JP2011102249A - Method of producing acrylic acid - Google Patents
Method of producing acrylic acid Download PDFInfo
- Publication number
- JP2011102249A JP2011102249A JP2009256897A JP2009256897A JP2011102249A JP 2011102249 A JP2011102249 A JP 2011102249A JP 2009256897 A JP2009256897 A JP 2009256897A JP 2009256897 A JP2009256897 A JP 2009256897A JP 2011102249 A JP2011102249 A JP 2011102249A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- acrylic acid
- molybdenum
- element selected
- molecular oxygen
- 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.)
- Pending
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 129
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 239000011733 molybdenum Substances 0.000 claims abstract description 20
- 238000012856 packing Methods 0.000 claims abstract description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000012808 vapor phase Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 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 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 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
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 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
- 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
- 239000011133 lead Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012018 catalyst precursor Substances 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 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 4
- 238000011049 filling Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000020169 heat generation Effects 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
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- -1 organic acid salts Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 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
- 239000011248 coating agent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は、プロピレンの接触気相酸化によりアクリル酸の製造する方法に関する。 The present invention relates to a process for producing acrylic acid by catalytic gas phase oxidation of propylene.
アクリル酸は、各種合成樹脂、塗料、可塑剤の原料として工業的に重要であり、現在、全世界で数百万トン／年の規模で生産されている。また、近年では、吸水性樹脂の原料としてその重要性が高まり、需要はさらに伸び、工業的規模でアクリル酸収率のさらなる向上が望まれている。アクリル酸の製法としては、プロピレンの接触気相酸化により主としてアクロレインを得て、さらに得られたアクロレインの接触気相酸化によってアクリル酸とする二段酸化方法が最も一般的である。 Acrylic acid is industrially important as a raw material for various synthetic resins, paints, and plasticizers, and is currently produced on a scale of several million tons / year worldwide. In recent years, the importance has increased as a raw material for water-absorbent resins, and the demand has further increased, and further improvement in the yield of acrylic acid is desired on an industrial scale. The most common method for producing acrylic acid is a two-stage oxidation method in which acrolein is mainly obtained by catalytic vapor phase oxidation of propylene, and acrylic acid is obtained by catalytic vapor phase oxidation of the obtained acrolein.
このような、プロピレンを分子状酸素または分子状酸素含有ガスの存在下で接触気相酸化してアクリル酸を製造する方法において、プロピレンを接触気相酸化してアクロレインを製造する第一工程に用いられる触媒あるいはアクロレインを接触気相酸化してアクリル酸を製造する第二工程に用いられる触媒として、その目的生成物の収率や触媒寿命等の触媒性能は必ずしも充分なものではなく、その性能の改善を目的として各社で検討がなされ様々な提案がされている。第一工程に用いられる触媒としては、例えば、Ｍｏ、Ｂｉ、Ｆｅ、ＳｂおよびＮｉを含み、更にＫ、Ｒｂ、Ｃｓの少なくとも一種の元素を必須成分とする触媒（特許文献１、特許文献２）、Ｍｏ、ＢｉおよびＦｅを含み、更にＮｉおよびＣｏの少なくとも一種の元素を必須成分とする触媒（特許文献３）、Ｍｏ、ＢｉおよびＦｅを含み、更にＭｇ、Ｃａ、Ｚｎ、ＣｄおよびＢａの少なくとも一種の元素を必須成分とする触媒（特許文献４）、Ｍｏ、ＢｉおよびＦｅを含み、更にＩＩＡおよびＩＩＢ族元素の少なくとも一種の元素を必須成分とする触媒（特許文献５）などが開示されている。また、第二工程に用いられる触媒としては、例えば、モリブデン、バナジウム、タングステンからなる触媒（特許文献６）、モリブデン、バナジウム、銅、タングステン、クロムからなる触媒（特許文献７）、モリブデン、バナジウムからなる触媒（特許文献８）、モリブデン、バナジウム、銅とアンチモン、ゲルマニウムの少なくとも１種の元素とからなる触媒（特許文献９）などが開示されている。 In such a method for producing acrylic acid by catalytic vapor phase oxidation of propylene in the presence of molecular oxygen or molecular oxygen-containing gas, it is used for the first step of producing acrolein by catalytic vapor phase oxidation of propylene. As a catalyst used in the second step of producing acrylic acid by catalytic gas phase oxidation of acrolein or acrolein, the catalyst performance such as the yield of the target product and the catalyst life is not necessarily sufficient, Various companies have been studied and various proposals have been made for the purpose of improvement. The catalyst used in the first step includes, for example, Mo, Bi, Fe, Sb, and Ni, and further contains at least one element of K, Rb, and Cs as essential components (Patent Document 1 and Patent Document 2). A catalyst containing at least one element of Ni and Co as an essential component (Patent Document 3), Mo, Bi and Fe, and at least Mg, Ca, Zn, Cd and Ba A catalyst containing one element as an essential component (Patent Document 4), a catalyst containing Mo, Bi and Fe and further containing at least one element of Group IIA and IIB elements as an essential component (Patent Document 5) are disclosed. Yes. Examples of the catalyst used in the second step include a catalyst made of molybdenum, vanadium, and tungsten (Patent Document 6), a catalyst made of molybdenum, vanadium, copper, tungsten, and chromium (Patent Document 7), molybdenum, and vanadium. And a catalyst comprising at least one element selected from molybdenum, vanadium, copper and antimony, and germanium (Patent Document 9).
