JP2934267B2 - Method for producing methacrolein and methacrylic acid - Google Patents
Method for producing methacrolein and methacrylic acidInfo
- Publication number
- JP2934267B2 JP2934267B2 JP1315163A JP31516389A JP2934267B2 JP 2934267 B2 JP2934267 B2 JP 2934267B2 JP 1315163 A JP1315163 A JP 1315163A JP 31516389 A JP31516389 A JP 31516389A JP 2934267 B2 JP2934267 B2 JP 2934267B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- methacrylic acid
- same manner
- results
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 27
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000003054 catalyst Substances 0.000 claims description 167
- 238000006243 chemical reaction Methods 0.000 claims description 74
- 239000007789 gas Substances 0.000 claims description 35
- 230000000694 effects Effects 0.000 claims description 34
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 24
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 14
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 12
- 238000005338 heat storage Methods 0.000 description 11
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 3
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ALRXDIKPRCRYAU-UHFFFAOYSA-N 2-methylpropan-2-ol Chemical compound CC(C)(C)O.CC(C)(C)O ALRXDIKPRCRYAU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 and finally Chemical compound 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 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 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、イソブチレン、ｔ−ブタノール（ターシャ
リーブタノール）およびメチル−ｔ−ブチルエーテル
（メチルターシャリーブチルエーテル）から選ばれる少
なくとも１種の化合物を出発原料とし、この出発原料を
分子状酸素または分子状酸素含有ガスにより気相接触酸
化してメタクロレインおよびメタクリル酸を製造する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention starts with at least one compound selected from isobutylene, t-butanol (tert-butanol) and methyl-t-butyl ether (methyl tert-butyl ether). The present invention relates to a method for producing methacrolein and methacrylic acid by subjecting this starting material to gas-phase catalytic oxidation with molecular oxygen or a gas containing molecular oxygen.
（従来の技術） イソブチレンおよび／またはｔ−ブタノールを高温気
相酸化してメタクロレインおよびメタクリル酸を製造す
る際に用いられる触媒に関しては数多くの提案がなされ
ている。これらは主として触媒を構成する成分およびそ
の比率の選択にかかわるものである。(Prior Art) Numerous proposals have been made regarding catalysts used for producing methacrolein and methacrylic acid by subjecting isobutylene and / or t-butanol to high-temperature vapor-phase oxidation. These are mainly concerned with the selection of the components constituting the catalyst and the ratio thereof.
上記酸化反応は非常な発熱反応であるため、触媒層で
の蓄熱が大きく、特にホットスポットと呼ばれる局所的
異常高温帯では過度の酸化反応により収率が低下するの
みならず、熱負荷による触媒の劣化により触媒寿命が大
きな影響を受けることになる。このため、工業的実施に
おいては、ホットスポット部における蓄熱が重大な問題
となり、特に生産性を上げるために出発原料濃度を高め
たり、空間速度を高めたりすると（以下、「高負荷反応
条件下」という場合もある）、ホットスポット部におけ
る蓄熱が顕著となる傾向があることから、反応条件に関
しかなりの制約を受けているのが現状である。Since the above-mentioned oxidation reaction is a very exothermic reaction, the heat storage in the catalyst layer is large, and particularly in a local abnormal high-temperature zone called a hot spot, not only the yield decreases due to an excessive oxidation reaction, but also the catalyst of the catalyst due to heat load. The catalyst life is greatly affected by the deterioration. For this reason, in industrial practice, heat storage in the hot spot becomes a serious problem, especially when the starting material concentration is increased or the space velocity is increased in order to increase productivity (hereinafter referred to as “high load reaction conditions”). However, since the heat storage in the hot spot tends to be remarkable, the reaction conditions are considerably restricted at present.
従って、このホットスポット部での蓄熱を抑えること
は、工業的に高収率でメタクロレインおよびメタクリル
酸を生産する上でも、また触媒の劣化を抑えて長期間に
わかり安定した運転を可能とする上でも非常に重要なこ
とである。特に、モリブデン系触媒の場合、モリブデン
成分が容易に昇華しやすいことからホットスポット部で
の蓄熱を防止することは重要である。Therefore, suppressing the heat storage in this hot spot portion enables industrially high production of methacrolein and methacrylic acid with a high yield, and also enables long-term stable operation by suppressing the deterioration of the catalyst. This is also very important above. In particular, in the case of a molybdenum-based catalyst, it is important to prevent heat storage at the hot spot portion because the molybdenum component is easily sublimated.
ホットスポット部での蓄熱を抑える方法として、過去
にいくつかの提案がなされている。例えば、特公昭62−
36740号公報には、触媒形状をリング状にすることが提
案されている。この公報には、イソブチレンまたはｔ−
ブタノールの酸化用触媒として通常用いられている成型
触媒において、形状を球状あるいは円柱状からリング状
にかえることにより、ホットスポット部での蓄熱を抑
え、過度の酸化反応を抑えることができるために、収率
の向上に大きな効果があると述べられている。しかし、
この方法は、熱負荷を低減させる効果は認められるもの
の、特に高負荷反応条件下では充分満足のいく結果が得
られるとはいえない。Some proposals have been made in the past as a method of suppressing heat storage in a hot spot. For example,
No. 36740 proposes that the shape of the catalyst be ring-shaped. This publication states that isobutylene or t-
By changing the shape from a spherical shape or a cylindrical shape to a ring shape in a molded catalyst generally used as a catalyst for oxidizing butanol, heat storage at a hot spot portion can be suppressed, and an excessive oxidation reaction can be suppressed. It is stated that there is a great effect on improving the yield. But,
Although this method has the effect of reducing the heat load, it cannot be said that sufficiently satisfactory results can be obtained, particularly under high load reaction conditions.
そのほか、触媒層を分割して複数個の反応帯を設け、
この複数個の反応帯に活性の異なる触媒を充填して酸化
反応に供する方法も、例えばプロピレンからアクロレイ
ンおよびアクリル酸を製造する方法として、特公昭63−
38331号公報によって知られている。In addition, the catalyst layer is divided to provide multiple reaction zones,
A method of filling a plurality of reaction zones with catalysts having different activities and subjecting them to an oxidation reaction is also known as a method for producing acrolein and acrylic acid from propylene, for example, as disclosed in
No. 38331 is known.
また、特開昭51−127013号公報には、プロピレンおよ
びイソブチレンから不飽和アルデヒドおよび酸を製造す
る方法として、本質的に同一組成からなる担持型触媒と
成型触媒との組合せが開示されているが、実施例中には
プロピレンからアクロレインならびにアクリル酸を製造
する例が示されているが、イソブチレンからメタクロレ
インならびにメタクリル酸を製造する場合については具
体的に開示されておらず、その効果について評価するの
は困難である。JP-A-51-227013 discloses a method for producing an unsaturated aldehyde and an acid from propylene and isobutylene using a combination of a supported catalyst and a molded catalyst having essentially the same composition. In the examples, examples of producing acrolein and acrylic acid from propylene are shown, but the case of producing methacrolein and methacrylic acid from isobutylene is not specifically disclosed, and the effects thereof are evaluated. It is difficult.
イソブチレン、ｔ−ブタノールあるいはメチル−ｔ−
ブチルエーテルを気相接触酸化してメタクロレインおよ
びメタクリル酸を生成する反応においては、これら出発
原料はいずれもプロピレンと異なりα−位にメチル基が
存在するために、並列反応、逐次反応などの副反応が多
く、副生成物は数、量とも多い。例えば、イソブチレン
からメタクロレインおよびメタクリル酸を生成する場合
の反応熱は、プロピレンからアクロレインおよびアクリ
ル酸を生成する場合のそれよりも大きく、このことが触
媒層の蓄熱を助長し、副反応による副生成物の増加を促
進している。しかも、メタクロレインは、アクロレイン
に比べて不安定で自動酸化などのいわゆる「後反応」を
起こし易く、これが収率を更に低下させる原因となって
いる。Isobutylene, t-butanol or methyl-t-
In the reaction to produce methacrolein and methacrylic acid by gas-phase catalytic oxidation of butyl ether, these starting materials are different from propylene in that a methyl group is present at the α-position. , And the number and amount of by-products are large. For example, the heat of reaction when producing methacrolein and methacrylic acid from isobutylene is greater than that when producing acrolein and acrylic acid from propylene, which promotes the heat storage of the catalyst layer and produces by-products by side reactions. It is promoting the increase of things. In addition, methacrolein is unstable compared to acrolein and easily causes so-called "post-reaction" such as autoxidation, which causes the yield to be further reduced.
