0.5 ≦ a, 0 ≦ c, 0.01 ≦ d ≦ 3, 0.005 ≦ e ≦ 3, 0 ≦ f, 0 ≦ g ≦ 3, 0.01 ≦ h ≦ 3, 0.1 ≦ i ≦ 20, and j is the valence of each component. The molar ratio of oxygen required to be satisfied.
本発明によれば、前記式（２）で表される組成を有する触媒前駆体から得られる触媒を用いることで、メタクリル酸の選択率が向上する。通常、メタクロレインが酸化されメタクリル酸となった後、さらに酸化反応が継続して一酸化炭素や二酸化炭素等が生成する逐次酸化反応が起こる。しかしながら、本発明に係る触媒前駆体から得られる触媒はこの逐次酸化反応を抑制するため、メタクリル酸の選択率が向上すると考えられる。 According to the present invention, the selectivity of methacrylic acid is improved by using a catalyst obtained from a catalyst precursor having a composition represented by the formula (2). Usually, after methacrolein is oxidized to methacrylic acid, the oxidation reaction continues and a sequential oxidation reaction occurs in which carbon monoxide, carbon dioxide and the like are produced. However, since the catalyst obtained from the catalyst precursor according to the present invention suppresses this sequential oxidation reaction, it is considered that the selectivity of methacrylic acid is improved.
前記メタクリル酸製造用触媒前駆体において、各成分のモル比率が前記式（２）で規定される範囲から外れると、目的生成物であるメタクリル酸の選択率が低下する。前記式（２）において、ｂ＝１２の時、リンとＡの合計量であるａ＋ｆは０．５≦ａ＋ｆ≦２．４を満たす。特に、２．４＜ａ＋ｆの場合はメタクリル酸の選択率が大幅に低下する。ａ＋ｆの下限は０．６以上が好ましく、０．８以上がより好ましく、０．９以上がさらに好ましく、１．３以上が最も好ましい。またａ＋ｆの上限は２．２以下が好ましく、２．０以下がより好ましく、１．８以下がさらに好ましい。ａは０．５≦ａを満たす。ａの下限は０．６以上が好ましく、０．７以上がより好ましい。ａの上限は１．９以下が好ましく、１．８以下がより好ましい。ｆは０≦ｆを満たす。ｆの下限は０．０１以上が好ましく、０．１以上がより好ましい。ｆの上限は１．０以下が好ましく、０．９以下がより好ましい。 In the catalyst precursor for methacrylic acid production, when the molar ratio of each component deviates from the range defined by the above formula (2), the selectivity of methacrylic acid, which is the target product, decreases. In the above formula (2), when b = 12, a + f, which is the total amount of phosphorus and A, satisfies 0.5 ≦ a + f ≦ 2.4. In particular, when 2.4 <a + f, the selectivity of methacrylic acid is significantly reduced. The lower limit of a + f is preferably 0.6 or more, more preferably 0.8 or more, further preferably 0.9 or more, and most preferably 1.3 or more. The upper limit of a + f is preferably 2.2 or less, more preferably 2.0 or less, and even more preferably 1.8 or less. a satisfies 0.5 ≦ a. The lower limit of a is preferably 0.6 or more, more preferably 0.7 or more. The upper limit of a is preferably 1.9 or less, and more preferably 1.8 or less. f satisfies 0 ≦ f. The lower limit of f is preferably 0.01 or more, more preferably 0.1 or more. The upper limit of f is preferably 1.0 or less, more preferably 0.9 or less.
また、ＶとＮｂの合計量であるｃ＋ｄは０．０１≦ｃ＋ｄ≦３を満たす。ただし、触媒前駆体はＮｂを少なくとも含み、０≦ｃ、０．０１≦ｄ≦３である。ｃ＋ｄの下限は０．１以上が好ましく、０．１５以上がより好ましく、０．２以上がさらに好ましい。またｃ＋ｄの上限は２．５以下が好ましく、２以下がより好ましく、１以下がさらに好ましい。ｄの下限は０．１以上が好ましく、０．１５以上がより好ましく、０．２以上がさらに好ましい。またｄの上限は２．５以下が好ましく、２以下がより好ましく、１以下がさらに好ましい。ｄ／（ｃ＋ｄ）は０．３５≦ｄ／（ｃ＋ｄ）≦１を満たすことが好ましい。これによりメタクリル酸の選択率がより向上する。ｄ／（ｃ＋ｄ）の下限は０．５以上がより好ましく、０．７５以上がさらに好ましく、０．９以上が特に好ましい。 Further, c + d, which is the total amount of V and Nb, satisfies 0.01 ≦ c + d ≦ 3. However, the catalyst precursor contains at least Nb and is 0 ≦ c and 0.01 ≦ d ≦ 3. The lower limit of c + d is preferably 0.1 or more, more preferably 0.15 or more, and even more preferably 0.2 or more. The upper limit of c + d is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1 or less. The lower limit of d is preferably 0.1 or more, more preferably 0.15 or more, and even more preferably 0.2 or more. The upper limit of d is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1 or less. It is preferable that d / (c + d) satisfies 0.35 ≦ d / (c + d) ≦ 1. This further improves the selectivity of methacrylic acid. The lower limit of d / (c + d) is more preferably 0.5 or more, further preferably 0.75 or more, and particularly preferably 0.9 or more.
ｅは０．００５≦ｅ≦３を満たす。ｅ＜０．００５の場合はメタクロレインの反応率が低下する。ｅの下限は０．０１以上が好ましく、０．０３以上がより好ましく、０．０５以上がさらに好ましい。またｅの上限は２以下が好ましく、１以下がより好ましく、０．５以下がさらに好ましい。 e satisfies 0.005 ≦ e ≦ 3. When e <0.005, the reaction rate of methacrolein decreases. The lower limit of e is preferably 0.01 or more, more preferably 0.03 or more, and even more preferably 0.05 or more. The upper limit of e is preferably 2 or less, more preferably 1 or less, and even more preferably 0.5 or less.
ｇは０≦ｇ≦３を満たす。ｈは０．０１≦ｈ≦３を満たす。ｈの下限は０．１以上が好ましく、０．３以上がより好ましく、０．５以上がさらに好ましい。またｈの上限は２．５以下が好ましく、２以下がより好ましく、１．５以下がさらに好ましい。ｉは０．１≦ｉ≦２０を満たす。ｉの下限は０．５以上が好ましく、１以上がより好ましい。ｉの上限は１８以下が好ましく、１６以下がより好ましい。 g satisfies 0 ≦ g ≦ 3. h satisfies 0.01 ≦ h ≦ 3. The lower limit of h is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. The upper limit of h is preferably 2.5 or less, more preferably 2 or less, and even more preferably 1.5 or less. i satisfies 0.1 ≦ i ≦ 20. The lower limit of i is preferably 0.5 or more, and more preferably 1 or more. The upper limit of i is preferably 18 or less, more preferably 16 or less.
本発明に係るメタクリル酸製造用触媒前駆体は、ケギン型構造を有する。これによりメタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する際に高い活性を示す。該触媒前駆体の構造は、赤外吸収分析測定により判断することができる。触媒前駆体がケギン型構造を有する場合、得られる赤外吸収スペクトルは、１０６０、９６０、８７０、７８０ｃｍ−１付近に特徴的なピークを有する。The catalyst precursor for methacrylic acid production according to the present invention has a kegin-type structure. As a result, methacrolein exhibits high activity when produced by vapor-phase catalytic oxidation with molecular oxygen to produce methacrylic acid. The structure of the catalyst precursor can be determined by infrared absorption analysis measurement. When the catalyst precursor has a kegin-type structure, the obtained infrared absorption spectrum has a characteristic peak near 1060, 960, 870, 780 cm- 1 .
なお、本発明に係るメタクリル酸製造用触媒が下記式（３）で表される組成を有する場合は、下記の原子比率を満たすことが好ましい。 When the catalyst for producing methacrylic acid according to the present invention has a composition represented by the following formula (3), it is preferable to satisfy the following atomic ratio.
ＰａＭｏｂＶｃＮｂｄＣｕｅＳｂｆＸｇＺｈＯｉ （３）
式（３）中、Ｐ、Ｍｏ、Ｖ、Ｎｂ、Ｃｕ、ＳｂおよびＯは、それぞれ、リン、モリブデン、バナジウム、ニオブ、銅、アンチモンおよび酸素を表す。Ｘはケイ素、チタン、ゲルマニウム、ヒ素、テルルおよびセレンからなる群から選択される少なくとも１種の元素を表す。Ｚはカリウム、ルビジウムおよびセシウムからなる群から選択される少なくとも１種の元素を表す。ａ〜ｈは、各元素の原子比率を表し、ｂ＝１２の時、０．５≦ａ≦３、０．０１≦ｃ＋ｄ≦３、０．０１≦ｄ≦３、０．０１≦ｅ≦２、０≦ｆ＜０．０１、０．０１≦ｇ≦３、０．０１≦ｈ≦３を満たし、ｉは前記各元素の原子価を満足するのに必要な酸素の原子比率である。P a Mo b V c Nb d Cu e Sb f X g Z h O i (3)
In formula (3), P, Mo, V, Nb, Cu, Sb and O represent phosphorus, molybdenum, vanadium, niobium, copper, antimony and oxygen, respectively. X represents at least one element selected from the group consisting of silicon, titanium, germanium, arsenic, tellurium and selenium. Z represents at least one element selected from the group consisting of potassium, rubidium and cesium. a to h represent the atomic ratio of each element, and when b = 12, 0.5 ≦ a ≦ 3, 0.01 ≦ c + d ≦ 3, 0.01 ≦ d ≦ 3, 0.01 ≦ e ≦ 2. , 0 ≦ f <0.01, 0.01 ≦ g ≦ 3, 0.01 ≦ h ≦ 3, and i is the atomic ratio of oxygen required to satisfy the valence of each element.