しかしながら、前記した技術はいずれも、目的とするアクリル酸の収率や触媒寿命等の面において、工業的な規模から見てなお改善の余地を残すものである。 However, all of the above-described techniques still leave room for improvement in terms of the yield of the target acrylic acid, catalyst life, and the like from an industrial scale.
かくして、本発明の目的は、プロピレンの接触気相酸化によりアクリル酸を製造する方法において、高収率で長期間にわたって安定してアクリル酸を製造する方法を提供することにある。 Thus, an object of the present invention is to provide a method for producing acrylic acid stably in a high yield over a long period of time in a method for producing acrylic acid by catalytic gas phase oxidation of propylene.
反応に使用する触媒量が多く、単位容積当たりに充填される触媒の表面積が大きいほど触媒性能および触媒寿命に対して好ましいことは当業者であれば当然認識していることである。 Those skilled in the art will naturally recognize that the greater the amount of catalyst used in the reaction and the greater the surface area of the catalyst packed per unit volume, the better for catalyst performance and catalyst life.
しかしながら、プロピレンあるいはアクロレインの酸化反応のような発熱を伴う反応では、局部的な異常発熱部（以下、「ホットスポット部」という）が発生し、長期間の反応の間に触媒の粉化、崩壊あるいは構成成分の触媒からの飛散、昇華などが発生し、触媒性能および触媒寿命が低下する傾向があり、１本当たりの反応管に充填される触媒量が多くなる、すなわち、触媒の充填密度が高くなるほどその傾向は強くなる。一方、１本当たりの反応管に充填される触媒量が少ないと反応ガスとの接触効率が低下するため、十分な活性が得られず、また、経時的な触媒の性能劣化が起こり易いなど、触媒性能および触媒寿命の面で好ましくない。また、充填された触媒の表面積に関しても同様の問題が発生する。 However, in reactions involving heat generation such as the oxidation reaction of propylene or acrolein, local abnormal heat generation portions (hereinafter referred to as “hot spot portions”) are generated, and the catalyst is pulverized and disintegrated during a long-term reaction. Alternatively, scattering of constituent components from the catalyst, sublimation, and the like occur, and the catalyst performance and the catalyst life tend to be reduced, and the amount of catalyst charged in one reaction tube increases, that is, the catalyst packing density increases. The higher the value, the stronger the tendency. On the other hand, if the amount of catalyst charged in one reaction tube is small, the contact efficiency with the reaction gas decreases, so that sufficient activity cannot be obtained, and the catalyst performance is likely to deteriorate over time, etc. It is not preferable in terms of catalyst performance and catalyst life. The same problem occurs with respect to the surface area of the packed catalyst.
本発明者らは上記問題を鑑み触媒の充填方法について鋭意検討した結果、固定床熱交換型反応器に触媒を充填するに際し、触媒の充填密度におよび単位容積当たりの触媒に起因する表面積が特定の範囲になるように触媒を充填することにより長期間安定して高い収率でアクリル酸を製造することができることを見出し本発明に至った。 As a result of intensive studies on the catalyst packing method in view of the above problems, the present inventors have determined the catalyst packing density and the surface area attributable to the catalyst per unit volume when packing the catalyst into the fixed bed heat exchange reactor. The inventors have found that acrylic acid can be produced stably and in a high yield for a long period of time by filling the catalyst so as to be in the above range.
本発明の方法によれば、高収率で長期間にわたって安定してアクリル酸を製造することができる。 According to the method of the present invention, acrylic acid can be produced stably over a long period of time with a high yield.