以上のように、イソブチレン、ｔ−ブタノールあるい
はメチル−ｔ−ブチルエーテルを酸化してメタクロレイ
ンおよびメタクリル酸を生成する反応は、プロピレンを
酸化してアクロレインおよびアクリル酸を生成する反応
に比べ、複雑で、目的物を高収率で得ることが困難であ
る。従って、従来より、アクロレイン、アクリル酸など
の製造で得られている知見をそのままメタクロレインあ
るいはメタクリル酸の製造に適用しても充分な効果を得
ることが期待できず、メタクロレインあるいはメタクリ
ル酸の製造に好適な触媒もしくは方法を開発するには更
なる検討が必要とされてきた。As described above, the reaction of oxidizing isobutylene, t-butanol or methyl-t-butyl ether to produce methacrolein and methacrylic acid is more complicated than the reaction of oxidizing propylene to produce acrolein and acrylic acid, It is difficult to obtain the desired product in high yield. Therefore, it is not expected that a sufficient effect can be expected even if the knowledge obtained in the production of acrolein or acrylic acid is applied to the production of methacrolein or methacrylic acid as it is, and the production of methacrolein or methacrylic acid is not expected. Further studies have been needed to develop suitable catalysts or methods.
（発明が解決しようとする課題） 本発明の一つの目的は、イソブチレン、ｔ−ブタノー
ルおよびメチル−ｔ−ブチルエーテルから選ばれる少な
くとも１種を気相接触酸化してメタクロレインおよびメ
タクリル酸を高収率で製造する方法を提供することであ
る。(Problems to be Solved by the Invention) An object of the present invention is to provide a high yield of methacrolein and methacrylic acid by subjecting at least one selected from isobutylene, t-butanol and methyl-t-butyl ether to gas phase catalytic oxidation. It is to provide a method of manufacturing with.
本発明の他の目的は、イソブチレン、ｔ−ブタノール
およびメチル−ｔ−ブチルエーテルから選ばれる少なく
とも１種を気相接触酸化してメタクロレインおよびメタ
クリル酸を製造する際、触媒層内のホットスポット部に
おける蓄熱を抑制し、メタクロレインおよびメタクリル
酸の収率の向上を図るとともに触媒の劣化を防止して触
媒を長時間にわたって安定に使用できるようにしたメタ
クロレインおよびメタクリル酸の製造方法を提供するこ
とである。Another object of the present invention is to provide at least one selected from isobutylene, t-butanol and methyl-t-butyl ether in the gas phase catalytic oxidation to produce methacrolein and methacrylic acid. By providing a method for producing methacrolein and methacrylic acid, which suppresses heat storage, improves the yield of methacrolein and methacrylic acid, and prevents catalyst deterioration so that the catalyst can be used stably for a long time. is there.
本発明の他の目的は、イソブチレン、ｔ−ブタノール
およびメチル−ｔ−ブチルエーテルから選ばれる少なく
とも１種を高負荷反応条件下において気相接触酸化して
メタクロレインおよびメタクリル酸を製造する際、触媒
層内のホットスポット部における蓄熱を抑制し、メタク
ロレインおよびメタクリル酸の収率の向上をはかるとと
もに触媒の劣化を防止して触媒を長時間にわたって安定
に使用できるようにし、ひいては生産性を著しく向上さ
せたメタクロレインおよびメタクリル酸の製造方法を提
供することである。Another object of the present invention is to provide a catalyst layer for producing methacrolein and methacrylic acid by subjecting at least one selected from isobutylene, t-butanol and methyl-t-butyl ether to gas-phase catalytic oxidation under high-load reaction conditions. In order to improve the yield of methacrolein and methacrylic acid and to prevent the catalyst from deteriorating, the catalyst can be used stably over a long period of time, thereby significantly improving the productivity. To provide a method for producing methacrolein and methacrylic acid.
（課題を解決するための手段） 本発明者らは、複数個の活性の異なる特定のモリブデ
ン系触媒を調製し、一方触媒層を２層以上に分割して複
数個の反応帯を設け、これら複数個の反応帯に上記活性
の異なる複数個のモリブデン系触媒を原料ガス入口部か
ら出口部に向かって活性がより高くなるように充填する
ことにより上記目的が達成できることを知り、この知見
に基づいて本発明を完成するに至った。(Means for Solving the Problems) The present inventors prepared a plurality of specific molybdenum-based catalysts having different activities, and provided a plurality of reaction zones by dividing a catalyst layer into two or more layers. It was found that the above object can be achieved by filling a plurality of reaction zones with a plurality of molybdenum-based catalysts having different activities from the raw material gas inlet to the outlet so that the activity becomes higher. Thus, the present invention has been completed.
すなわち、本発明は、固定床多管型反応器を用いてイ
ソブチレン、ｔ−ブタノールおよびメチル−ｔ−ブチル
エーテルから選ばれる少なくとも１種を分子状酸素また
は分子状酸素含有ガスにより気相接触酸化によりメタク
ロレインおよびメタクリル酸を製造する方法において、 （イ）触媒として、下記一般式（Ｉ） MoaWbBicFedAeBfCgDhEiOx （式中、Moはモリブデン、Ｗはタングステン、Biはビス
マス、Feは鉄、Ａはニッケルおよびコバルトから選ばれ
る少なくとも１種の元素、Ｂはアルカル金属およびタリ
ウムから選ばれる少なくとも１種の元素、Ｃはアルカリ
土類金属から選ばれる少なくとも１種の元素、Ｄはリ
ン、テルル、アンチモン、スズ、セリウム、鉛、ニオ
ブ、マンガン、ヒ素および亜鉛から選ばれる少なくとも
１種の元素、Ｅはシリコン、アルミニウム、チタニウム
およびジルコニウムから選ばれる少なくとも１種の元
素、Ｏは酸素を表し、またａ、ｂ、ｃ、ｄ、ｅ、ｆ、
ｇ、ｈ、ｉおよびｘはそれぞれMo、Ｗ、Bi、Fe、Ａ、
Ｂ、Ｃ、Ｄ、ＥおよびＯの原子数を表し、ａ＝12とした
とき、ｂ＝０〜10、ｃ＝0.1〜10、ｄ＝0.1〜20、ｅ＝２
〜20、ｆ＝0.001〜10、ｇ＝０〜10、ｈ＝０〜４、ｉ＝
０〜30、ｘ＝各々の元素の酸化状態によって定まる数値
である） で表される複合酸化物を使用し、 （ロ）各反応管内に触媒層を管軸方向に２層以上に分割
して設けた複数個の反応帯に、 （ハ）上記（イ）の触媒において、一般式（Ｉ）におけ
るＢ群元素の種類および／または量を変更して調製した
活性の異なる複数個の触媒を原料ガス入口部から出口部
に向かって活性がより高くなるように充填することを特
徴とするメタクロレインおよびメタクリル酸の製造方法
に関する。That is, the present invention uses a fixed-bed multitubular reactor to convert at least one selected from isobutylene, t-butanol and methyl-t-butyl ether by molecular gas oxidation or a gas containing a molecular oxygen by gas phase catalytic oxidation. a process for preparing and methacrylic acid, as (i) a catalyst, the following general formula (I) in Mo a W b Bi c Fe d a e B f C g D h E i O x ( wherein, Mo is molybdenum, W is tungsten, Bi is bismuth, Fe is iron, A is at least one element selected from nickel and cobalt, B is at least one element selected from alkali metals and thallium, and C is selected from alkaline earth metals At least one element, wherein D is at least one element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic, and zinc At least one element E is selected silicon, aluminum, titanium and zirconium, O represents oxygen, also a, b, c, d, e, f,
g, h, i and x are Mo, W, Bi, Fe, A,
Represents the number of atoms of B, C, D, E and O, and when a = 12, b = 0 to 10, c = 0.1 to 10, d = 0.1 to 20, e = 2
-20, f = 0.001-10, g = 0-10, h = 0-4, i =
0 to 30, x = a value determined by the oxidation state of each element). (B) The catalyst layer is divided into two or more layers in the tube axis direction in each reaction tube. (C) a plurality of catalysts having different activities prepared by changing the type and / or amount of the group B element in the general formula (I) in the catalyst of the above (a); The present invention relates to a method for producing methacrolein and methacrylic acid, which is filled so that the activity becomes higher from the gas inlet toward the outlet.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明で使用する出発原料は、イソブチレン、ｔ−ブ
タノールおよびメチル−ｔ−ブチルエーテルから選ばれ
る少なくとも１種の化合物であり、通常、分子状酸素、
水蒸気、不活性ガス、例えば窒素、炭酸ガスなどととも
に混合ガスとして反応に供する。The starting material used in the present invention is at least one compound selected from isobutylene, t-butanol and methyl-t-butyl ether.