前記式（３）において、ｂ＝１２の時、ａは０．５≦ａ≦３を満たし、好ましくは０．６≦ａ≦２．５を満たし、より好ましくは０．８≦ａ≦２を満たし、さらに好ましくは０．９≦ａ≦１．３を満たす。ｃ＋ｄは、０．０１≦ｃ＋ｄ≦３を満たし、好ましくは０．１≦ｃ＋ｄ≦２．５を満たし、より好ましくは０．１５≦ｃ＋ｄ≦２を満たし、さらに好ましくは０．２≦ｃ＋ｄ≦１を満たす。ｄは、０．０１≦ｄ≦３を満たし、好ましくは０．１≦ｄ≦２．５を満たし、より好ましくは０．１５≦ｄ≦２を満たし、さらに好ましくは０．２≦ｄ≦１を満たす。ｅは、０．０１≦ｅ≦２を満たし、好ましくは０．０３≦ｅ≦１．５を満たし、より好ましくは０．０４≦ｅ≦１を満たし、さらに好ましくは０．０５≦ｅ≦０．５を満たす。ｆは、０≦ｆ＜０．０１を満たし、好ましくは０≦ｆ≦０．００５を満たし、より好ましくは０≦ｆ≦０．００１を満たし、さらに好ましくはｆ＝０を満たす。ｇは、０．０１≦ｇ≦３を満たし、好ましくは０．１≦ｇ≦２．５を満たし、より好ましくは０．３≦ｇ≦２を満たし、さらに好ましくは０．５≦ｇ≦１を満たす。ｈは、０．０１≦ｈ≦３を満たし、好ましくは０．１≦ｈ≦２．５を満たし、より好ましくは０．３≦ｈ≦２を満たし、さらに好ましくは０．５≦ｈ≦１．５を満たす。 In the above formula (3), when b = 12, a satisfies 0.5 ≦ a ≦ 3, preferably 0.6 ≦ a ≦ 2.5, and more preferably 0.8 ≦ a ≦ 2. Satisfy, more preferably 0.9 ≦ a ≦ 1.3. c + d satisfies 0.01 ≦ c + d ≦ 3, preferably 0.1 ≦ c + d ≦ 2.5, more preferably 0.15 ≦ c + d ≦ 2, and even more preferably 0.2 ≦ c + d ≦ 1. Meet. d satisfies 0.01 ≦ d ≦ 3, preferably 0.1 ≦ d ≦ 2.5, more preferably 0.15 ≦ d ≦ 2, and further preferably 0.2 ≦ d ≦ 1. Meet. e satisfies 0.01 ≦ e ≦ 2, preferably 0.03 ≦ e ≦ 1.5, more preferably 0.04 ≦ e ≦ 1, and further preferably 0.05 ≦ e ≦ 0. .5 is satisfied. f satisfies 0 ≦ f <0.01, preferably 0 ≦ f ≦ 0.005, more preferably 0 ≦ f ≦ 0.001, and further preferably f = 0. g satisfies 0.01 ≦ g ≦ 3, preferably 0.1 ≦ g ≦ 2.5, more preferably 0.3 ≦ g ≦ 2, and further preferably 0.5 ≦ g ≦ 1. Meet. h satisfies 0.01 ≦ h ≦ 3, preferably 0.1 ≦ h ≦ 2.5, more preferably 0.3 ≦ h ≦ 2, and further preferably 0.5 ≦ h ≦ 1. .5 is satisfied.
各元素の原子比率が前記式（３）で規定される範囲から外れると、目的生成物であるメタクリル酸の選択率が低下する場合がある。特に、メタクリル酸の選択率向上の観点から、アンチモンを含まない、すなわちｆ＝０が好ましい。なお、３＜ｄの場合、メタクロレインの反応率が低下する。 If the atomic ratio of each element deviates from the range defined by the above formula (3), the selectivity of methacrylic acid, which is the target product, may decrease. In particular, from the viewpoint of improving the selectivity of methacrylic acid, it is preferable that antimony is not contained, that is, f = 0. When 3 <d, the reaction rate of methacrolein decreases.
また、ｄ／（ｃ＋ｄ）の値は、０．５≦ｄ／（ｃ＋ｄ）≦１を満たすことが好ましく、０．７５≦ｄ／（ｃ＋ｄ）≦１を満たすことがより好ましく、０．９≦ｄ／（ｃ＋ｄ）≦１を満たすことがさらに好ましい。０．５≦ｄ／（ｃ＋ｄ）≦１を満たすことにより、メタクリル酸の選択率がより向上する。 Further, the value of d / (c + d) preferably satisfies 0.5 ≦ d / (c + d) ≦ 1, more preferably 0.75 ≦ d / (c + d) ≦ 1, and 0.9 ≦. It is more preferable to satisfy d / (c + d) ≦ 1. By satisfying 0.5 ≦ d / (c + d) ≦ 1, the selectivity of methacrylic acid is further improved.
［メタクリル酸製造用触媒前駆体の製造方法］
本発明に係るメタクリル酸製造用触媒前駆体の製造方法は、以下の工程（ｉ）から（ｉｉｉ）を含み、かつ前記工程（ｉ）および（ｉｉ）において、前記スラリー（Ｉ）、前記溶液（Ｉ）および前記スラリー（ＩＩ）のｐＨを０．１〜６．５の範囲内に維持する。
（ｉ）少なくともモリブデンの原料を含むスラリー（Ｉ）または溶液（Ｉ）を調製する工程。
（ｉｉ）前記スラリー（Ｉ）または前記溶液（Ｉ）にアンモニウム化合物を添加して、アンモニウム塩を含むスラリー（ＩＩ）を調製する工程。
（ｉｉｉ）前記スラリー（ＩＩ）を乾燥し、前記ケギン型構造を有するメタクリル酸製造用触媒前駆体を得る工程。[Method for producing catalyst precursor for methacrylic acid production]
The method for producing a catalyst precursor for producing methacrylic acid according to the present invention comprises the following steps (i) to (iii), and in the steps (i) and (ii), the slurry (I) and the solution (ii) The pH of I) and the slurry (II) is maintained in the range of 0.1 to 6.5.
(I) A step of preparing a slurry (I) or a solution (I) containing at least a molybdenum raw material.
(Ii) A step of adding an ammonium compound to the slurry (I) or the solution (I) to prepare a slurry (II) containing an ammonium salt.
(Iii) A step of drying the slurry (II) to obtain a catalyst precursor for producing methacrylic acid having the kegin-type structure.
また、本発明に係るメタクリル酸製造用触媒前駆体の製造方法は、後述する成形工程をさらに有してもよい。該方法によれば、本発明に係るメタクリル酸製造用触媒前駆体を好適に製造することができる。 Further, the method for producing a catalyst precursor for producing methacrylic acid according to the present invention may further include a molding step described later. According to the method, the catalyst precursor for methacrylic acid production according to the present invention can be suitably produced.
（工程（ｉ））
工程（ｉ）では、少なくともモリブデンの原料を含むスラリー（Ｉ）または溶液（Ｉ）を調製する。前記スラリー（Ｉ）または前記溶液（Ｉ）はいずれであっても良く、例えば、調製容器を用いて触媒成分の原料化合物を溶媒に懸濁させることでスラリー（Ｉ）を、溶媒に溶解させることで溶液（Ｉ）を、それぞれ調製することができる。前記スラリー（Ｉ）または前記溶液（Ｉ）は少なくともモリブデンの原料を含み、前記式（２）で表される組成に含まれる成分を含むことができ、ニオブの原料を含むことが好ましい。(Step (i))
In step (i), a slurry (I) or solution (I) containing at least a molybdenum raw material is prepared. The slurry (I) or the solution (I) may be either, and for example, the slurry (I) is dissolved in the solvent by suspending the raw material compound of the catalyst component in the solvent using a preparation container. Can be prepared for each of the solutions (I). The slurry (I) or the solution (I) contains at least a molybdenum raw material, can contain components contained in the composition represented by the formula (2), and preferably contains a niobium raw material.