以下、本発明にかかるアクリル酸の製造方法について詳しく説明するが、本発明の範囲はこれらの説明に拘束されることはなく、以下の例示以外についても本発明の趣旨を損なわない範囲で適宜変更し、実施することができる。 Hereinafter, although the manufacturing method of acrylic acid concerning this invention is demonstrated in detail, the range of this invention is not restrained by these description, and changes suitably in the range which does not impair the meaning of this invention except the following illustrations. And can be implemented.
本発明において、固定床熱交換型反応器の各反応管に触媒を充填するに際して、各反応管に充填されるべき触媒の充填密度および表面積を特定の範囲内に調整する必要がある。具体的には、プロピレンを接触気相酸化してアクロレインを製造する第一工程において、固定床熱交換型反応器の各反応管にモリブデン、ビスマスおよび鉄を必須成分とする触媒を充填密度が０．７５ｇ／ｃｍ３以上、より好ましくは０．７５〜１．２ｇ／ｃｍ３の範囲、かつ触媒１Ｌ（リッター）当たりの表面積が７，０００〜１２，０００ｍ２、より好ましくは８，０００〜１１，０００ｍ２の範囲になるように触媒を充填し、第一工程で得られたアクロレインをさらに接触気相酸化してアクリル酸を製造する第二工程において、固定床熱交換型反応器の各反応管にモリブデンおよびバナジウムを必須成分とする触媒の充填密度を０．９０ｇ／ｃｍ３以上、より好ましくは１．００〜１．６０ｇ／ｃｍ３の範囲、かつ触媒１Ｌ（リッター）当たりの表面積が２，０００〜６，０００ｍ２、より好ましくは２，１００〜４，０００ｍ２の範囲になるように触媒を充填する。 In the present invention, when the catalyst is filled in each reaction tube of the fixed bed heat exchange reactor, it is necessary to adjust the packing density and surface area of the catalyst to be filled in each reaction tube within a specific range. Specifically, in the first step of producing acrolein by catalytic vapor phase oxidation of propylene, the packing density of the catalyst containing molybdenum, bismuth and iron as essential components is zero in each reaction tube of the fixed bed heat exchange reactor. .75 g / cm 3 or more, more preferably in the range of 0.75 to 1.2 g / cm 3 , and the surface area per liter of the catalyst is 7,000 to 12,000 m 2 , more preferably 8,000 to 11 In the second step of preparing acrylic acid by further catalytic gas phase oxidation of the acrolein obtained in the first step and filling the catalyst so as to be in the range of 1,000,000 m 2 , each reaction of the fixed bed heat exchange reactor tube molybdenum and vanadium the packing density of the catalyst as an essential component 0.90 g / cm 3 or more, more preferably in the range of 1.00~1.60g / cm 3, and the catalyst 1L (liter The catalyst is charged so that the surface area per ter) is in the range of 2,000 to 6,000 m 2 , more preferably 2,100 to 4,000 m 2 .
触媒の充填密度および表面積が上記範囲未満の場合、触媒と反応ガスとの接触効率が低下するため、十分な活性が得られず第一工程におけるアクロレインの収量および第二工程におけるアクリル酸の収量が低く、また、触媒の経時劣化も進み易く触媒寿命も短い。一方、反応管内に充填された触媒の充填密度および表面積が上記範囲より大きい場合、圧力損失が増加し、ブロワー等のランニングコストが増加すると共に逐次反応の増加により、結果として第一工程におけるアクロレインの収量および第二工程におけるアクリル酸の収量が低くなる。更に先述したように高温のホットスポット部の発生により局部的な触媒の劣化の点からも不利である。 When the packing density and surface area of the catalyst are less than the above ranges, the contact efficiency between the catalyst and the reaction gas is reduced, so that sufficient activity cannot be obtained and the yield of acrolein in the first step and the yield of acrylic acid in the second step are reduced. In addition, the catalyst is easily deteriorated with time and the catalyst life is short. On the other hand, when the packing density and surface area of the catalyst packed in the reaction tube are larger than the above ranges, the pressure loss increases, the running cost of the blower and the like increases, and the sequential reaction increases, resulting in the acrolein in the first step. The yield and the yield of acrylic acid in the second step are low. Further, as described above, it is disadvantageous in terms of local catalyst deterioration due to the generation of a hot spot portion.
本発明における反応管に充填された触媒の充填密度および触媒１Ｌ（リッター）当たりの表面積は、下記式により算出される。
充填密度（ｇ／ｃｍ３）
＝反応管に充填された触媒の質量（ｇ）／反応管に充填された触媒の容量（ｃｍ３）
ここで、
反応管に充填された触媒の容量（ｃｍ３）
＝反応管に充填された触媒の充填層長×（（反応管内径／２）２×円周率）
であり、
表面積（ｍ２）＝充填密度（ｇ／ｃｍ３）×比表面積（ｍ２／ｇ）×１，０００（ｃｍ３）
なお、比表面積は、この種の測定に一般的に用いられるＢＥＴ比表面積計などの装置を用いて測定できる。
The packing density of the catalyst packed in the reaction tube and the surface area per 1 L (liter) of the catalyst in the present invention are calculated by the following equations.