The mixture is supplied to the reaction as a mixed gas together with steam, an inert gas such as nitrogen and carbon dioxide.
本発明で使用する触媒は、上記一般式（Ｉ）によって
表される複合酸化物である。この触媒の調製方法および
原料については特に制限はなく、この種の触媒の調製に
一般に使用されている方法および原料を用いて調製する
ことができる。The catalyst used in the present invention is a composite oxide represented by the general formula (I). The method for preparing the catalyst and the raw materials are not particularly limited, and the catalyst can be prepared using the methods and raw materials generally used for preparing this type of catalyst.
なお、上記一般式（Ｉ）において、Ｗ成分、Ｃ成分、
Ｄ成分およびＥ成分は任意成分である。In the above general formula (I), W component, C component,
The D component and the E component are optional components.
本発明においては、一般式（Ｉ）で表される、活性の
異なる複数個の触媒を調製して、これら複数個の触媒を
特定の配列で充填するが、活性の異なる触媒は一般式
（Ｉ）においてＢ群元素の種類および／または量を変え
ることによって容易に調製することができる。すなわ
ち、リチウム、ナトリウム、カリウム、ルビジウム、セ
シウムなどのアルカリ金属およびタリウムから選ばれる
少なくとも１種の元素の種類および／または量（但し、
一般式（Ｉ）において、ｆによって規定される原子比内
で）を変えることによって活性の異なる触媒が得られ
る。In the present invention, a plurality of catalysts having different activities represented by the general formula (I) are prepared, and the plurality of catalysts are packed in a specific sequence. ) Can be easily prepared by changing the type and / or amount of the group B element. That is, the kind and / or amount of at least one element selected from alkali metals such as lithium, sodium, potassium, rubidium and cesium and thallium (however,
By changing the general formula (I) (within the atomic ratio defined by f), catalysts having different activities can be obtained.
本発明で使用する触媒は、一般式（Ｉ）で表される元
素成分から構成され、これら元素成分の組合せによって
本発明の目的が達成されるが、これら元素成分のうち、
特にタングステン成分は触媒活性の向上に有効であり、
これをＢ群元素と併用することによって触媒の選択性を
低下させることなく触媒活性の著しい向上が認められ
る。このタングステン成分の添加割合は、モリブデン成
分を12としたとき、０〜10、好ましくは0.5〜10であ
る。The catalyst used in the present invention is composed of the elemental components represented by the general formula (I), and the object of the present invention is achieved by a combination of these elemental components.
In particular, the tungsten component is effective for improving the catalytic activity,
When this is used in combination with the group B element, a remarkable improvement in the catalytic activity can be observed without lowering the selectivity of the catalyst. When the molybdenum component is 12, the addition ratio of the tungsten component is 0 to 10, preferably 0.5 to 10.
なお、本発明における「活性」とは、出発原料の転化
率を意味する。In the present invention, "activity" means the conversion of the starting material.
本発明で使用する触媒は、通常の成型法、例えば押出
成型法あるいは打錠成型法などによって成型してもよ
く、また触媒成分としての一般式（Ｉ）によって表され
る複合酸化物を、炭化ケイ素、アルミナ、酸化ジルコニ
ウム、酸化チタンなどの一般に担体として使用されてい
る不活性な担体に担持してもよい。The catalyst used in the present invention may be molded by a usual molding method, for example, an extrusion molding method or a tablet molding method, and a composite oxide represented by the general formula (I) as a catalyst component is carbonized. It may be supported on an inert carrier generally used as a carrier, such as silicon, alumina, zirconium oxide, and titanium oxide.
本発明で使用する触媒の形状については、特に制限は
なく、球状、円柱状、リング状などいずれでもよい。特
に、リング状触媒を使用するとホットスポット部におけ
る蓄熱が防止され、収率の向上、触媒劣化の防止などの
他、触媒層での圧力損失の低下など種々の利点が得られ
ることから、本発明においてはリング状触媒が好適に使
用される。リンク状触媒としては、外径が３〜10mm、長
さが外径の0.5〜２倍、長さ方向への貫通孔の内径が外
径の0.1〜0.7倍となるようなリング状触媒が好適に使用
される。The shape of the catalyst used in the present invention is not particularly limited, and may be any of a sphere, a column, and a ring. In particular, when a ring-shaped catalyst is used, heat accumulation in a hot spot portion is prevented, and various advantages such as a reduction in pressure loss in a catalyst layer can be obtained in addition to an improvement in yield and prevention of catalyst deterioration. In the above, a ring-shaped catalyst is preferably used. As the link catalyst, a ring catalyst having an outer diameter of 3 to 10 mm, a length of 0.5 to 2 times the outer diameter, and an inner diameter of the through hole in the length direction of 0.1 to 0.7 times the outer diameter is preferable. Used for
本発明においては、各反応管内の触媒層を管軸方向に
２層以上に分割して複数個の反応帯を設け、これら反応
帯に上記活性の異なる複数個の触媒を原料ガスの入口部
から出口部に向かって活性が順次高くなるように配置す
る。すなわち、活性が最も低い触媒を入口部に、一方活
性が最も高い触媒を出口部に配置する。このように活性
の異なる複数個の触媒を配列することによって、ホット
スポット部における蓄熱を抑え、また高選択率で目的物
を得ることができる。In the present invention, the catalyst layer in each reaction tube is divided into two or more layers in the tube axis direction to provide a plurality of reaction zones, and a plurality of catalysts having different activities are supplied to the reaction zones from the inlet of the raw material gas. It arrange | positions so that activity may become high sequentially toward an exit part. That is, the catalyst with the lowest activity is located at the inlet, while the catalyst with the highest activity is located at the outlet. By arranging a plurality of catalysts having different activities in this manner, heat storage in the hot spot portion can be suppressed, and the target product can be obtained with a high selectivity.
触媒層の分割は数多くするほど、触媒層の温度分布を
抑制しやすくなるが、工業的には２〜３層にすることに
よって充分目的とする効果を得ることができる。また、
分割比については、各層の触媒をいかなる組成、形状な
どにするかによって左右されるため一概に特定できず、
全体としての最適な活性、選択率が得られるように適宜
選択すればよい。The more the catalyst layer is divided, the more easily the temperature distribution of the catalyst layer can be suppressed. However, industrially, the desired effect can be sufficiently obtained by using two or three layers. Also,
Since the splitting ratio depends on the composition, shape, etc. of the catalyst of each layer, it cannot be specified unconditionally,
What is necessary is just to select suitably so that the optimal activity and selectivity as a whole may be obtained.
本発明における気相接触酸化反応は、通常の単流通法
でも、あるいはリサイクル法であってもよく、またこの
種の反応に一般に用いられている条件下に実施すること
ができる。例えば、原料ガスとして、イソブチレン、ｔ
−ブタノールおよびメチル−ｔ−ブチルエーテルから選
ばれる少なくとも１種の化合物１〜10容量％、分子状酸
素３〜20容量％、水蒸気０〜60容量％、窒素、炭酸ガス
などの不活性ガス20〜80容量％などからなる混合ガスを
前記触媒上に250〜450℃の温度範囲、常圧〜10気圧の圧
力下、空間速度300〜5000hr-1で導入する。The gas phase catalytic oxidation reaction in the present invention may be an ordinary single flow method or a recycling method, and can be carried out under conditions generally used for this type of reaction. For example, as raw material gas, isobutylene, t
1 to 10% by volume of at least one compound selected from butanol and methyl-t-butyl ether, 3 to 20% by volume of molecular oxygen, 0 to 60% by volume of steam, and 20 to 80% of an inert gas such as nitrogen and carbon dioxide. A mixed gas consisting of, for example, volume% is introduced onto the catalyst under a temperature range of 250 to 450 ° C., a pressure of normal pressure to 10 atm and a space velocity of 300 to 5000 hr −1 .
本発明の方法によれば、生産性を上げることを目的と
した高負荷反応条件下、例えばより高い原料濃度、ある
いはより高い空間速度の条件下において、従来法に比べ
て、特に著しい好結果が得られる。According to the method of the present invention, under a high load reaction condition for the purpose of increasing productivity, for example, under a condition of a higher raw material concentration or a higher space velocity, particularly remarkable good results are obtained as compared with the conventional method. can get.