使用する原料化合物としては特に限定はなく、各元素の硝酸塩、炭酸塩、酢酸塩、アンモニウム塩、酸化物、ハロゲン化物、オキソ酸、オキソ酸塩などが挙げられ、それらを組み合わせて使用することもできる。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、塩化モリブデンなどが挙げられる。リン原料としては、例えば正リン酸、五酸化リン、又は、リン酸アンモニウム、リン酸セシウム等のリン酸塩などが挙げられる。銅原料としては、例えば硫酸銅、硝酸銅、酸化銅、炭酸銅、酢酸銅、塩化銅などが挙げられる。バナジウム原料としては、例えばリンバナドモリブデン酸、メタバナジン酸アンモニウム、五酸化バナジウム、塩化バナジウムなどが挙げられる。ただし、バナジウム原料としてリンバナドモリブデン酸を用いる場合、リンバナドモリブデン酸中には、モリブデン元素およびリン元素が同時に含まれるため、リンバナドモリブデン酸の添加量に応じて目標の触媒前駆体組成となるようにモリブデン原料、リン原料の添加量を調整する。ニオブ原料としては、例えばニオブ酸、五酸化ニオブ、塩化ニオブ、シュウ酸水素ニオブ、ニオブ酸シュウ酸アンモニウムなどが挙げられる。触媒前駆体の調製時の溶媒として水を用いる場合には、ニオブ原料としてシュウ酸水素ニオブ、ニオブ酸シュウ酸アンモニウム等の水溶性原料を用いることが好ましい。一方、例えば五酸化ニオブのような非水溶性原料を用いる場合には、水にシュウ酸や過酸化水素を添加するなどニオブ原料が水に溶解する調製方法を選択することが好ましい。これにより、後述する工程（ｉｉｉ）において好ましい構造を有する触媒前駆体を得ることができる。 The raw material compound to be used is not particularly limited, and examples thereof include nitrates, carbonates, acetates, ammonium salts, oxides, halides, oxoacids, oxoacids, etc. of each element, and they may be used in combination. it can. Examples of the molybdenum raw material include ammonium paramolybdate, molybdenum trioxide, molybdenum acid, molybdenum chloride and the like. Examples of the phosphorus raw material include orthophosphoric acid, phosphorus pentoxide, and phosphates such as ammonium phosphate and cesium phosphate. Examples of the copper raw material include copper sulfate, copper nitrate, copper oxide, copper carbonate, copper acetate, copper chloride and the like. Examples of the vanadium raw material include limvanado molybdic acid, ammonium metavanadate, vanadium pentoxide, vanadium chloride and the like. However, when limbanado molybdic acid is used as the vanadium raw material, the molybdenum element and the phosphorus element are contained at the same time in the limbanado molybdic acid, so that the target catalyst precursor composition is obtained depending on the amount of the limbanado molybdic acid added. Adjust the amount of molybdenum raw material and phosphorus raw material added. Examples of the niobium raw material include niobium acid, niobium pentoxide, niobium chloride, niobium hydrogen oxalate, and ammonium oxalate oxalate. When water is used as the solvent in the preparation of the catalyst precursor, it is preferable to use a water-soluble raw material such as niobium hydrogen oxalate or ammonium oxalate oxalate as the niobium raw material. On the other hand, when a water-insoluble raw material such as niobium pentoxide is used, it is preferable to select a preparation method in which the niobium raw material is dissolved in water, such as adding oxalic acid or hydrogen peroxide to water. As a result, a catalyst precursor having a preferable structure can be obtained in the step (iii) described later.
前記スラリー（Ｉ）または前記溶液（Ｉ）は、触媒前駆体を構成する元素を含有する原料を溶媒へ添加し、混合して得ることができる。該溶媒としては、水、有機溶媒等を使用できるが、工業的な観点から水を使用することが好ましい。また、必要に応じて前記スラリー（Ｉ）または前記溶液（Ｉ）を加熱処理してもよい。調製時の原料の添加順序は特に限定されないが、工程（ｉ）において、前記スラリー（Ｉ）または前記溶液（Ｉ）のｐＨは０．１〜６．５に維持しながら調製する。これによりメタクリル酸の選択率が向上する。該ｐＨの下限は０．５以上が好ましく、１．０以上がより好ましい。また該ｐＨの上限は６以下が好ましい。なお、前記スラリー（Ｉ）または前記溶液（Ｉ）のｐＨは、ＨＯＲＩＢＡ製ポータブル型ｐＨメータＤ−７２（商品名）等により測定することができる。前記スラリー（Ｉ）または前記溶液（Ｉ）のｐＨを制御する方法としては、触媒前駆体を構成する各成分の原料やアンモニウム根の添加量等を適宜選択し、硝酸、シュウ酸等を適宜添加する方法が挙げられる。 The slurry (I) or the solution (I) can be obtained by adding a raw material containing an element constituting a catalyst precursor to a solvent and mixing the mixture. As the solvent, water, an organic solvent and the like can be used, but it is preferable to use water from an industrial point of view. Further, the slurry (I) or the solution (I) may be heat-treated, if necessary. The order of adding the raw materials at the time of preparation is not particularly limited, but in the step (i), the pH of the slurry (I) or the solution (I) is maintained at 0.1 to 6.5. This improves the selectivity of methacrylic acid. The lower limit of the pH is preferably 0.5 or more, more preferably 1.0 or more. The upper limit of the pH is preferably 6 or less. The pH of the slurry (I) or the solution (I) can be measured with a portable pH meter D-72 (trade name) manufactured by HORIBA. As a method for controlling the pH of the slurry (I) or the solution (I), the raw materials of each component constituting the catalyst precursor, the amount of ammonium root added, and the like are appropriately selected, and nitric acid, oxalic acid, and the like are appropriately added. There is a way to do it.
（工程（ｉｉ））
工程（ｉｉ）では、前記スラリー（Ｉ）または前記溶液（Ｉ）にアンモニウム化合物を添加して、アンモニウム塩を含むスラリー（ＩＩ）を調製する。アンモニウム化合物としては、炭酸水素アンモニウム、炭酸アンモニウム、硝酸アンモニウム、アンモニア水等が挙げられる。これらのアンモニウム化合物は、一種を用いてもよく、二種以上を併用してもよい。また工程（ｉｉ）では、アンモニウム化合物に加えて金属カチオン含有化合物を添加することが好ましい。金属カチオン含有化合物としては、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から選択される少なくとも１種の元素（前記式（２）のＧに相当）を含む化合物を用いることが好ましい。(Step (ii))
In the step (ii), an ammonium compound is added to the slurry (I) or the solution (I) to prepare a slurry (II) containing an ammonium salt. Examples of the ammonium compound include ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrate, aqueous ammonia and the like. These ammonium compounds may be used alone or in combination of two or more. Further, in the step (ii), it is preferable to add a metal cation-containing compound in addition to the ammonium compound. As the metal cation-containing compound, it is preferable to use a compound containing at least one element (corresponding to G in the above formula (2)) selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium.
また、前記スラリー（ＩＩ）を加熱処理することが好ましい。加熱処理の温度は特に限定されないが、モリブデン、ニオブ、銅、リンおよび必要により他の金属元素を含有する化合物が溶解または他の化合物と反応できる温度まで加熱することが好ましく、具体的には７５〜１３０℃が好ましく、９５〜１３０℃がより好ましい。用いる溶媒の蒸気圧に応じて、加熱時に濃縮、還流したり、密閉容器の中で操作することにより加圧条件にて加熱処理したりしてもよい。昇温速度は特に限定されないが、０．８〜１５℃／分が好ましい。昇温速度が０．８℃／分以上であることにより、スラリー調製時間を短縮できる。また、昇温速度が１５℃／分以下であることにより、通常の昇温設備を用いて昇温を行うことができる。 Moreover, it is preferable to heat-treat the slurry (II). The temperature of the heat treatment is not particularly limited, but it is preferable to heat the compound to a temperature at which a compound containing molybdenum, niobium, copper, phosphorus and, if necessary, other metal elements can dissolve or react with other compounds, specifically 75. ~ 130 ° C. is preferable, and 95 to 130 ° C. is more preferable. Depending on the vapor pressure of the solvent used, it may be concentrated and refluxed at the time of heating, or may be heat-treated under pressurized conditions by operating in a closed container. The rate of temperature rise is not particularly limited, but is preferably 0.8 to 15 ° C./min. When the heating rate is 0.8 ° C./min or more, the slurry preparation time can be shortened. Further, since the temperature rising rate is 15 ° C./min or less, the temperature can be raised by using a normal temperature raising facility.
工程（ｉｉ）において、前記スラリー（ＩＩ）のｐＨを０．１〜６．５に維持しながら調製する。これによりメタクリル酸の選択率が向上する。該ｐＨの下限は０．５以上が好ましく、１．０以上がより好ましい。また上限は６．０以下が好ましい。工程（ｉｉ）において加熱処理を行った場合、得られる加熱処理後のスラリー（ＩＩ）のｐＨは、０．１〜３．０であることが好ましく、下限は１．０以上、上限は２．５以下がより好ましい。なお、前記スラリー（ＩＩ）のｐＨは、ＨＯＲＩＢＡ製ポータブル型ｐＨメータＤ−７２（商品名）等により測定することができる。前記スラリー（ＩＩ）のｐＨを制御する方法としては、触媒前駆体を構成する各成分の原料やアンモニウム根の添加量等を適宜選択し、硝酸、シュウ酸等を適宜添加する方法が挙げられる。これにより、後述する工程（ｉｉｉ）において好ましい構造を有する触媒前駆体を得ることができる。 In step (ii), the pH of the slurry (II) is maintained at 0.1 to 6.5 for preparation. This improves the selectivity of methacrylic acid. The lower limit of the pH is preferably 0.5 or more, more preferably 1.0 or more. The upper limit is preferably 6.0 or less. When the heat treatment is performed in the step (ii), the pH of the obtained slurry (II) after the heat treatment is preferably 0.1 to 3.0, the lower limit is 1.0 or more, and the upper limit is 2. 5 or less is more preferable. The pH of the slurry (II) can be measured with a portable pH meter D-72 (trade name) manufactured by HORIBA. Examples of the method for controlling the pH of the slurry (II) include a method in which a raw material for each component constituting the catalyst precursor, an amount of ammonium root added, and the like are appropriately selected, and nitric acid, oxalic acid, and the like are appropriately added. As a result, a catalyst precursor having a preferable structure can be obtained in the step (iii) described later.