Packing density (g / cm 3 )
= Mass of catalyst charged in reaction tube (g) / capacity of catalyst charged in reaction tube (cm 3 )
here,
Capacity of the catalyst filled in the reaction tube (cm 3 )
= Packed bed length of catalyst packed in reaction tube × ((reaction tube inner diameter / 2) 2 × circumference ratio)
And
Surface area (m 2 ) = packing density (g / cm 3 ) × specific surface area (m 2 / g) × 1,000 (cm 3 )
The specific surface area can be measured using an apparatus such as a BET specific surface area meter generally used for this type of measurement.
本発明におけるプロピレンを接触気相酸化してアクロレインを製造する第一工程に用いられる触媒としては、触媒成分としてモリブデン、ビスマスおよび鉄を必須成分とする触媒であって、下記一般式（１）
Ｍｏ１２ＢｉａＦｅｂＡｃＢｄＣｅＤｆＯｘ （１）
（ここで、Ｍｏはモリブデン、Ｂｉはビスマス、Ｆｅは鉄、Ａはコバルトおよびニッケルから選ばれる少なくとも１種の元素、Ｂはアルカリ金属、アルカリ土類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はタングステン、ケイ素、アルミニウム、ジルコニウムおよびチタン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、砒素、ホウ素および亜鉛から選ばれる少なくとも１種の元素、Ｏは酸素であり、ａ、ｂ、ｃ、ｄ、ｅ、ｆおよびｘはそれぞれＢｉ、Ｆｅ、Ａ、Ｂ、Ｃ、ＤおよびＯの原子比を表し、０＜ａ≦１０、０＜ｂ≦２０、２≦ｃ≦２０、０＜ｄ≦１０、０≦ｅ≦３０、０≦ｆ≦４であり、ｘはそれぞれの元素の酸化状態によって定まる数値である。）で表される触媒が好適である。
The catalyst used in the first step of producing acrolein by catalytic vapor phase oxidation of propylene in the present invention is a catalyst having molybdenum, bismuth and iron as essential components as catalyst components, and the following general formula (1)
Mo 12 Bi a Fe b A c B d C e D f O x (1)
(Where Mo is molybdenum, Bi is bismuth, Fe is iron, A is at least one element selected from cobalt and nickel, B is at least one element selected from alkali metals, alkaline earth metals and thallium, C is at least one element selected from tungsten, silicon, aluminum, zirconium and titanium, D is at least one element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic, boron and zinc The element, O is oxygen, a, b, c, d, e, f and x represent the atomic ratios of Bi, Fe, A, B, C, D and O, respectively, and 0 <a ≦ 10, 0 < b ≦ 20, 2 ≦ c ≦ 20, 0 <d ≦ 10, 0 ≦ e ≦ 30, 0 ≦ f ≦ 4, and x is a numerical value determined by the oxidation state of each element. In catalyst represented it is preferred.
また、本発明におけるアクロレインを接触気相酸化してアクリル酸を製造する第二工程に用いられる触媒としては、触媒成分としてモリブデンおよびバナジウムを必須成分とする触媒であって、下記一般式（２）
Ｍｏ１２ＶｐＡｑＢｒＣｓＤｔＯｚ （２）
（ここで、Ｍｏはモリブデン、Ｖはバナジウム、Ａはニオブおよび／またはタングステン、Ｂはクロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、およびビスマスからなる群より選ばれる少なくとも１種の元素、Ｃはスズ、アンチモン、テルルからなる群より選ばれる少なくとも１種の元素、Ｄはチタン、アルミニウム、ケイ素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ｐ、ｑ、ｒ、ｓ、ｔおよびｚはそれぞれＶ、Ａ、Ｂ、Ｃ、ＤおよびＯの原子比を表し、ｐ＝１〜１４、ｑ＝０〜１２、ｒ＝０〜１０、ｓ＝０〜６、ｔ＝０〜４０であり、ｚは各元素の酸化状態によって定まる数値である）で表される触媒が好適である。
The catalyst used in the second step of producing acrylic acid by catalytic vapor phase oxidation of acrolein in the present invention is a catalyst having molybdenum and vanadium as essential components as catalyst components, and the following general formula (2)
Mo 12 V p A q B r C s D t O z (2)
(Where Mo is molybdenum, V is vanadium, A is niobium and / or tungsten, B is at least one element selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, zinc, and bismuth, C represents at least one element selected from the group consisting of tin, antimony and tellurium, D represents at least one element selected from titanium, aluminum, silicon and zirconium, O represents oxygen, and p, q, r, s, t and z represent atomic ratios of V, A, B, C, D and O, respectively, p = 1 to 14, q = 0 to 12, r = 0 to 10, s = 0 to 6, t = 0 to 40, and z is a numerical value determined by the oxidation state of each element).