（発明の効果） 本発明においては、活性の異なる複数個の特定のモリ
ブデン系触媒を複数個に分割した触媒層に原料ガス入口
部から出口部に向かって活性がより高くなるように充填
することによって、 （ａ）高収率でメタクロレインおよびメタクリル酸が得
られる、 （ｂ）ホットスポット部における蓄熱を効果的に抑制で
きる、 （ｃ）ホットスポット部における過度の酸化反応が防止
され、高収率で目的とするメタクロレインおよびメタク
リル酸を得ることができる、 （ｄ）熱負荷による触媒の劣化が防止され、触媒を長期
間安定して使用することができる、 （ｅ）高原料濃度、高空間速度など高負荷反応条件下で
も目的とするメタクロレインおよびメタクリル酸を高収
率で得られることから生産性を大幅に上げることができ
るなどの効果が得られる。(Effect of the Invention) In the present invention, a plurality of specific molybdenum-based catalysts having different activities are filled into a plurality of divided catalyst layers so that the activity becomes higher from the raw material gas inlet toward the outlet. Thereby, (a) methacrolein and methacrylic acid can be obtained in high yield, (b) heat storage in the hot spot portion can be effectively suppressed, and (c) excessive oxidation reaction in the hot spot portion is prevented, and high yield is obtained. (D) Prevention of catalyst deterioration due to heat load and stable use of the catalyst for a long period of time; (e) High raw material concentration, high The target methacrolein and methacrylic acid can be obtained in high yield even under high-load reaction conditions such as space velocity, so that productivity can be greatly increased. It is obtained.
さらに、リング状触媒を使用することによって、上記
の効果の他に （ｆ）触媒層での圧力損失の低下によって消費電力を低
減することができる などの効果も得られる。Further, by using the ring-shaped catalyst, in addition to the above-described effects, there is also obtained an effect that (f) the power consumption can be reduced by reducing the pressure loss in the catalyst layer.
従って、本発明の方法は、メタクロレインおよびメタ
クリル酸の工業的生産に極めて有用な方法である。Therefore, the method of the present invention is a very useful method for industrial production of methacrolein and methacrylic acid.
（実施例） 以下、実施例を上げて本発明を更に具体的に説明す
る。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.
なお、転化率、選択率および合計単流収率は次の式に
よって定義される。The conversion, selectivity and total single-stream yield are defined by the following equations.
実施例１ 水1000mlに硝酸コバルト1456gおよび硝酸第二鉄202g
を溶解した。また、硝酸ビスマス243gを濃硝酸30mlと水
120mlとの硝酸水溶液に溶解した。 Example 1 1456 g of cobalt nitrate and 202 g of ferric nitrate in 1000 ml of water
Was dissolved. Also, 243 g of bismuth nitrate was added to 30 ml of concentrated nitric acid and water
Dissolved in 120 ml of aqueous nitric acid.
別に、水3000mlを加熱撹拌しつつその中にパラモリブ
デン酸アンモニウム1059gおよびパラタングステン酸ア
ンモニウム265gを溶解し、得られた水溶液に上記別途調
製した２つの水溶液を滴下、混合し、次いで硝酸セシウ
ム68.3gを水200mlに溶解した水溶液、更に20重量％濃度
のシリカゾル203gを順次添加し、混合した。Separately, 1059 g of ammonium paramolybdate and 265 g of ammonium paratungstate are dissolved therein while heating and stirring 3,000 ml of water, and the above two separately prepared aqueous solutions are dropped and mixed into the obtained aqueous solution, and then 68.3 g of cesium nitrate Was dissolved in 200 ml of water, and 203 g of silica sol having a concentration of 20% by weight were sequentially added and mixed.
このようにして得られた懸濁液を加熱撹拌し、蒸発乾
固した後、外径6mm、長さ6.6mmのペレット状に成型し、
空気流通下に500℃で６時間焼成して触媒（１）を得
た。この触媒（１）の組成は、酸素を除いた原子比で Mo12W2Bi1Fe1Co10Cs0.7Si1.35であった。The suspension thus obtained was heated and stirred, evaporated to dryness, molded into a pellet having an outer diameter of 6 mm and a length of 6.6 mm,
The catalyst (1) was obtained by calcining at 500 ° C. for 6 hours under flowing air. The composition of this catalyst (1) was Mo 12 W 2 Bi 1 Fe 1 Co 10 Cs 0.7 Si 1.35 in atomic ratio excluding oxygen.
上記触媒（１）の調製法において、硝酸セシウムの量
を9.8gとした以外は触媒（１）と同様にして触媒（２）
を調製した。この触媒（２）の組成は、酸素を除いた原
子比で Mo12W2Bi1Fe1Co10Cs0.1Si1.35であった。Catalyst (2) was prepared in the same manner as in the preparation of catalyst (1) except that the amount of cesium nitrate was changed to 9.8 g.
Was prepared. The composition of this catalyst (2) was Mo 12 W 2 Bi 1 Fe 1 Co 10 Cs 0.1 Si 1.35 in atomic ratio excluding oxygen.
上記触媒（１）、（２）の活性については、後記比較
例１、２の結果から明らかなように、触媒（２）のほう
が触媒（１）よりも活性が高い。Regarding the activities of the catalysts (1) and (2), as is clear from the results of Comparative Examples 1 and 2 described later, the activity of the catalyst (2) is higher than that of the catalyst (1).
直径25.4mmの鋼鉄製反応管の原料ガス入口部に上記触
媒（１）750mlを充填し、一方原料ガス出口部上記に触
媒（２）750mlを充填した。The raw material gas inlet of a steel reaction tube having a diameter of 25.4 mm was filled with 750 ml of the catalyst (1), while the raw gas outlet was filled with 750 ml of the catalyst (2).
上記反応管入口からイソブチレン６容量％、酸素13.2
容量％、水蒸気10容量％、窒素70.8容量％からなる組成
の混合ガスを導入し、反応温度340℃、空間速度（SV）1
600hr-1（STP）で反応を行った。結果を表１に示す。6 volume% isobutylene, oxygen 13.2
A mixed gas consisting of 10% by volume, 10% by volume of steam, and 70.8% by volume of nitrogen was introduced, and the reaction temperature was 340 ° C and the space velocity (SV) 1
The reaction was performed at 600 hr -1 (STP). Table 1 shows the results.
比較例１ 実施例１において、触媒（２）を使用することなく触
媒（１）のみを1500ml充填した以外は実施例１と同様に
反応を行った。結果を表１に示す。Comparative Example 1 A reaction was carried out in the same manner as in Example 1, except that the catalyst (2) was not used and only the catalyst (1) was charged in an amount of 1500 ml. Table 1 shows the results.
比較例２ 実施例１において、触媒（１）を使用することなく触
媒（２）のみを1500ml充填した以外は実施例１と同様に
反応を行った。結果を表１に示す。Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that the catalyst (1) was not used and only the catalyst (2) was charged in an amount of 1500 ml. Table 1 shows the results.
比較例３ 実施例１の触媒（１）の調製において、硝酸セシウム
の使用量を39gとした以外は触媒（１）と同様にして触
媒（３）を調製した。この触媒（３）の組成は、酸素を
除いた原子比で Mo12W2Bi1Fe1Co10Cs0.4Si1.35であった。Comparative Example 3 A catalyst (3) was prepared in the same manner as in the preparation of the catalyst (1) of Example 1, except that the amount of cesium nitrate used was changed to 39 g. The composition of this catalyst (3) was Mo 12 W 2 Bi 1 Fe 1 Co 10 Cs 0.4 Si 1.35 in atomic ratio excluding oxygen.
実施例１において、上記触媒（３）1500mlのみを反応
管に充填した以外は実施例１と同様に反応を行った。結
果を表１に示す。The reaction was carried out in the same manner as in Example 1 except that only 1500 ml of the catalyst (3) was charged into the reaction tube. Table 1 shows the results.
実施例１および比較例１〜３の結果から、触媒（１）
の活性は非常に低く、一方触媒（２）は高活性である
が、いずれも合計単流収率が低いのに対し、これら触媒
（１）、（２）を組み合わせた本発明の触媒系において
は合計単流収率が高く、目的とするメタクロレインおよ
びメタクリル酸が高収率で得られることが理解される。From the results of Example 1 and Comparative Examples 1 to 3, catalyst (1)
Is very low, whereas catalyst (2) is highly active, but the total single-stream yield is low, whereas the catalyst system of the present invention combining these catalysts (1) and (2) Shows that the total single stream yield is high and the desired methacrolein and methacrylic acid can be obtained in high yield.