（工程（ｉｉｉ））
工程（ｉｉｉ）では、前記スラリー（ＩＩ）を乾燥し、前記ケギン型構造を有するメタクリル酸製造用触媒前駆体を得る。乾燥方法に特に制限はなく、ドラム乾燥、凍結乾燥、噴霧乾燥、蒸発乾固等が挙げられる。これらのうち本発明に係る方法では、ドラム乾燥、噴霧乾燥または蒸発乾固が好ましい。(Step (iii))
In the step (iii), the slurry (II) is dried to obtain a catalyst precursor for producing methacrylic acid having the kegin-type structure. The drying method is not particularly limited, and examples thereof include drum drying, freeze drying, spray drying, and evaporation drying. Of these, in the method according to the present invention, drum drying, spray drying or evaporation drying is preferable.
工程（ｉｉｉ）においてケギン型構造を有する触媒前駆体を得る方法としては、前記工程（ｉｉ）において得られる加熱処理後の前記スラリー（ＩＩ）のｐＨを３以下、好ましくは２．５以下に調整する方法が挙げられる。該触媒前駆体の構造は、赤外吸収分析測定により判断することができる。該触媒前駆体がケギン型構造を有する場合、得られる赤外吸収スペクトルは、１０６０、９６０、８７０、７８０ｃｍ−１付近に特徴的なピークを有する。As a method for obtaining a catalyst precursor having a kegin-type structure in the step (iii), the pH of the slurry (II) after the heat treatment obtained in the step (ii) is adjusted to 3 or less, preferably 2.5 or less. There is a way to do it. The structure of the catalyst precursor can be determined by infrared absorption analysis measurement. When the catalyst precursor has a kegin-type structure, the obtained infrared absorption spectrum has a characteristic peak near 1060, 960, 870, 780 cm- 1 .
（成形工程）
成形工程では、前記触媒前駆体または後述する焼成工程で得られる焼成後の触媒を成形する。本発明に係る方法により製造される触媒は、固定床型反応器や流動床型反応器のいずれでも使用することができるため、該触媒の形状はそれぞれの反応の形態に好適な形状から適宜選択すればよい。例えば固定床型反応器で使用される触媒の成形方法は特に限定はなく、公知の方法から適宜選択することができるが、反応時の圧力損失が大きくならない形状に成形することが好ましい。成形方法としては、打錠成形、湿式成形、加圧成形、転動造粒等が挙げられ、使用条件に応じて好適な大きさおよび形状とすればよい。また、例えば流動床型反応器で使用される触媒を製造する場合には、噴霧乾燥により微粉とした触媒前駆体を湿式成形することが好ましい。(Molding process)
In the molding step, the catalyst precursor or the fired catalyst obtained in the firing step described later is molded. Since the catalyst produced by the method according to the present invention can be used in either a fixed bed type reactor or a fluidized bed type reactor, the shape of the catalyst is appropriately selected from the shapes suitable for each reaction form. do it. For example, the method for molding the catalyst used in the fixed-bed reactor is not particularly limited and can be appropriately selected from known methods, but it is preferable to mold the catalyst into a shape that does not increase the pressure loss during the reaction. Examples of the molding method include tableting molding, wet molding, pressure molding, rolling granulation and the like, and the size and shape may be suitable according to the conditions of use. Further, for example, in the case of producing a catalyst used in a fluidized bed reactor, it is preferable to wet-mold a catalyst precursor made into fine powder by spray drying.
［メタクリル酸製造用触媒の製造方法］
本発明に係るメタクリル酸製造用触媒の製造方法は、前記工程（ｉｉｉ）で得られた触媒前駆体、または前記成形工程で得られた触媒前駆体の成形物（以下、まとめて触媒前駆体とも言う）を焼成する工程（以下、焼成工程とも言う）を含む。[Manufacturing method of catalyst for methacrylic acid production]
The method for producing a catalyst for producing methacrylic acid according to the present invention is a catalyst precursor obtained in the step (iii) or a molded product of the catalyst precursor obtained in the molding step (hereinafter collectively referred to as a catalyst precursor). Includes a step of firing (hereinafter also referred to as a firing step).
（焼成工程）
焼成工程では、前記触媒前駆体を焼成し、メタクリル酸製造用触媒を得る。焼成方法に特に限定はなく、静置焼成、流動焼成等から好適な方法を適宜選択すればよい。静置焼成としては、例えば箱型電気炉、環状焼成炉等を用いて焼成する方法が挙げられる。流動焼成としては、例えば流動焼成炉、ロータリーキルン等を用いて焼成する方法が挙げられる。焼成ガスは、空気、窒素等から適宜選択することができる。なお、所望の焼成ガス雰囲気が維持できれば、焼成ガスは流通させても、流通させなくてもよい。触媒活性およびメタクリル酸選択率が高い触媒が得られる観点から、焼成温度は２００〜５００℃が好ましく、下限は３００℃以上、上限は４５０℃以下がより好ましい。焼成時間は０．５〜４０時間が好ましく、１〜４０時間がより好ましく、２〜４０時間がさらに好ましい。(Baking process)
In the firing step, the catalyst precursor is fired to obtain a catalyst for producing methacrylic acid. The firing method is not particularly limited, and a suitable method may be appropriately selected from static firing, fluid firing and the like. Examples of the static firing include a method of firing using a box-type electric furnace, an annular firing furnace, or the like. Examples of the flow firing include a method of firing using a flow firing furnace, a rotary kiln, or the like. The firing gas can be appropriately selected from air, nitrogen and the like. If the desired firing gas atmosphere can be maintained, the firing gas may or may not be circulated. From the viewpoint of obtaining a catalyst having high catalytic activity and methacrylic acid selectivity, the firing temperature is preferably 200 to 500 ° C., the lower limit is 300 ° C. or higher, and the upper limit is 450 ° C. or lower. The firing time is preferably 0.5 to 40 hours, more preferably 1 to 40 hours, still more preferably 2 to 40 hours.
なお、得られる触媒は単体で用いてもよいが、シリカ、アルミナ、シリカ・アルミナ、シリコンカーバイド等の不活性担体に担持させるか、またはこれらと混合して用いてもよい。また、本発明に係る製造方法以外の方法で製造された触媒と混合して用いても良い。 The obtained catalyst may be used alone, or may be supported on an inert carrier such as silica, alumina, silica-alumina, or silicon carbide, or mixed with these. Further, it may be mixed with a catalyst produced by a method other than the production method according to the present invention.
［メタクリル酸の製造方法］
本発明に係るメタクリル酸の製造方法は、本発明に係るメタクリル酸製造用触媒を用いて、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する。また、本発明に係るメタクリル酸の製造方法は、本発明に係る方法によりメタクリル酸製造用触媒を製造し、該メタクリル酸製造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してメタクリル酸を製造する。また、本発明に係るメタクリル酸の製造方法は、本発明に係る方法により製造されたメタクリル酸製造用触媒を用いて、メタクロレインを分子状酸素により気相接触酸化してメタクリル酸を製造する。これらの方法によれば、高選択率でメタクリル酸を製造することができる。[Method for producing methacrylic acid]
In the method for producing methacrylic acid according to the present invention, methacrolein is vapor-phase catalytically oxidized with molecular oxygen using the catalyst for producing methacrylic acid according to the present invention to produce methacrylic acid. Further, in the method for producing methacrylic acid according to the present invention, a catalyst for producing methacrylic acid is produced by the method according to the present invention, and methacrolein is vapor-phase catalytically oxidized with molecular oxygen using the catalyst for producing methacrylic acid. Produces methacrylic acid. Further, in the method for producing methacrylic acid according to the present invention, methacrolein is vapor-phase contact-oxidized with molecular oxygen using a catalyst for producing methacrylic acid produced by the method according to the present invention to produce methacrylic acid. According to these methods, methacrylic acid can be produced with high selectivity.
前記方法は、メタクロレインと分子状酸素とを含む原料ガスを前記メタクリル酸製造用触媒に接触させて行うことができる。原料ガス中のメタクロレインの濃度は特に限定されないが、１〜２０容量％が好ましく、３〜１０容量％がより好ましい。原料であるメタクロレインは、水、低級飽和アルデヒド等の本反応に実質的な影響を与えない不純物を少量含んでいてもよい。 The method can be carried out by bringing a raw material gas containing methacrolein and molecular oxygen into contact with the catalyst for producing methacrylic acid. The concentration of methacrolein in the raw material gas is not particularly limited, but is preferably 1 to 20% by volume, more preferably 3 to 10% by volume. The raw material, methacrolein, may contain a small amount of impurities such as water and lower saturated aldehyde that do not substantially affect the reaction.