前記した第一工程および第二工程に用いられる触媒の調製には、一般的に用いられる方法を用いて製造することができ、下記に一例を示す。 For the preparation of the catalyst used in the first step and the second step described above, it can be produced by a generally used method, and an example is shown below.
触媒活性成分の原料として、各成分元素の酸化物、水酸化物、アンモニウム塩、硝酸塩、炭酸塩、硫酸塩、有機酸塩などの塩類や、それらの水溶液、ゾルなど、あるいは、複数の元素を含む化合物などを、例えば、水に混合して水溶液あるいは水性スラリー（以下、「出発原料混合液」）とする。 As raw materials for catalytically active components, oxides, hydroxides, ammonium salts, nitrates, carbonates, sulfates, organic acid salts, etc. of each component element, their aqueous solutions, sols, etc., or multiple elements The compound or the like is mixed with water to form an aqueous solution or an aqueous slurry (hereinafter referred to as “starting raw material mixture”).
次に、必要に応じて、得られた出発原料混合液を、加熱や減圧など各種方法により乾燥させて触媒前駆体とする。加熱による乾燥方法としては、例えば、スプレードライヤー、ドラムドライヤー等を用いて粉末状の触媒前駆体を得ることもできるし、箱型乾燥機、トンネル型乾燥機等を用いて気流中で加熱してブロック状またはフレーク状の触媒前駆体を得ることもできる。また、一旦、出発原料混合液を濃縮、蒸発乾固してケーキ状の固形物を得て、この固形物をさらに上記加熱処理する方法も採用できる。減圧による乾燥方法としては、例えば、真空乾燥機を用いて、ブロック状または粉末状の触媒前駆体を得ることができる。 Next, if necessary, the obtained starting material mixture is dried by various methods such as heating and decompression to obtain a catalyst precursor. As a drying method by heating, for example, a powdered catalyst precursor can be obtained using a spray dryer, a drum dryer or the like, or heated in an air stream using a box-type dryer, a tunnel-type dryer or the like. Block or flake catalyst precursors can also be obtained. Alternatively, a method of once concentrating the starting raw material mixture and evaporating to dryness to obtain a cake-like solid and further subjecting the solid to the above heat treatment can also be employed. As a drying method by reduced pressure, for example, a block or powdery catalyst precursor can be obtained using a vacuum dryer.
得られた乾燥物は、必要に応じて適当な粒度の粉体を得るための粉砕工程や分級工程を経て、続く成形工程に送られる。なお、上記触媒前駆体の粉体の粒度は、特に限定されないが、成形性に優れる点で５００μｍ以下が好ましい。 The obtained dried product is sent to a subsequent molding step through a pulverization step and a classification step for obtaining a powder having an appropriate particle size as required. The particle size of the catalyst precursor powder is not particularly limited, but is preferably 500 μm or less in terms of excellent moldability.
触媒の成形方法としては、前記触媒前駆体あるいは前記触媒前駆体と粉体状の不活性担体との混合物を押し出し成形法や打錠成形法などにより一定の形状に成形する方法、触媒成分を一定の形状を有する任意の不活性担体上に担持する担持法がある。 As a method for molding the catalyst, a method of molding the catalyst precursor or a mixture of the catalyst precursor and a powdery inert carrier into a certain shape by an extrusion molding method or a tableting molding method, a constant catalyst component is used. There is a supporting method of supporting on an arbitrary inert carrier having the following shape.
押し出し成形法や打錠成形法等の場合、その形状に特に制限はなく、球状、円柱状、リング状、不定形などのいずれの形状でもよい。もちろん球状の場合、真球である必要はなく実質的に球状であればよく、円柱状およびリング状についても同様である。 In the case of an extrusion molding method or a tableting molding method, the shape is not particularly limited, and may be any shape such as a spherical shape, a cylindrical shape, a ring shape, and an indeterminate shape. Of course, in the case of a spherical shape, it does not need to be a true sphere, and may be substantially spherical, and the same applies to a cylindrical shape and a ring shape.