また、触媒（１）と触媒（２）との中間的組成を有す
る触媒（３）と触媒（１）、（２）を組み合わせた本発
明の触媒系とを比較すると、触媒（３）では合計単流収
率が低く、さらには反応温度はホットスポット部温度と
の温度差（ΔＴ）が非常に大きいことから熱負荷による
触媒劣化が著しいものと考えられる。すなわち、本発明
の触媒系と組成をほぼ同一にした単一の触媒（３）を単
独で使用しても本発明の効果を達成することができない
ことが理解される。Also, when comparing the catalyst (3) having an intermediate composition between the catalyst (1) and the catalyst (2) with the catalyst system of the present invention in which the catalysts (1) and (2) are combined, the catalyst (3) has a total Since the single stream yield is low and the temperature difference (ΔT) between the reaction temperature and the hot spot temperature is very large, it is considered that the catalyst is significantly deteriorated due to the heat load. That is, it is understood that the effect of the present invention cannot be achieved even if a single catalyst (3) having a composition substantially the same as that of the catalyst system of the present invention is used alone.
実施例２ 実施例１において、触媒（１）、（２）をともに外径
6mm、長さ6.6mm、貫通孔内径1mmのリング状に成型した
以外は実施例１と同様にして反応を行った。結果を表１
に示す。Example 2 In Example 1, both the catalysts (1) and (2) had the same outer diameter.
The reaction was carried out in the same manner as in Example 1 except that a ring was formed having a length of 6 mm, a length of 6.6 mm, and an inner diameter of the through-hole of 1 mm. Table 1 shows the results
Shown in
比較例４ 比較例１において、触媒（１）を外径6mm、長さ6.6m
m、貫通孔内径1mmのリング状に成型した以外は比較例１
と同様にして反応を行った。結果を表１に示す。Comparative Example 4 In Comparative Example 1, the catalyst (1) was changed to have an outer diameter of 6 mm and a length of 6.6 m.
m, Comparative Example 1 except that it was molded into a ring shape with a through hole inner diameter of 1 mm.
The reaction was carried out in the same manner as described above. Table 1 shows the results.
比較例５ 比較例２において、触媒（２）を外径6mm、長さ6.6m
m、貫通孔内径1mmのリング状に成型した以外は比較例２
と同様にして反応を行った。結果を表１に示す。Comparative Example 5 In Comparative Example 2, the catalyst (2) was changed to have an outer diameter of 6 mm and a length of 6.6 m.
m, Comparative Example 2 except that it was molded into a ring shape with a through-hole inner diameter of 1 mm
The reaction was carried out in the same manner as described above. Table 1 shows the results.
比較例６ 比較例３において、触媒（３）を外径6mm、長さ6.6m
m、貫通孔内径1mmのリング状に成型した以外は比較例３
と同様にして反応を行った。結果を表１に示す。Comparative Example 6 In Comparative Example 3, the catalyst (3) was changed to have an outer diameter of 6 mm and a length of 6.6 m.
Comparative Example 3 except that it was molded into a ring shape with an inner diameter of 1 mm and a through hole of 1 mm
The reaction was carried out in the same manner as described above. Table 1 shows the results.
実施例２および比較例４〜６は、触媒（１）〜（３）
の形状をペレット状からリング状に変更したものであ
る。表１の結果から、触媒（１）〜（３）のいずれの場
合も形状をリング状に変更すると収率の向上とΔＴの低
下が認められるが、触媒（１）〜（３）を各々単独で使
用した場合に比較して触媒（１）、（２）を組み合わせ
た本発明の触媒系のほうが収率およびΔＴがともに優れ
ていることが理解される。Example 2 and Comparative Examples 4 to 6 correspond to catalysts (1) to (3)
Is changed from a pellet shape to a ring shape. From the results shown in Table 1, when the shape of each of the catalysts (1) to (3) is changed to a ring shape, an improvement in yield and a decrease in ΔT are observed, but the catalysts (1) to (3) are used alone. It is understood that the catalyst system of the present invention in which the catalysts (1) and (2) are combined is superior in both the yield and ΔT as compared with the case where the catalyst is used.
実施例３ 実施例１において、反応を4000時間まで長期にわたっ
て行った以外は実施例１と同様にして反応を行った。結
果を表１に示す。Example 3 A reaction was carried out in the same manner as in Example 1 except that the reaction was carried out for a long time up to 4000 hours. Table 1 shows the results.
表１の結果から、4000時間反応後でも活性低下は非常
に低く、収率の低下は殆ど無視できる程度であり、本発
明の触媒系の場合、長期にわたって非常に安定した連続
運転を行うことができることが理解される。From the results in Table 1, the activity decrease is very low even after 4000 hours of reaction, and the decrease in yield is almost negligible. In the case of the catalyst system of the present invention, very stable continuous operation can be performed over a long period of time. It is understood that it is possible.
比較例７ 比較例３において、反応時間を4000時間に変更した以
外は比較例３と同様に反応を行った。結果を表１に示
す。Comparative Example 7 A reaction was carried out in the same manner as in Comparative Example 3, except that the reaction time was changed to 4000 hours. Table 1 shows the results.
表１の結果から、実施例３の場合に比べ、活性および
収率の低下がともに大きく、触媒の安定性に問題あるこ
とが理解される。From the results shown in Table 1, it is understood that both the activity and the yield are greatly reduced as compared with the case of Example 3, and there is a problem in the stability of the catalyst.
実施例４ 実施例２において、反応温度は360℃に、また空間速
度を3000hr-1（STP）に変更した以外は実施例２と同様
に反応を行った。結果を表１に示す。Example 4 A reaction was carried out in the same manner as in Example 2 except that the reaction temperature was changed to 360 ° C. and the space velocity was changed to 3000 hr −1 (STP). Table 1 shows the results.
比較例８ 比較例４において、反応時間を360℃に、また空間速
度を3000hr-1（STP）に変更した以外は比較例４と同様
に反応を行った。結果を表１に示す。Comparative Example 8 The reaction was carried out in the same manner as in Comparative Example 4, except that the reaction time was changed to 360 ° C. and the space velocity was changed to 3000 hr −1 (STP). Table 1 shows the results.
比較例９ 比較例６において、反応温度は360℃に、また空間速
度を3000hr-1（STP）に変更した以外は比較例６と同様
に反応を行った。結果を表１に示す。Comparative Example 9 The reaction was carried out in the same manner as in Comparative Example 6, except that the reaction temperature was changed to 360 ° C. and the space velocity was changed to 3000 hr −1 (STP). Table 1 shows the results.
実施例４および比較例８〜９の結果から、空間速度を
上げた場合でも、触媒（１）、（２）を組み合わせた本
発明の触媒系の触媒（１）または（３）に対する、活性
および収率における優位差がそのまま現れることが理解
される。From the results of Example 4 and Comparative Examples 8 to 9, even when the space velocity was increased, the activity and activity of the catalyst system of the present invention combining the catalysts (1) and (2) with respect to the catalyst (1) or (3) were improved. It is understood that the superior difference in yield appears.
実施例５ 実施例２において、原料ガス中のイソブチレンおよび
窒素の割合をそれぞれ７容量％および69.8容量％に変更
した以外は実施例２と同様に反応を行った。結果を表１
に示す。Example 5 A reaction was carried out in the same manner as in Example 2 except that the proportions of isobutylene and nitrogen in the raw material gas were changed to 7% by volume and 69.8% by volume, respectively. Table 1 shows the results
Shown in
比較例10 比較例４において、原料ガス中のイソブチレンおよび
窒素の割合をそれぞれ７容量％および69.8容量％に変更
した以外は比較例４と同様に反応を行った。結果を表１
に示す。Comparative Example 10 A reaction was carried out in the same manner as in Comparative Example 4, except that the proportions of isobutylene and nitrogen in the raw material gas were changed to 7% by volume and 69.8% by volume, respectively. Table 1 shows the results
Shown in
比較例11 比較例６において、原料ガス中のイソブチレンおよび
窒素の割合をそれぞれ７容量％および69.8容量％に変更
した以外は比較例６と同様に反応を行った。結果を表１
に示す。Comparative Example 11 A reaction was carried out in the same manner as in Comparative Example 6, except that the proportions of isobutylene and nitrogen in the raw material gas were changed to 7% by volume and 69.8% by volume, respectively. Table 1 shows the results
Shown in
実施例５および比較例10〜11の結果から、イソブチレ
ン濃度を上げた場合にも、触媒（１）、（２）を組み合
わせた本発明の触媒系の触媒（１）または触媒（３）に
対する、収率およびΔＴにおける優位差がそのまま現れ
ることが理解される。特に、触媒層のΔＴの増加につい
ては、本発明の触媒系は単独触媒に比べてかなり小さい
ことから、本発明のように触媒を配列することは、熱負
荷による触媒劣化を極力小さくすることに効果があるも
のと考えられる。From the results of Example 5 and Comparative Examples 10 to 11, even when the isobutylene concentration was increased, the catalyst system of the present invention in which the catalysts (1) and (2) were combined with respect to the catalyst (1) or (3) It is understood that the dominant differences in yield and ΔT appear intact. In particular, regarding the increase in ΔT of the catalyst layer, since the catalyst system of the present invention is considerably smaller than the single catalyst, arranging the catalyst as in the present invention minimizes catalyst deterioration due to heat load. It seems to be effective.