原料ガス中の分子状酸素の濃度は、メタクロレイン１モルに対して０．４〜４モルが好ましく、０．５〜３モルがより好ましい。分子状酸素源としては、経済性の観点から空気が好ましい。必要であれば、空気に純酸素を加えて分子状酸素を富化した気体を用いてもよい。 The concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4 mol, more preferably 0.5 to 3 mol, relative to 1 mol of methacrolein. As the molecular oxygen source, air is preferable from the viewpoint of economy. If necessary, a gas enriched with molecular oxygen by adding pure oxygen to air may be used.
原料ガスは、メタクロレイン及び分子状酸素を、窒素、炭酸ガス等の不活性ガスで希釈したものであってもよい。さらに、原料ガスに水蒸気を加えてもよい。水の存在下で反応を行うことにより、メタクリル酸をより高選択率、高収率で得ることができる。原料ガス中の水蒸気の濃度は、０．１〜５０容量％が好ましく、１〜４０容量％がより好ましい。 The raw material gas may be a gas obtained by diluting methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide. Further, water vapor may be added to the raw material gas. By carrying out the reaction in the presence of water, methacrylic acid can be obtained with higher selectivity and higher yield. The concentration of water vapor in the raw material gas is preferably 0.1 to 50% by volume, more preferably 1 to 40% by volume.
原料ガスとメタクリル酸製造用触媒との接触時間は、１．５〜１５秒が好ましく、２〜１０秒がより好ましい。反応圧力は、０．１〜１ＭＰａ（Ｇ）が好ましい。ただし、（Ｇ）はゲージ圧であることを意味する。反応温度は２００〜４５０℃が好ましく、２５０〜４００℃がより好ましい。 The contact time between the raw material gas and the catalyst for producing methacrylic acid is preferably 1.5 to 15 seconds, more preferably 2 to 10 seconds. The reaction pressure is preferably 0.1 to 1 MPa (G). However, (G) means that it is a gauge pressure. The reaction temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C.
［メタクリル酸エステルの製造方法］
本発明に係るメタクリル酸エステルの製造方法は、本発明に係る方法により製造されたメタクリル酸をエステル化する。また、本発明に係るメタクリル酸エステルの製造方法は、本発明に係る方法によりメタクリル酸を製造し、該メタクリル酸をエステル化する。これらの方法によれば、メタクロレインの気相接触酸化により得られるメタクリル酸を用いて、メタクリル酸エステルを得ることができる。メタクリル酸と反応させるアルコールとしては特に限定されず、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、イソブタノール等が挙げられる。得られるメタクリル酸エステルとしては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル等が挙げられる。反応は、スルホン酸型カチオン交換樹脂等の酸性触媒の存在下で行うことができる。反応温度は５０〜２００℃が好ましい。[Method for producing methacrylic acid ester]
The method for producing a methacrylic acid ester according to the present invention esterifies the methacrylic acid produced by the method according to the present invention. Further, in the method for producing a methacrylic acid ester according to the present invention, methacrylic acid is produced by the method according to the present invention, and the methacrylic acid is esterified. According to these methods, a methacrylic acid ester can be obtained by using the methacrylic acid obtained by the vapor phase catalytic oxidation of methacrolein. The alcohol to be reacted with methacrylic acid is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, n-butanol, and isobutanol. Examples of the obtained methacrylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like. The reaction can be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin. The reaction temperature is preferably 50 to 200 ° C.
以下、実施例および比較例により本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。実施例および比較例中の「部」は質量部を意味する。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. “Parts” in Examples and Comparative Examples means parts by mass.
触媒前駆体および触媒における各元素の組成比は、触媒または触媒前駆体をアンモニア水に溶解した成分をＩＣＰ発光分析法で分析することによって求めた。またアンモニウム根のモル比率は、触媒または触媒前駆体をケルダール法で分析することによって求めた。また、スラリーおよび溶液のｐＨは、ＨＯＲＩＢＡ製ポータブル型ｐＨメータＤ−７２（商品名）を用いて測定した。 The composition ratio of the catalyst precursor and each element in the catalyst was determined by analyzing the catalyst or a component obtained by dissolving the catalyst precursor in aqueous ammonia by ICP emission spectrometry. The molar ratio of ammonium roots was determined by analyzing the catalyst or catalyst precursor by the Kjeldahl method. The pH of the slurry and the solution was measured using a portable pH meter D-72 (trade name) manufactured by HORIBA.
原料ガスおよび生成物の分析は、ガスクロマトグラフィーを用いて行った。ガスクロマトグラフィーの結果から、メタクロレインの反応率およびメタクリル酸の選択率を下記式にて求めた。 Analysis of the source gas and product was performed using gas chromatography. From the results of gas chromatography, the reaction rate of methacrolein and the selectivity of methacrylic acid were determined by the following formulas.
メタクロレインの反応率（％）＝反応したメタクロレインのモル数／供給したメタクロレインのモル数×１００
メタクリル酸の選択率（％）＝生成したメタクリル酸のモル数／反応したメタクロレインのモル数×１００。Reaction rate of methacrolein (%) = number of moles of methacrolein reacted / number of moles of supplied methacrolein x 100
Methacrylic acid selectivity (%) = number of moles of methacrylic acid produced / number of moles of reacted methacrolein x 100.
［実施例１］
室温の純水１２００部に、三酸化モリブデン３００部、ニオブ酸シュウ酸アンモニウム２１部、８５質量％リン酸水溶液２０．１部を純水１８部で希釈した希釈物、６０質量％ヒ酸水溶液２４．６部を純水１８部で希釈した希釈物、および硝酸銅（ＩＩ）三水和物４．２部を純水９．０部に溶解した溶解物を混合し、スラリー（Ｉ）を得た。スラリー（Ｉ）を室温で撹拌しながら、重炭酸セシウム２３．５部および重炭酸カリウム５．２部を室温の純水６０部に溶解した溶解物と、炭酸アンモニウム２７．５部を室温の純水７３部に溶解した溶解物を滴下し、スラリー（ＩＩ）を得た。得られたスラリー（ＩＩ）を２℃／分で昇温し、９５℃にて２時間加熱撹拌した。スラリー（Ｉ）およびスラリー（ＩＩ）の調製において、スラリー（Ｉ）およびスラリー（ＩＩ）のｐＨは１．４〜５．５の範囲内で変化し、加熱撹拌後に得られたスラリー（ＩＩ）のｐＨは１．４〜２．５の範囲内であった。該スラリー（ＩＩ）を加熱して蒸発乾固させ、触媒前駆体を得た。得られた触媒前駆体の酸素を除く組成比を表１に示す。また、該触媒前駆体はケギン型構造を有していた。[Example 1]
A dilution of 1200 parts of pure water at room temperature, 300 parts of molybdenum trioxide, 21 parts of ammonium oxalate, 20.1 parts of 85 mass% phosphate aqueous solution diluted with 18 parts of pure water, and 60 mass% hydric acid aqueous solution 24. A dilution of .6 parts diluted with 18 parts of pure water and a solution of 4.2 parts of copper (II) nitrate trihydrate dissolved in 9.0 parts of pure water were mixed to obtain slurry (I). Diluted. While stirring the slurry (I) at room temperature, 23.5 parts of cesium carbonate and 5.2 parts of potassium bicarbonate were dissolved in 60 parts of pure water at room temperature, and 27.5 parts of ammonium carbonate were pure at room temperature. The dissolved solution was added dropwise to 73 parts of water to obtain a slurry (II). The temperature of the obtained slurry (II) was raised at 2 ° C./min, and the mixture was heated and stirred at 95 ° C. for 2 hours. In the preparation of the slurry (I) and the slurry (II), the pH of the slurry (I) and the slurry (II) varied in the range of 1.4 to 5.5, and the slurry (II) obtained after heating and stirring. The pH was in the range of 1.4-2.5. The slurry (II) was heated to evaporate to dryness to obtain a catalyst precursor. Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. In addition, the catalyst precursor had a kegin-type structure.
得られた触媒前駆体を加圧成形し、破砕し、粒径が７１０μｍ〜２．３６ｍｍの範囲内になるように篩いを用いて分級したものを、空気流通下、３８０℃で５時間焼成することで、触媒を製造した。得られた触媒の酸素を除く組成比を表２に示す。なお、該触媒におけるアンモニウム根のモル比率は０≦ｉ≦１であった。 The obtained catalyst precursor is pressure-molded, crushed, classified using a sieve so that the particle size is within the range of 710 μm to 2.36 mm, and calcined at 380 ° C. for 5 hours under air flow. This produced a catalyst. Table 2 shows the composition ratio of the obtained catalyst excluding oxygen. The molar ratio of ammonium roots in the catalyst was 0 ≦ i ≦ 1.