担持法としては、例えば、一定の形状を有する所望の不活性担体に、出発原料混合液を乾燥させずに水溶液あるいは水性スラリーのまま、加熱しながら塗布あるいは付着させて乾燥担持させる蒸発乾固法や、不活性担体に前記触媒前駆体を粉体状で担持させる造粒法にしたがって製造することができる。中でも、特に特開昭６３−２００８３９号公報および特開昭６４−８５１３９号公報に記載の遠心流動コーティング法、特開平１０−２８８７７号公報および特開平８−２９９７９７号公報に記載の転動造粒法、特開２００４−１３６２６７号公報に記載のロッキングミキサー法を用いて不活性担体に担持する造粒法が好ましい。 As the loading method, for example, an evaporation to dryness method in which a starting inert liquid mixture or an aqueous slurry is applied to or adhered to a desired inert carrier having a certain shape while being heated or dried while being dried and supported. Alternatively, it can be produced according to a granulation method in which the catalyst precursor is supported in powder form on an inert carrier. Among them, the centrifugal fluid coating method described in JP-A 63-200839 and JP-A 64-85139, and rolling granulation described in JP-A 10-28877 and JP-A 8-299797 are particularly preferable. And a granulation method in which the carrier is supported on an inert carrier using the rocking mixer method described in JP-A No. 2004-136267 is preferable.
不活性担体としては、アルミナ、シリカ、シリカ−アルミナ、チタニア、マグネシア、ステアタイト、コージェライト、シリカ−マグネシア、炭化ケイ素、窒化ケイ素、ゼオライト等が挙げられる。担持法で使用する場合、その形状についても特に制限はなく、球状、円柱状、リング状など公知の形状のものが使用できる。 Examples of the inert carrier include alumina, silica, silica-alumina, titania, magnesia, steatite, cordierite, silica-magnesia, silicon carbide, silicon nitride, zeolite, and the like. When used in the supporting method, the shape is not particularly limited, and known shapes such as a spherical shape, a cylindrical shape, and a ring shape can be used.
成形工程においては、成形性を向上させるための成形補助剤やバインダー、触媒に適度な細孔を形成させるための気孔形成剤などを用いることができる。具体例としては、エチレングリコール、グリセリン、プロピオン酸、マレイン酸、ベンジルアルコール、プロピルアルコール、ブチルアルコールまたはフェノール類の有機化合物や水、硝酸、硝酸アンモニウム、炭酸アンモニウムなどが挙げられる。 In the molding step, a molding aid or binder for improving moldability, a pore forming agent for forming appropriate pores in the catalyst, or the like can be used. Specific examples include organic compounds such as ethylene glycol, glycerin, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, butyl alcohol or phenols, water, nitric acid, ammonium nitrate, and ammonium carbonate.
また、別に触媒の機械強度を向上させる目的で、セラミック繊維、ガラス繊維、炭化ケイ素、窒化ケイ素などの補強剤を用いることもできる。補強剤は、出発原料混合液に添加しておいてもよいし、触媒前駆体に配合してもよい。 In addition, for the purpose of improving the mechanical strength of the catalyst, reinforcing agents such as ceramic fibers, glass fibers, silicon carbide, and silicon nitride can be used. The reinforcing agent may be added to the starting raw material mixture or may be blended with the catalyst precursor.
上記成形工程で得られた成形体あるいは担持体は、続く焼成工程に送られる。焼成温度としてはプロピレンを接触気相酸化してアクロレインを製造する第一工程で用いられるモリブデン、ビスマスおよび鉄を必須成分とする触媒の場合、３５０℃〜６００℃、好ましくは４００℃〜５５０℃、更に好ましくは４２０℃〜４９０℃、焼成時間としては好ましくは１〜１０時間であり、アクロレインを接触気相酸化してアクリル酸を製造する第二工程で用いられるモリブデンおよびバナジウムを必須成分とする触媒の場合、３００℃〜５００℃、好ましくは３５０℃〜４５０℃、更に好ましくは３７０℃〜４３０℃、焼成時間としては好ましくは１〜１０時間である。焼成雰囲気としては、酸化雰囲気であれば良いが、分子状酸素含有ガス雰囲気が好ましく、特に、分子状酸素含有ガス流通下に焼成工程を行うのが好ましい。分子状酸素含有ガスとしては空気が好適に用いられる。 The molded body or carrier obtained in the molding process is sent to the subsequent firing process. In the case of a catalyst having molybdenum, bismuth and iron as essential components used in the first step of producing acrolein by catalytic vapor phase oxidation of propylene as a firing temperature, 350 ° C to 600 ° C, preferably 400 ° C to 550 ° C, More preferably, the catalyst is 420 ° C. to 490 ° C., and the firing time is preferably 1 to 10 hours. The catalyst mainly contains molybdenum and vanadium used in the second step of producing acrylic acid by catalytic gas phase oxidation of acrolein. In this case, it is 300 ° C. to 500 ° C., preferably 350 ° C. to 450 ° C., more preferably 370 ° C. to 430 ° C., and the firing time is preferably 1 to 10 hours. The firing atmosphere may be an oxidizing atmosphere, but a molecular oxygen-containing gas atmosphere is preferable, and it is particularly preferable to perform the firing step under the flow of the molecular oxygen-containing gas. Air is suitably used as the molecular oxygen-containing gas.