実施例６ 実施例１において、イソブチレンの代わりにｔ−ブタ
ノールを使用した以外は実施例１と同様に反応を行っ
た。結果を表２に示す。Example 6 A reaction was carried out in the same manner as in Example 1, except that t-butanol was used instead of isobutylene. Table 2 shows the results.
比較例12 比較例１において、イソブチレンの代わりにｔ−ブタ
ノールを使用した以外は比較例１と同様に反応を行っ
た。結果を表２に示す。Comparative Example 12 A reaction was carried out in the same manner as in Comparative Example 1, except that t-butanol was used instead of isobutylene. Table 2 shows the results.
比較例13 比較例３において、イソブチレンの代わりにｔ−ブタ
ノールを使用した以外は比較例３と同様に反応を行っ
た。結果を表２に示す。Comparative Example 13 The reaction was carried out in the same manner as in Comparative Example 3 except that t-butanol was used instead of isobutylene. Table 2 shows the results.
実施例７ 実施例２において、原料ガスとしてメチル−ｔ−ブチ
ルエーテル（MTBE）５容量％、酸素13.2容量％、水蒸気
10容量％、窒素71.8容量％の原料ガスを使用し、さらに
反応温度を360℃、空間速度を1000hr-1（STP）に変更し
た以外は実施例２と同様に反応を行った。結果を表３に
示す。Example 7 In Example 2, the raw material gas was methyl-t-butyl ether (MTBE) 5% by volume, oxygen 13.2% by volume, steam
The reaction was carried out in the same manner as in Example 2, except that a raw material gas of 10% by volume and 71.8% by volume of nitrogen was used, the reaction temperature was changed to 360 ° C., and the space velocity was changed to 1000 hr −1 (STP). Table 3 shows the results.
比較例14 比較例４において、原料ガスとしてMTBE5容量％、酸
素13.2容量％、水蒸気10容量％、窒素71.8容量％の原料
ガスを使用し、さらに反応温度を360℃、空間速度を100
0hr-1（STP）に変更した以外は比較例４と同様に反応を
行った。結果を表３に示す。Comparative Example 14 In Comparative Example 4, a raw material gas containing 5% by volume of MTBE, 13.2% by volume of oxygen, 10% by volume of steam, and 71.8% by volume of nitrogen was used as the raw material gas, and the reaction temperature was 360 ° C. and the space velocity was 100%.
The reaction was carried out in the same manner as in Comparative Example 4 except that the time was changed to 0 hr -1 (STP). Table 3 shows the results.
比較例15 比較例６において、原料ガスとしてMTBE5容量％、酸
素13.2容量％、水蒸気10容量％、窒素71.8容量％の原料
ガスを使用し、さらに反応温度を360℃、空間速度を100
0hr-1（STP）に変更した以外は比較例６と同様に反応を
行った。結果を表３に示す。Comparative Example 15 In Comparative Example 6, a raw material gas containing 5% by volume of MTBE, 13.2% by volume of oxygen, 10% by volume of steam, and 71.8% by volume of nitrogen was used as the raw material gas, and the reaction temperature was 360 ° C. and the space velocity was 100%.
The reaction was carried out in the same manner as in Comparative Example 6, except that the time was changed to 0 hr -1 (STP). Table 3 shows the results.
実施例８ 実施例１において、硝酸コバルトの代わりに硝酸ニッ
ケルを使用すること、パラタングステン酸アンモニウム
の後にリン酸を添加すること、硝酸セシウムの代わりに
硝酸ルビジウムを使用すること、硝酸ルビジウムの後に
酸化第二スズを添加すること、さらにシリカゾルの代わ
りに硝酸アルミニウムを使用すること以外は実施例１と
同様にして触媒（４）を調製した。Example 8 In Example 1, using nickel nitrate instead of cobalt nitrate, adding phosphoric acid after ammonium paratungstate, using rubidium nitrate instead of cesium nitrate, oxidizing after rubidium nitrate A catalyst (4) was prepared in the same manner as in Example 1 except that stannic acid was added and aluminum nitrate was used instead of silica sol.
この触媒（４）の組成は、酸素を除いた原子比として Mo12W2Bi3Fe1Ni7Rb1P0.2Sn0.5Al1 であった。The composition of this catalyst (4) was Mo 12 W 2 Bi 3 Fe 1 Ni 7 Rb 1 P 0.2 Sn 0.5 Al 1 as an atomic ratio excluding oxygen.
硝酸ルビジウムの使用量を変更する以外は上記触媒
（４）と同様にして触媒（５）を調製した。A catalyst (5) was prepared in the same manner as the catalyst (4), except that the amount of rubidium nitrate was changed.
この触媒（５）の組成は、酸素を除いた原子比として Mo12W2Bi3Fe1Ni7Rb0.2P0.2Sn0.5Al1 であった。The composition of this catalyst (5) was Mo 12 W 2 Bi 3 Fe 1 Ni 7 Rb 0.2 P 0.2 Sn 0.5 Al 1 as an atomic ratio excluding oxygen.
直径25.4mmの鋼鉄製反応管のガス入口側に触媒（４）
750mlを充填し、一方ガス出口側には触媒（５）750mlを
充填した。Catalyst (4) on the gas inlet side of a 25.4 mm diameter steel reaction tube
The gas outlet side was filled with 750 ml of the catalyst (5).
以下、実施例１と同様にして反応を行った。結果を表
４に示す。Thereafter, the reaction was carried out in the same manner as in Example 1. Table 4 shows the results.
比較例16 実施例８において、触媒（５）を使用することなく触
媒（４）のみを1500ml充填した以外は実施例８と同様に
して反応を行った。結果を表４に示す。Comparative Example 16 The reaction was carried out in the same manner as in Example 8, except that the catalyst (5) was not used and only the catalyst (4) was charged in an amount of 1500 ml. Table 4 shows the results.
比較例17 実施例８において、触媒（４）を使用することなく触
媒（５）のみを1500ml充填した以外は実施例８と同様に
して反応を行った。結果を表４に示す。Comparative Example 17 The reaction was carried out in the same manner as in Example 8, except that the catalyst (4) was not used and the catalyst (5) alone was filled with 1500 ml. Table 4 shows the results.
実施例９ 実施例１において、パラタングテン酸アンモニウムを
用いないこと、硝酸セシウムの代わりに硝酸カリウム、
硝酸リチウム、硝酸マグネシウムおよび硝酸カルシウム
を添加すること、シリカゾルの代わりに二酸化チタンを
使用すること、さらに最後に硝酸第一セリウムと五酸化
ニオブを使用する以外は実施例１と同様にして触媒
（６）を得た。この触媒（６）の組成は、酸素を除く原
子比で Mo12Bi1Fe1Co10K1.2Li0.5Ca0.2Mg0.2Nb0.5Ce1Ti1 であった。Example 9 In Example 1, no ammonium paratungstate was used, potassium nitrate was used instead of cesium nitrate,
A catalyst (6) was prepared in the same manner as in Example 1 except that lithium nitrate, magnesium nitrate, and calcium nitrate were added, titanium dioxide was used instead of silica sol, and finally, cerous nitrate and niobium pentoxide were used. ) Got. The composition of this catalyst (6) was Mo 12 Bi 1 Fe 1 Co 10 K 1.2 Li 0.5 Ca 0.2 Mg 0.2 Nb 0.5 Ce 1 Ti 1 in atomic ratio excluding oxygen.
硝酸カリウムと硝酸リチウムの量を変えた以外は触媒
（６）と同様にして触媒（７）を調製した。この触媒
（７）の組成は、酸素を除く原子比で Mo12Bi1Fe1Co10K0.5Li0.2Ca0.2Mg0.2Nb0.5Ce1Ti1 であった。A catalyst (7) was prepared in the same manner as the catalyst (6), except that the amounts of potassium nitrate and lithium nitrate were changed. The composition of this catalyst (7) was Mo 12 Bi 1 Fe 1 Co 10 K 0.5 Li 0.2 Ca 0.2 Mg 0.2 Nb 0.5 Ce 1 Ti 1 in atomic ratio excluding oxygen.