前記触媒を反応器に充填して、メタクロレイン５容量％、酸素１０容量％、水蒸気３０容量％および窒素５５容量％からなる原料ガスを流通させ、反応温度２８５℃にて反応評価を行った。なお触媒充填量は、メタクロレインの反応率が１３〜２７％の範囲内となるように調節した。反応後のガスを捕集し、ガスクロマトグラフィーで分析してメタクロレイン反応率とメタクリル酸選択率を算出した。結果を表２に示す。 The catalyst was filled in a reactor, and a raw material gas composed of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor and 55% by volume of nitrogen was circulated, and the reaction was evaluated at a reaction temperature of 285 ° C. The catalyst filling amount was adjusted so that the reaction rate of methacrolein was within the range of 13 to 27%. The gas after the reaction was collected and analyzed by gas chromatography to calculate the methacrolein reaction rate and the methacrylic acid selectivity. The results are shown in Table 2.
［実施例２］
実施例１において、ニオブ酸シュウ酸アンモニウムの仕込み量を１７部に、６０質量％ヒ酸水溶液の仕込み量を２０．５部に変更した点以外は、実施例１と同様の方法で触媒前駆体を製造した。スラリー（Ｉ）およびスラリー（ＩＩ）の調製において、スラリー（Ｉ）およびスラリー（ＩＩ）のｐＨは１．４〜５．６の範囲内で変化し、加熱撹拌後に得られたスラリー（ＩＩ）のｐＨは１．４〜２．５の範囲内であった。また、得られた触媒前駆体の酸素を除く組成比を表１に示す。また、該触媒前駆体はケギン型構造を有していた。[Example 2]
In Example 1, the catalyst precursor was prepared in the same manner as in Example 1 except that the amount of ammonium oxalate charged was changed to 17 parts and the amount of 60 mass% arsenic acid aqueous solution was changed to 20.5 parts. Manufactured. In the preparation of the slurry (I) and the slurry (II), the pH of the slurry (I) and the slurry (II) varied in the range of 1.4 to 5.6, and the slurry (II) obtained after heating and stirring The pH was in the range of 1.4-2.5. Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. In addition, the catalyst precursor had a kegin-type structure.
得られた触媒前駆体を、実施例１と同様の方法で成形および焼成して触媒を製造し、該触媒を用いて実施例１と同様の方法で反応評価を行った。触媒の酸素を除く組成比および反応評価結果を表２に示す。なお、該触媒におけるアンモニウム根のモル比率は０≦ｉ≦１であった。 The obtained catalyst precursor was molded and fired in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated using the catalyst in the same manner as in Example 1. Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results. The molar ratio of ammonium roots in the catalyst was 0 ≦ i ≦ 1.
［実施例３］
室温の純水１２００部に、三酸化モリブデン３００部、メタバナジン酸アンモニウム０．２２部、ニオブ酸シュウ酸アンモニウム１３部、８５質量％リン酸水溶液２０．１部を純水１８部で希釈した希釈物、６０質量％ヒ酸水溶液２４．６部を純水１８部で希釈した希釈物、および硝酸銅（ＩＩ）三水和物４．２部を純水９．０部に溶解した溶解物を混合し、スラリー（Ｉ）を得た。スラリー（Ｉ）を室温で撹拌しながら、重炭酸セシウム３３．６部を室温の純水６０部に溶解した溶解物と、炭酸アンモニウム２７．５部を室温の純水７３部に溶解した溶解物を滴下し、スラリー（ＩＩ）を得た。得られたスラリー（ＩＩ）を２℃／分で昇温し、９５℃にて２時間加熱撹拌した。スラリー（Ｉ）およびスラリー（ＩＩ）の調製において、スラリー（Ｉ）およびスラリー（ＩＩ）のｐＨは１．４〜５．６の範囲内で変化し、加熱撹拌後に得られたスラリー（ＩＩ）のｐＨは１．４〜２．５の範囲内であった。該スラリー（ＩＩ）を加熱して蒸発乾固させ、触媒前駆体を得た。得られた触媒前駆体の酸素を除く組成比を表１に示す。また、該触媒前駆体はケギン型構造を有していた。[Example 3]
A dilution of 1200 parts of pure water at room temperature, 300 parts of molybdenum trioxide, 0.22 parts of ammonium metavanadate, 13 parts of ammonium oxalate niobate, and 20.1 parts of 85 mass% aqueous phosphate solution diluted with 18 parts of pure water. , A dilution of 24.6 parts of a 60 mass% hydric acid aqueous solution diluted with 18 parts of pure water, and a solution of 4.2 parts of copper (II) nitrate trihydrate dissolved in 9.0 parts of pure water. The slurry (I) was obtained. While stirring the slurry (I) at room temperature, a solution in which 33.6 parts of cesium carbonate was dissolved in 60 parts of pure water at room temperature and a solution in which 27.5 parts of ammonium carbonate was dissolved in 73 parts of pure water at room temperature. Was added dropwise to obtain a slurry (II). The temperature of the obtained slurry (II) was raised at 2 ° C./min, and the mixture was heated and stirred at 95 ° C. for 2 hours. In the preparation of the slurry (I) and the slurry (II), the pH of the slurry (I) and the slurry (II) varied in the range of 1.4 to 5.6, and the slurry (II) obtained after heating and stirring The pH was in the range of 1.4-2.5. The slurry (II) was heated to evaporate to dryness to obtain a catalyst precursor. Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. In addition, the catalyst precursor had a kegin-type structure.
得られた触媒前駆体を、実施例１と同様の方法で成形および焼成して触媒を製造し、該触媒を用いて実施例１と同様の方法で反応評価を行った。触媒の酸素を除く組成比および反応評価結果を表２に示す。なお、該触媒におけるアンモニウム根のモル比率は０≦ｉ≦１であった。 The obtained catalyst precursor was molded and fired in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated using the catalyst in the same manner as in Example 1. Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results. The molar ratio of ammonium roots in the catalyst was 0 ≦ i ≦ 1.
［実施例４］
実施例３において、メタバナジン酸アンモニウムの仕込み量を２部に変更した点以外は、実施例３と同様の方法で触媒前駆体を製造した。スラリー（Ｉ）およびスラリー（ＩＩ）の調製において、スラリー（Ｉ）およびスラリー（ＩＩ）のｐＨは１．５〜５．７の範囲内で変化し、加熱撹拌後に得られたスラリー（ＩＩ）のｐＨは１．５〜２．５の範囲内であった。得られた触媒前駆体の酸素を除く組成比を表１に示す。また、該触媒前駆体はケギン型構造を有していた。[Example 4]
A catalyst precursor was produced in the same manner as in Example 3 except that the amount of ammonium metavanadate charged was changed to 2 parts in Example 3. In the preparation of the slurry (I) and the slurry (II), the pH of the slurry (I) and the slurry (II) varied in the range of 1.5 to 5.7, and the slurry (II) obtained after heating and stirring The pH was in the range of 1.5-2.5. Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. In addition, the catalyst precursor had a kegin-type structure.
得られた触媒前駆体を、実施例１と同様の方法で成形および焼成して触媒を製造し、該触媒を用いて実施例１と同様の方法で反応評価を行った。触媒の酸素を除く組成比および反応評価結果を表２に示す。なお、該触媒におけるアンモニウム根のモル比率は０≦ｉ≦１であった。 The obtained catalyst precursor was molded and fired in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated using the catalyst in the same manner as in Example 1. Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results. The molar ratio of ammonium roots in the catalyst was 0 ≦ i ≦ 1.
［実施例５］
室温の純水１２００部に、三酸化モリブデン３００部、メタバナジン酸アンモニウム４．１部、ニオブ酸シュウ酸アンモニウム１０．５部、８５質量％リン酸水溶液２０．１部を純水１８部で希釈した希釈物、６０質量％ヒ酸水溶液２４．６部を純水１８部で希釈した希釈物、および硝酸銅（ＩＩ）三水和物４．２部を純水９．０部に溶解した溶解物を混合し、スラリー（Ｉ）を得た。スラリー（Ｉ）を室温で撹拌しながら、重炭酸セシウム３０．３部および重炭酸カリウム１．７部を室温の純水６０部に溶解した溶解物と、炭酸アンモニウム２７．５部を室温の純水７３部に溶解した溶解物を滴下し、スラリー（ＩＩ）を得た。得られたスラリー（ＩＩ）を２℃／分で昇温し、９５℃にて２時間加熱撹拌した。スラリー（Ｉ）およびスラリー（ＩＩ）の調製において、スラリー（Ｉ）およびスラリー（ＩＩ）のｐＨは１．５〜５．７の範囲内で変化し、加熱撹拌後に得られたスラリー（ＩＩ）のｐＨは１．５〜２．５の範囲内であった。該スラリー（ＩＩ）を加熱して蒸発乾固させ、触媒前駆体を得た。得られた触媒前駆体の酸素を除く組成比を表１に示す。また、該触媒前駆体はケギン型構造を有していた。[Example 5]
300 parts of molybdenum trioxide, 4.1 parts of ammonium metavanadate, 10.5 parts of ammonium oxalate niobate, and 20.1 parts of 85 mass% phosphoric acid aqueous solution were diluted with 18 parts of pure water in 1200 parts of pure water at room temperature. Diluted product, diluted product obtained by diluting 24.6 parts of 60% by mass aqueous phosphoric acid solution with 18 parts of pure water, and dissolved product in which 4.2 parts of copper (II) nitrate trihydrate was dissolved in 9.0 parts of pure water. Was mixed to obtain a slurry (I). While stirring the slurry (I) at room temperature, 30.3 parts of cesium carbonate and 1.7 parts of potassium bicarbonate were dissolved in 60 parts of pure water at room temperature, and 27.5 parts of ammonium carbonate were pure at room temperature. The dissolved solution was added dropwise to 73 parts of water to obtain a slurry (II). The temperature of the obtained slurry (II) was raised at 2 ° C./min, and the mixture was heated and stirred at 95 ° C. for 2 hours. In the preparation of the slurry (I) and the slurry (II), the pH of the slurry (I) and the slurry (II) varied in the range of 1.5 to 5.7, and the slurry (II) obtained after heating and stirring The pH was in the range of 1.5-2.5. The slurry (II) was heated to evaporate to dryness to obtain a catalyst precursor. Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. In addition, the catalyst precursor had a kegin-type structure.