なお、焼成工程で用いる焼成炉としては特に制限はなく、一般的に使用される箱型焼成炉あるいはトンネル型焼成炉等を用いればよい。 In addition, there is no restriction | limiting in particular as a baking furnace used by a baking process, What is necessary is just to use the box-type baking furnace or tunnel type baking furnace etc. which are generally used.
本発明における固定床熱交換型反応器の各反応管に充填された触媒の充填密度および表面積が上記範囲になるようにするためには、充填される触媒の物性、特に密度、比表面積等を制御する必要があり、触媒調製時の条件調整が特に重要である。 In order to make the packing density and surface area of the catalyst packed in each reaction tube of the fixed bed heat exchange reactor in the present invention fall within the above range, the physical properties of the catalyst to be packed, particularly the density, specific surface area, etc. are set. It is necessary to control, and adjustment of conditions during catalyst preparation is particularly important.
具体的には、前記した成形工程において用いられる成形補助剤、バインダー、気孔形成剤、補強剤の添加量を制御する方法、打錠成型する場合における圧縮する圧力（打圧）を制御する方法、等を挙げることが出来る。また、触媒が充填される反応管の内径に対して触媒の粒径を制御することによっても前記範囲内になるように制御することが可能であり、もちろん、これらを組み合わせてもよい。 Specifically, a method for controlling the amount of the molding auxiliary, binder, pore forming agent, and reinforcing agent used in the molding step described above, a method for controlling the compression pressure (compression pressure) when tableting molding, Etc. can be mentioned. It is also possible to control the particle diameter of the catalyst with respect to the inner diameter of the reaction tube filled with the catalyst so that it falls within the above range. Of course, these may be combined.
本発明におけるプロピレンを分子状酸素又は分子状酸素含有ガスにより接触気相酸化してアクリル酸を製造するのに用いられる反応器については、固定床反応器である限り特段の制限はないが、特に固定床多管式反応器が好ましい。その際、プロピレンを接触気相酸化してアクロレインを製造する第一反応器（第一工程）と得られたアクロレインを接触気相酸化してアクリル酸を製造する第二反応器（第二工程）の二つの反応器を用い、第一反応器からのアクロレインを含有する反応ガスと、リサイクルガス、酸素、あるいは窒素や水蒸気などの不活性ガスとを第二反応器に導入しアクロレインを接触気相酸化してアクリル酸を製造する方法、一つの反応器を二つの反応帯に分割し、一方の反応帯にはプロピレンの酸化用触媒を充填（第一工程）し、もう一方の反応帯にはアクロレインの酸化用触媒を充填（第二工程）した一つの反応器を用いプロピレンからアクリル酸を製造する方法など公知の方法が採用できる。その反応管の内径は通常１５〜５０ｍｍ、より好ましくは２０〜４０ｍｍ、さらに好ましくは２２〜３８ｍｍである。 The reactor used for producing acrylic acid by catalytic gas phase oxidation of propylene in the present invention with molecular oxygen or a molecular oxygen-containing gas is not particularly limited as long as it is a fixed bed reactor, A fixed bed multitubular reactor is preferred. At that time, a first reactor for producing acrolein by catalytic vapor phase oxidation of propylene (first step) and a second reactor for producing acrylic acid by catalytic vapor phase oxidation of the obtained acrolein (second step) The reaction gas containing acrolein from the first reactor and the recycle gas, oxygen, or an inert gas such as nitrogen or water vapor are introduced into the second reactor and acrolein is contacted in the gas phase. A method of producing acrylic acid by oxidation, one reactor is divided into two reaction zones, one reaction zone is filled with propylene oxidation catalyst (first step), the other reaction zone is A known method such as a method of producing acrylic acid from propylene using one reactor filled with an acrolein oxidation catalyst (second step) can be employed. The inner diameter of the reaction tube is usually 15 to 50 mm, more preferably 20 to 40 mm, and still more preferably 22 to 38 mm.