直径25.4mmの鋼鉄製反応管のガス入口部に触媒（６）
750mlを充填し、次にガス出口部に触媒（７）750mlを充
填した。Catalyst at the gas inlet of a 25.4 mm diameter steel reaction tube (6)
750 ml were charged, and then 750 ml of the catalyst (7) was charged at the gas outlet.
以下、実施例１と同様にして反応を行った。結果を表
４に示す。Thereafter, the reaction was carried out in the same manner as in Example 1. Table 4 shows the results.
比較例18 実施例９において、触媒（７）を使用することなく触
媒（６）のみを1500ml充填した以外は実施例９と同様に
反応を行った。結果を表４に示す。Comparative Example 18 The reaction was carried out in the same manner as in Example 9 except that the catalyst (7) was not used and only the catalyst (6) was charged in an amount of 1500 ml. Table 4 shows the results.
比較例19 実施例９において、触媒（６）を使用することなく触
媒（７）のみを1500ml充填した以外は実施例９と同様に
反応を行った。結果を表４に示す。Comparative Example 19 A reaction was carried out in the same manner as in Example 9, except that the catalyst (6) was not used and only the catalyst (7) was charged in an amount of 1500 ml. Table 4 shows the results.
実施例10 実施例１において、パラタングステン酸アンモニウム
を用いないこと、硝酸セシウムの代わりに硝酸第一タリ
ウムと硝酸ストロンチウムを用い、その後に酸化テル
ル、硝酸鉛および硝酸亜鉛を添加すること、またシリカ
ゾルの代わりに二酸化チタンを用いること以外は実施例
１と同様にして懸濁液を調製した。Example 10 In Example 1, no ammonium paratungstate was used, and instead of cesium nitrate, thallous nitrate and strontium nitrate were used, and then tellurium oxide, lead nitrate and zinc nitrate were added. A suspension was prepared in the same manner as in Example 1 except that titanium dioxide was used instead.
得られた懸濁液を加熱撹拌し、蒸発乾固した後、外径
6mm、長さ6.6mm、貫通孔内径2mmのリング状に成型し、
空気流通下に500℃で６時間焼成して触媒（８）を得
た。この触媒（８）の組成は、酸素を除く原子比で Mo12Bi1Fe3Co7Tl0.7Sr0.3Te0.3Pb1Zn0.5Ti1 であった。The resulting suspension is heated and stirred, and evaporated to dryness.
Molded into a ring shape with 6mm, length 6.6mm, through hole 2mm inside diameter,
It was calcined at 500 ° C. for 6 hours under air flow to obtain a catalyst (8). The composition of this catalyst (8) was Mo 12 Bi 1 Fe 3 Co 7 Tl 0.7 Sr 0.3 Te 0.3 Pb 1 Zn 0.5 Ti 1 in atomic ratio excluding oxygen.
硝酸第一タリウムの量を変えた以外は触媒（８）と同
様にして触媒（９）を得た。この触媒の組成は、酸素を
除いた原子比として Mo12Bi1Fe3Co7Tl0.05Sr0.3Te0.3Pb1Zn0.5Ti1 であった。A catalyst (9) was obtained in the same manner as the catalyst (8) except that the amount of thallous nitrate was changed. The composition of this catalyst was Mo 12 Bi 1 Fe 3 Co 7 Tl 0.05 Sr 0.3 Te 0.3 Pb 1 Zn 0.5 Ti 1 as an atomic ratio excluding oxygen.
直径25.4mmの鋼鉄製反応器のガス入口側に触媒触媒
（８）750mlを充填し、一方ガス出口側には触媒（９）7
50mlを充填した。The gas inlet side of a steel reactor having a diameter of 25.4 mm is filled with 750 ml of catalyst (8), while the catalyst outlet (9)
50 ml was filled.
以下、実施例１と同様に反応を行った。結果を表４に
示す。Thereafter, the reaction was carried out in the same manner as in Example 1. Table 4 shows the results.
比較例20 実施例10において、触媒（９）を使用することなく触
媒（８）のみを1500ml充填した以外は実施例10と同様に
反応を行った。結果を表４に示す。Comparative Example 20 The reaction was carried out in the same manner as in Example 10, except that the catalyst (9) was not used and only the catalyst (8) was charged in an amount of 1500 ml. Table 4 shows the results.
比較例21 実施例10において、触媒（８）を使用することなく触
媒（９）のみを1500ml充填した以外は実施例10と同様に
反応を行った。結果を表４に示す。Comparative Example 21 The reaction was carried out in the same manner as in Example 10 except that the catalyst (8) was not used and only the catalyst (9) was charged in an amount of 1500 ml. Table 4 shows the results.
実施例11 実施例１において、硝酸セシウムの代わりに硝酸カリ
ウム、硝酸バリウムおよび硝酸ベリリウムを用いるこ
と、その後に三酸化アンチモンと硝酸マンガンを添加す
ること、またシリカゾルの代わりに硝酸ジルコニウムを
使用すること以外は実施例１と同様にして懸濁液を調製
した。Example 11 In Example 1, except that potassium nitrate, barium nitrate and beryllium nitrate were used in place of cesium nitrate, antimony trioxide and manganese nitrate were added, and zirconium nitrate was used instead of silica sol. A suspension was prepared in the same manner as in Example 1.
この懸濁液を用い、実施例10と同様にして触媒（10）
を調製した。この触媒（10）の組成は、酸素を除いた原
子比で Mo12W1.5Bi1Fe1.2Co5K1.8Ba0.2Be0.2Sb1Mn0.5Zr1 であった。Using this suspension, a catalyst (10) was prepared in the same manner as in Example 10.
Was prepared. The composition of this catalyst (10) was Mo 12 W 1.5 Bi 1 Fe 1.2 Co 5 K 1.8 Ba 0.2 Be 0.2 Sb 1 Mn 0.5 Zr 1 in atomic ratio excluding oxygen.
また、硝酸カリウムの代わりに硝酸ナトリウムを用い
た以外は触媒（10）と同様にして触媒（11）を得た。こ
の触媒（11）の組成は、酸素を除いた原子比で Mo12W1.5Bi1Fe1.2Co5Na1.0Ba0.2Be0.2Sb1Mn0.5Zr1 であった。Also, a catalyst (11) was obtained in the same manner as the catalyst (10) except that sodium nitrate was used instead of potassium nitrate. The composition of this catalyst (11) was Mo 12 W 1.5 Bi 1 Fe 1.2 Co 5 Na 1.0 Ba 0.2 Be 0.2 Sb 1 Mn 0.5 Zr 1 in atomic ratio excluding oxygen.
直径25.4mmの鋼鉄製反応管のガス入口部に触媒（10）
750mlを充填し、一方ガス出口側に触媒（11）750mlを充
填した。Catalyst (10) at the gas inlet of a 25.4 mm diameter steel reaction tube
On the other hand, 750 ml of the catalyst (11) was charged on the gas outlet side.
以下、実施例１と同様にして反応を行った。結果を表
４に示す。Thereafter, the reaction was carried out in the same manner as in Example 1. Table 4 shows the results.
比較例22 実施例11において、触媒（11）を使用することなく触
媒（10）のみを1500ml充填した以外は実施例11と同様に
反応を行った。結果を表４に示す。Comparative Example 22 The reaction was carried out in the same manner as in Example 11, except that the catalyst (11) was not used and only the catalyst (10) was charged in an amount of 1500 ml. Table 4 shows the results.