得られた触媒前駆体を、実施例１と同様の方法で成形および焼成して触媒を製造し、該触媒を用いて実施例１と同様の方法で反応評価を行った。触媒の酸素を除く組成比および反応評価結果を表２に示す。なお、該触媒におけるアンモニウム根のモル比率は０≦ｉ≦１であった。 The obtained catalyst precursor was molded and fired in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated using the catalyst in the same manner as in Example 1. Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results. The molar ratio of ammonium roots in the catalyst was 0 ≦ i ≦ 1.
［比較例１］
実施例５において、メタバナジン酸アンモニウムの仕込み量を８．２部に、重炭酸セシウムの仕込み量を２３．５部に、重炭酸カリウムの仕込み量を５．２部に変更し、ニオブ酸シュウ酸アンモニウムを用いなかった点以外は、実施例５と同様の方法で触媒前駆体を製造した。スラリー（Ｉ）およびスラリー（ＩＩ）の調製において、スラリー（Ｉ）およびスラリー（ＩＩ）のｐＨは１．５〜５．７の範囲内で変化し、加熱撹拌後に得られたスラリー（ＩＩ）のｐＨは１．５〜２．５の範囲内であった。得られた触媒前駆体の酸素を除く組成比を表１に示す。また、該触媒前駆体はケギン型構造を有していた。[Comparative Example 1]
In Example 5, the amount of ammonium metavanadate charged was changed to 8.2 parts, the amount of cesium bicarbonate charged was changed to 23.5 parts, and the amount of potassium bicarbonate charged was changed to 5.2 parts. A catalyst precursor was produced in the same manner as in Example 5 except that ammonium was not used. In the preparation of the slurry (I) and the slurry (II), the pH of the slurry (I) and the slurry (II) varied in the range of 1.5 to 5.7, and the slurry (II) obtained after heating and stirring The pH was in the range of 1.5-2.5. Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. In addition, the catalyst precursor had a kegin-type structure.
得られた触媒前駆体を、実施例１と同様の方法で成形および焼成して触媒を製造し、該触媒を用いて実施例１と同様の方法で反応評価を行った。触媒の酸素を除く組成比および反応評価結果を表２に示す。なお、該触媒におけるアンモニウム根のモル比率は０≦ｉ≦１であった。 The obtained catalyst precursor was molded and fired in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated using the catalyst in the same manner as in Example 1. Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results. The molar ratio of ammonium roots in the catalyst was 0 ≦ i ≦ 1.
［比較例２］
純水１２００部に、三酸化モリブデン３００部、メタバナジン酸アンモニウム４．１部、ニオブ酸シュウ酸アンモニウム１０．５部、五酸化アンチモン２２．８部、８５質量％リン酸水溶液２０．１部を純水１８部で希釈した希釈物、６０質量％ヒ酸水溶液２４．６部を純水１８部で希釈した希釈物、および硝酸銅（ＩＩ）三水和物４．２部を純水９．０部に溶解した溶解物を混合し、スラリー（Ｉ）を得た。スラリー（Ｉ）を室温で撹拌しながら、重炭酸セシウム３０．３部および重炭酸カリウム１．７部を室温の純水６０部に溶解した溶解物と、炭酸アンモニウム２７．５部を室温の純水７３部に溶解した溶解物を滴下し、スラリー（ＩＩ）を得た。得られたスラリー（ＩＩ）を２℃／分で昇温し、９５℃にて２時間加熱撹拌した。スラリー（Ｉ）およびスラリー（ＩＩ）の調製において、スラリー（Ｉ）およびスラリー（ＩＩ）のｐＨは１．５〜５．７の範囲内で変化し、加熱撹拌後に得られたスラリー（ＩＩ）のｐＨは１．５〜２．５の範囲内であった。該スラリー（ＩＩ）を加熱して蒸発乾固させ、触媒前駆体を得た。得られた触媒前駆体の酸素を除く組成比を表１に示す。また、該触媒前駆体はケギン型構造を有していた。[Comparative Example 2]
In 1200 parts of pure water, 300 parts of molybdenum trioxide, 4.1 parts of ammonium metavanadate, 10.5 parts of ammonium oxalate niobate, 22.8 parts of antimony pentoxide, and 20.1 parts of 85 mass% phosphoric acid aqueous solution are pure. A diluted solution diluted with 18 parts of water, a diluted solution of 24.6 parts of a 60 mass% phosphoric acid aqueous solution diluted with 18 parts of pure water, and 4.2 parts of copper (II) nitrate trihydrate in pure water 9.0. The lysate dissolved in the part was mixed to obtain a slurry (I). While stirring the slurry (I) at room temperature, 30.3 parts of cesium carbonate and 1.7 parts of potassium bicarbonate were dissolved in 60 parts of pure water at room temperature, and 27.5 parts of ammonium carbonate were pure at room temperature. The dissolved solution was added dropwise to 73 parts of water to obtain a slurry (II). The temperature of the obtained slurry (II) was raised at 2 ° C./min, and the mixture was heated and stirred at 95 ° C. for 2 hours. In the preparation of the slurry (I) and the slurry (II), the pH of the slurry (I) and the slurry (II) varied in the range of 1.5 to 5.7, and the slurry (II) obtained after heating and stirring The pH was in the range of 1.5-2.5. The slurry (II) was heated to evaporate to dryness to obtain a catalyst precursor. Table 1 shows the composition ratio of the obtained catalyst precursor excluding oxygen. In addition, the catalyst precursor had a kegin-type structure.
得られた触媒前駆体を、実施例１と同様の方法で成形および焼成して触媒を製造し、該触媒を用いて実施例１と同様の方法で反応評価を行った。触媒の酸素を除く組成比および反応評価結果を表２に示す。なお、該触媒におけるアンモニウム根のモル比率は０≦ｉ≦１であった。 The obtained catalyst precursor was molded and fired in the same manner as in Example 1 to produce a catalyst, and the reaction was evaluated using the catalyst in the same manner as in Example 1. Table 2 shows the composition ratio of the catalyst excluding oxygen and the reaction evaluation results. The molar ratio of ammonium roots in the catalyst was 0 ≦ i ≦ 1.
表１および表２に示されるように、実施例１〜５では、触媒前駆体および触媒の組成比が本発明の範囲内にあり、メタクリル酸選択率が高い触媒であることが確認された。一方、ニオブ組成比が本発明の範囲外である比較例１およびａ＋ｆの値が本発明の範囲外である比較例２は、実施例１〜５と比較してメタクリル酸選択率が低い結果となった。 As shown in Tables 1 and 2, it was confirmed that in Examples 1 to 5, the composition ratio of the catalyst precursor and the catalyst was within the range of the present invention, and the catalyst had a high methacrylic acid selectivity. On the other hand, Comparative Example 1 in which the niobium composition ratio is outside the range of the present invention and Comparative Example 2 in which the value of a + f is outside the range of the present invention have a result that the methacrylic acid selectivity is lower than that in Examples 1 to 5. became.
なお、本実施例で得られたメタクリル酸をエステル化することで、メタクリル酸エステルを得ることができる。 A methacrylic acid ester can be obtained by esterifying the methacrylic acid obtained in this example.
この出願は、２０１７年２月１７日に出願された日本出願特願２０１７−０２８１７４を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application claims priority on the basis of Japanese application Japanese Patent Application No. 2017-028174 filed on February 17, 2017, the entire disclosure of which is incorporated herein by reference.
以上、実施形態および実施例を参照して本願発明を説明したが、本願発明は上記実施形態および実施例に限定されるものではない。本願発明の構成や詳細には、本願発明のスコープ内で当業者が理解し得る様々な変更をすることができる。 Although the present invention has been described above with reference to the embodiments and examples, the present invention is not limited to the above embodiments and examples. Various changes that can be understood by those skilled in the art can be made within the scope of the present invention in terms of the structure and details of the present invention.
本発明に係るメタクリル酸製造用触媒は、高い選択率でメタクリル酸を製造することができるため、工業的にメタクリル酸を製造する際に有用である。 The catalyst for producing methacrylic acid according to the present invention can produce methacrylic acid with a high selectivity, and is therefore useful for industrially producing methacrylic acid.
Claims (9)
ＰａＭｏｂＶｃＮｂｄＣｕｅＡｆＥｇＧｈ（ＮＨ４）ｉＯｊ （１）
（式（１）中、Ｐ、Ｍｏ、Ｖ、Ｎｂ、Ｃｕ、ＮＨ４およびＯは、それぞれ、リン、モリブデン、バナジウム、ニオブ、銅、アンモニウム根および酸素を表す。Ａはケイ素、ゲルマニウム、ヒ素およびアンチモンからなる群から選択される少なくとも１種の元素を表す。Ｅはビスマス、ジルコニウム、テルル、銀、セレン、タングステン、ホウ素、鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、インジウム、硫黄、パラジウム、ガリウム、セリウムおよびランタンからなる群から選択される少なくとも１種の元素を示す。Ｇ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から選択される少なくとも１種の元素を表す。ａ〜ｊは、各成分のモル比率を表し、ｂ＝１２の時、１．３≦ａ＋ｆ≦２．１、０．０１≦ｃ＋ｄ≦３、０．３５≦ｄ／（ｃ＋ｄ）≦１、０．５≦ａ、０≦ｃ、０．０１≦ｄ≦３、０．００５≦ｅ≦３、０≦ｆ、０≦ｇ≦３、０．０１≦ｈ≦３、０≦ｉ≦５を満たし、ｊは前記各成分の価数を満足するのに必要な酸素のモル比率である。） A catalyst for producing methacrylic acid having a composition represented by the following formula (1), which is used when methacrolein is vapor-phase catalytically oxidized with molecular oxygen to produce methacrylic acid.
P a Mo b V c Nb d Cu e A f E g G h (NH 4 ) i O j (1)
(In formula (1), P, Mo, V, Nb, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, niobium, copper, ammonium root and oxygen, respectively. A represents silicon, germanium, arsenic and Represents at least one element selected from the group consisting of antimony. E represents bismuth, zirconium, tellurium, silver, selenium, tungsten, boron, iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, Indicates at least one element selected from the group consisting of manganese, barium, titanium, tin, lead, indium, sulfur, palladium, gallium, cerium and lanthanum. G is from lithium, sodium, potassium, rubidium, cesium and tarium. Represents at least one element selected from the group. A to j represent the molar ratio of each component, and when b = 12, 1.3 ≤ a + f ≤ 2.1, 0.01 ≤ c + d ≤ 3. , 0.35 ≦ d / (c + d) ≦ 1, 0.5 ≦ a, 0 ≦ c, 0.01 ≦ d ≦ 3, 0.005 ≦ e ≦ 3, 0 ≦ f, 0 ≦ g ≦ 3,0 .01 ≦ h ≦ 3 and 0 ≦ i ≦ 5 are satisfied, and j is the molar ratio of oxygen required to satisfy the valence of each component.)
ＰａＭｏｂＶｃＮｂｄＣｕｅＡｆＥｇＧｈ（ＮＨ４）ｉＯｊ （２）
（式（２）中、Ｐ、Ｍｏ、Ｖ、Ｎｂ、Ｃｕ、ＮＨ４およびＯは、それぞれ、リン、モリブデン、バナジウム、ニオブ、銅、アンモニウム根および酸素を表す。Ａはケイ素、ゲルマニウム、ヒ素およびアンチモンからなる群から選択される少なくとも１種の元素を表す。Ｅはビスマス、ジルコニウム、テルル、銀、セレン、タングステン、ホウ素、鉄、亜鉛、クロム、マグネシウム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、バリウム、チタン、スズ、鉛、インジウム、硫黄、パラジウム、ガリウム、セリウムおよびランタンからなる群から選択される少なくとも１種の元素を示す。Ｇ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から選択される少なくとも１種の元素を表す。ａ〜ｊは、各成分のモル比率を表し、ｂ＝１２の時、１．３≦ａ＋ｆ≦２．４、０．０１≦ｃ＋ｄ≦３、０．３５≦ｄ／（ｃ＋ｄ）≦１、０．５≦ａ、０≦ｃ、０．０１≦ｄ≦３、０．００５≦ｅ≦３、０≦ｆ、０≦ｇ≦３、０．０１≦ｈ≦３、０．１≦ｉ≦２０を満たし、ｊは前記各成分の価数を満足するのに必要な酸素のモル比率である。） It is a precursor of a catalyst used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen, has a kegin-type structure, and has a composition represented by the following formula (2). Catalyst precursor for methacrylic acid production.
P a Mo b V c Nb d Cu e A f E g G h (NH 4 ) i O j (2)
(In formula (2), P, Mo, V, Nb, Cu, NH 4 and O represent phosphorus, molybdenum, vanadium, niobium, copper, ammonium root and oxygen, respectively. A represents silicon, germanium, arsenic and Represents at least one element selected from the group consisting of antimony. E represents bismuth, zirconium, tellurium, silver, selenium, tungsten, boron, iron, zinc, chromium, magnesium, calcium, strontium, tantalum, cobalt, nickel, Indicates at least one element selected from the group consisting of manganese, barium, titanium, tin, lead, indium, sulfur, palladium, gallium, cerium and lanthanum. G is from lithium, sodium, potassium, rubidium, cesium and tarium. Represents at least one element selected from the group. A to j represent the molar ratio of each component, and when b = 12, 1.3 ≤ a + f ≤ 2.4, 0.01 ≤ c + d ≤ 3. , 0.35 ≦ d / (c + d) ≦ 1, 0.5 ≦ a, 0 ≦ c, 0.01 ≦ d ≦ 3, 0.005 ≦ e ≦ 3, 0 ≦ f, 0 ≦ g ≦ 3,0 0.01 ≦ h ≦ 3 and 0.1 ≦ i ≦ 20, and j is the molar ratio of oxygen required to satisfy the valence of each component.)
（ｉ）少なくともモリブデンの原料を含むスラリー（Ｉ）または溶液（Ｉ）を調製する工程と、
（ｉｉ）前記スラリー（Ｉ）または前記溶液（Ｉ）にアンモニウム化合物を添加して、アンモニウム塩を含むスラリー（ＩＩ）を調製する工程と、
（ｉｉｉ）前記スラリー（ＩＩ）を乾燥し、前記ケギン型構造を有するメタクリル酸製造用触媒前駆体を得る工程と、
を含み、
前記工程（ｉ）および（ｉｉ）において、前記スラリー（Ｉ）、前記溶液（Ｉ）、および前記スラリー（ＩＩ）のｐＨを０．１〜６．５の範囲内に維持するメタクリル酸製造用触媒前駆体の製造方法。 The method for producing a catalyst precursor for producing methacrylic acid according to claim 2 .
(I) A step of preparing a slurry (I) or a solution (I) containing at least a molybdenum raw material, and
(Ii) A step of adding an ammonium compound to the slurry (I) or the solution (I) to prepare a slurry (II) containing an ammonium salt.
(Iii) A step of drying the slurry (II) to obtain a catalyst precursor for producing methacrylic acid having the kegin-type structure.
Including
A catalyst for producing methacrylic acid that maintains the pH of the slurry (I), the solution (I), and the slurry (II) in the range of 0.1 to 6.5 in the steps (i) and (ii). Method for producing a precursor.
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| JP7441474B2 (en) * | 2020-03-31 | 2024-03-01 | 三菱ケミカル株式会社 | Catalyst, method for producing isobutyraldehyde and methacrolein, method for producing methacrylic acid, and method for producing methacrylic acid ester |
| CA3173600A1 (en) * | 2020-05-08 | 2021-11-11 | Air Company Holdings, Inc. | Molybdenum-based catalysts for carbon dioxide conversion |
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| US4252682A (en) * | 1978-12-26 | 1981-02-24 | Halcon Research And Development Corp. | Catalyst for producing methacrylic acid |
| JPH0832644B2 (en) * | 1988-04-05 | 1996-03-29 | 旭化成工業株式会社 | Method for producing methacrylic acid and / or methacrolein |
| JP3370589B2 (en) * | 1997-12-25 | 2003-01-27 | 三菱レイヨン株式会社 | Catalyst for producing methacrylic acid and method for producing methacrylic acid using the same |
| JPH11228487A (en) | 1998-02-18 | 1999-08-24 | Mitsubishi Rayon Co Ltd | Production of methacrylic acid |
| JP4045693B2 (en) * | 1999-04-27 | 2008-02-13 | 住友化学株式会社 | Method for producing methacrylic acid |
| JP4222721B2 (en) * | 2000-12-25 | 2009-02-12 | 三菱レイヨン株式会社 | Method for producing methacrylic acid |
| SG156608A1 (en) * | 2003-10-27 | 2009-11-26 | Mitsubishi Rayon Co | Method for producing catalyst for methacrylic acid production, catalyst for methacrylic acid production, and method for producing methacrylic acid |
| JP2006314923A (en) * | 2005-05-12 | 2006-11-24 | Nippon Kayaku Co Ltd | Manufacturing method of catalyst for producing methacrylic acid |
| JP2012102129A (en) * | 2012-01-05 | 2012-05-31 | Mitsubishi Rayon Co Ltd | Methacrylic acid purification method |
| JP5915895B2 (en) * | 2012-03-16 | 2016-05-11 | 三菱レイヨン株式会社 | Method for producing a catalyst for methacrylic acid production |
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