比較例23 実施例11において、触媒（10）を使用することなく触
媒（11）のみを1500ml充填した以外は実施例11と同様に
反応を行った。結果を表４に示す。Comparative Example 23 The reaction was carried out in the same manner as in Example 11, except that the catalyst (10) was not used and only the catalyst (11) was charged in an amount of 1500 ml. Table 4 shows the results.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｃ 45/37 Ｃ０７Ｃ 45/37 47/22 47/22 Ａ 57/05 57/05 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 青木 幸雄 兵庫県姫路市網干区興浜字西沖992番地 の１ 日本触媒化学工業株式会社触媒研 究所内 合議体 審判長 嶋矢 督 審判官 谷口 操 審判官 星野 浩一 (56)参考文献 特開 昭64−56634（ＪＰ，Ａ) 特公 昭62−36740（ＪＰ，Ｂ２) 特公 昭63−38331（ＪＰ，Ｂ２)Continued on the front page (51) Int.Cl. 6 Identification code FI C07C 45/37 C07C 45/37 47/22 47/22 A 57/05 57/05 // C07B 61/00 300 C07B 61/00 300 (72 Inventor Yukio Aoki 992, Nishioki, Okihama-shi, Abashiri-ku, Himeji-shi, Hyogo Prefecture, Japan Nippon Shokubai Chemical Industry Co., Ltd. -56634 (JP, A) JP-B 62-36740 (JP, B2) JP-B 63-38331 (JP, B2)
Claims (3)
ン、ｔ−ブタノールおよびメチル−ｔ−ブチルエーテル
から選ばれる少なくとも１種を分子状酸素または分子状
酸素含有ガスにより気相接触酸化してメタクロレインお
よびメタクリル酸を製造する方法において、 （イ）触媒として、下記一般式（Ｉ） MoaWbBicFedAeBfCgDh EiOx （式中、Moはモリブデン、Ｗはタングステン、Biはビス
マス、Feは鉄、Ａはニッケルおよびコバルトから選ばれ
る少なくとも１種の元素、Ｂはアルカル金属およびタリ
ウムから選ばれる少なくとも１種の元素、Ｃはアルカリ
土類金属から選ばれる少なくとも１種の元素、Ｄはリ
ン、テルル、アンチモン、スズ、セリウム、鉛、ニオ
ブ、マンガン、ヒ素および亜鉛から選ばれる少なくとも
１種の元素、Ｅはシリコン、アルミニウム、チタニウム
およびジルコニウムから選ばれる少なくとも１種の元
素、Ｏは酸素を表し、またａ、ｂ、ｃ、ｄ、ｅ、ｆ、
ｇ、ｈ、ｉおよびｘは、それぞれ、Mo、Ｗ、Bi、Fe、
Ａ、Ｂ、Ｃ、Ｄ、ＥおよびＯの原子数を表し、ａ＝12と
したとき、ｂ＝０〜10、ｃ＝0.1〜10、ｄ＝0.1〜20、ｅ
＝２〜20、ｆ＝0.001〜10、ｇ＝０〜10、ｈ＝０〜４、
ｉ＝０〜30、ｘ＝各々の元素の酸化状態によって定まる
数値である）で表される複合酸化物を使用し、 （ロ）各反応管内の触媒層を管軸方向に２層以上に分割
して設けた複数個の反応帯に、 （ハ）上記（イ）の触媒において、一般式（Ｉ）におけ
るＢ群元素の種類および／または量を変更して調製した
活性の異なる複数個の触媒を原料ガス入口部から出口部
に向かって活性がより高くなるように充填し、さらに （ニ）上記複数個の触媒の少なくとも１つとして、一般
式（Ｉ）において、Ｂ群元素の原子比が0.6〜10の範囲
にある複合酸化物を使用することを特徴とするメタクロ
レインおよびメタクリル酸の製造方法。1. A process comprising the step of subjecting at least one selected from isobutylene, t-butanol and methyl-t-butyl ether to gas-phase catalytic oxidation with molecular oxygen or a molecular oxygen-containing gas using a fixed-bed multitubular reactor. a process for preparing and methacrylic acid, as (i) a catalyst, the following general formula (I) in Mo a W b Bi c Fe d a e B f C g D h E i O x ( wherein, Mo is molybdenum, W is tungsten, Bi is bismuth, Fe is iron, A is at least one element selected from nickel and cobalt, B is at least one element selected from alkali metals and thallium, and C is selected from alkaline earth metals At least one element, D is at least one element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic and zinc, and E is silicon. Emissions, aluminum, at least one element selected from titanium and zirconium, O represents oxygen, also a, b, c, d, e, f,
g, h, i and x are Mo, W, Bi, Fe,
Represents the number of atoms of A, B, C, D, E and O, and when a = 12, b = 0 to 10, c = 0.1 to 10, d = 0.1 to 20, e
= 2-20, f = 0.001-10, g = 0-10, h = 0-4,
i = 0 to 30, x = a value determined by the oxidation state of each element). (b) The catalyst layer in each reaction tube is divided into two or more layers in the tube axis direction. (C) a plurality of catalysts having different activities prepared by changing the type and / or amount of the group B element in the general formula (I) in the catalyst of the above (a). Is charged so that the activity becomes higher from the inlet portion of the raw material gas toward the outlet portion. (D) As at least one of the plurality of catalysts, in the general formula (I), the atomic ratio of group B elements is A method for producing methacrolein and methacrylic acid, comprising using a composite oxide in the range of 0.6 to 10.
（１）に記載のメタクロレインおよびメタクリル酸の製
造方法。2. The method for producing methacrolein and methacrylic acid according to claim 1, wherein the number of reaction zones is two or three.
5〜２倍、長さ方向への貫通孔の内径が外径の0.1〜0.7
倍のリング状触媒である請求項（１）または（２）に記
載のメタクロレインおよびメタクリル酸の製造方法。3. The catalyst has an outer diameter of 3 to 10 mm and a length of 0.
5 to 2 times, the inner diameter of the through hole in the length direction is 0.1 to 0.7 of the outer diameter
The method for producing methacrolein and methacrylic acid according to claim (1) or (2), which is a double ring catalyst.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1315163A JP2934267B2 (en) | 1989-12-06 | 1989-12-06 | Method for producing methacrolein and methacrylic acid |
| KR1019910700846A KR950006522B1 (en) | 1989-12-06 | 1990-12-06 | Process for producing methacrolein and methacrylic acid |
| ES91900057T ES2092557T3 (en) | 1989-12-06 | 1990-12-06 | PROCEDURE TO PRODUCE METALOCREINE AND METHACRYLIC ACID. |
| EP91900057A EP0456837B1 (en) | 1989-12-06 | 1990-12-06 | Process for producing methacrolein and methacrylic acid |
| ES94103673T ES2130297T3 (en) | 1989-12-06 | 1990-12-06 | PROCEDURE TO PRODUCE METACROLEIN AND METACRILIC ACID. |
| DE69028843T DE69028843T2 (en) | 1989-12-06 | 1990-12-06 | METHOD FOR PRODUCING METHACROLEIN AND METHACRYLIC ACID |
| PCT/JP1990/001594 WO1991008185A1 (en) | 1989-12-06 | 1990-12-06 | Process for producing methacrolein and methacrylic acid |
| EP94103673A EP0608917B1 (en) | 1989-12-06 | 1990-12-06 | Process for producing methacrolein and methacrylic acid |
| SG1996008755A SG50687A1 (en) | 1989-12-06 | 1990-12-06 | Process for producing methacrolein and methacrylic acid |
| DE69033068T DE69033068T2 (en) | 1989-12-06 | 1990-12-06 | Process for the production of methacrolein and methacrylic acid |
| US07/721,574 US5276178A (en) | 1989-12-06 | 1990-12-06 | Process for producing methacrolein and methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1315163A JP2934267B2 (en) | 1989-12-06 | 1989-12-06 | Method for producing methacrolein and methacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03176440A JPH03176440A (en) | 1991-07-31 |
| JP2934267B2 true JP2934267B2 (en) | 1999-08-16 |
Family
ID=18062183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1315163A Expired - Lifetime JP2934267B2 (en) | 1989-12-06 | 1989-12-06 | Method for producing methacrolein and methacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2934267B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009060704A1 (en) * | 2007-11-06 | 2009-05-14 | Nippon Kayaku Kabushiki Kaisha | Process for producing methacrolein and/or methacrylic acid |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046499C (en) * | 1994-06-22 | 1999-11-17 | 旭化成工业株式会社 | Process for producing methacrolein |
| EP3321247B1 (en) * | 2015-07-10 | 2019-11-20 | Nippon Kayaku Kabushiki Kaisha | Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6236740A (en) * | 1985-08-09 | 1987-02-17 | Pioneer Electronic Corp | Optical pickup device |
| JPS6338331A (en) * | 1986-08-01 | 1988-02-18 | Nec Corp | Radio telephone equipment |
| JPH0699336B2 (en) * | 1987-03-05 | 1994-12-07 | 日本化薬株式会社 | Method for producing methacrolein and / or methacrylic acid |
| JPH07116070B2 (en) * | 1987-08-26 | 1995-12-13 | 株式会社日本触媒 | Process for producing methacrolein and methacrylic acid from methyl tert-butyl ether |
-
1989
- 1989-12-06 JP JP1315163A patent/JP2934267B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009060704A1 (en) * | 2007-11-06 | 2009-05-14 | Nippon Kayaku Kabushiki Kaisha | Process for producing methacrolein and/or methacrylic acid |
| JP2009114119A (en) * | 2007-11-06 | 2009-05-28 | Nippon Kayaku Co Ltd | Method for producing methacrolein and/or methacrylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03176440A (en) | 1991-07-31 |
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