固定床多管式反応器の各反応管には、必ずしも単一の触媒を充填する必要はなく、各反応管に充填される触媒の充填密度および単位容積当たりに充填される触媒の表面積が本発明の特定範囲内である限り、それぞれの工程において従来公知の複数種の触媒をそれぞれ層（以下、「反応帯」という）をなすように充填することも可能である。例えば、特開平４−２１７９３２号公報および特開平９−２４１２０９号公報のような異なる占有容積を有する複数の触媒を原料ガス入口側から出口側に向かって占有容積が小さくなるように充填する方法、あるいは特開平１０−１６８００３号公報および特開平７−１０８０２号公報のような担持率の異なる複数の触媒を原料ガス入口側から出口側に向かって担持率が高くなるように充填する方法、あるいは特開２００５−３２０３１５号公報のような触媒の一部を不活性な担体などで希釈する方法、あるいはこれらを組み合わせる方法などを採用してもよい。この時、反応帯の数は、反応条件や反応器の規模により適宜決定されるが、反応帯の数が多すぎると触媒の充填作業が煩雑になるなどの問題が発生するため工業的には２〜６程度までが望ましい。 Each reaction tube of the fixed bed multi-tubular reactor does not necessarily need to be filled with a single catalyst, but the packing density of the catalyst filled in each reaction tube and the surface area of the catalyst filled per unit volume are not limited. As long as it is within the specific range of the invention, it is possible to charge a plurality of conventionally known catalysts in each step so as to form layers (hereinafter referred to as “reaction zone”). For example, a method of filling a plurality of catalysts having different occupied volumes as disclosed in JP-A-4-217932 and JP-A-9-241209 so that the occupied volume decreases from the raw material gas inlet side toward the outlet side, Alternatively, a method of filling a plurality of catalysts having different loading ratios such as JP-A-10-168003 and JP-A-7-10802 so that the loading ratio increases from the raw material gas inlet side to the outlet side, or A method of diluting a part of the catalyst with an inert carrier or the like, or a method of combining these may be employed as disclosed in Japanese Unexamined Patent Application Publication No. 2005-320315. At this time, the number of reaction zones is appropriately determined depending on the reaction conditions and the scale of the reactor. However, if the number of reaction zones is too large, problems such as complicated packing of the catalyst may occur. About 2-6 is desirable.
本発明における反応条件には特に制限はなく、この種の反応に一般に用いられている条件であればいずれも実施することが可能である。例えば、原料ガスとして１〜１５容量％、好ましくは４〜１２容量％のプロピレン、０．５〜２５容量％、好ましくは２〜２０容量％の分子状酸素、０〜３０容量％、好ましくは０〜２５容量％の水蒸気、残部が窒素などの不活性ガスからなる混合ガスを０．１〜１．０ＭＰａの圧力下、３００〜５，０００Ｈｒ−１（ＳＴＰ）の空間速度で各工程の触媒に接触させればよい。第一工程および第二工程の好適な反応温度は、反応条件などによって適宜選択されるが、通常、第一工程では３００〜３８０℃であり、第二工程では、２５０〜３５０℃である。 There are no particular limitations on the reaction conditions in the present invention, and any of the conditions generally used for this type of reaction can be implemented. For example, the raw material gas is 1-15% by volume, preferably 4-12% by volume propylene, 0.5-25% by volume, preferably 2-20% by volume molecular oxygen, 0-30% by volume, preferably 0 A mixed gas consisting of ˜25% by volume of water vapor and the balance of an inert gas such as nitrogen is used as a catalyst in each step at a space velocity of 300 to 5,000 Hr −1 (STP) under a pressure of 0.1 to 1.0 MPa. What is necessary is just to contact. Suitable reaction temperatures in the first step and the second step are appropriately selected depending on the reaction conditions and the like, but are usually 300 to 380 ° C. in the first step and 250 to 350 ° C. in the second step.
反応原料ガスとしてのプロピレンのグレードについては特に制限はなく、ポリマーグレードやケミカルグレードのプロピレンなどを用いることができる。また、プロパンの酸化脱水素反応によって得られるプロピレン含有の混合ガスも使用可能であり、この混合ガスに必要に応じ、空気または酸素などを添加することもできる。 The grade of propylene as the reaction raw material gas is not particularly limited, and polymer grade or chemical grade propylene can be used. A propylene-containing mixed gas obtained by propane oxidative dehydrogenation can also be used, and air, oxygen, or the like can be added to the mixed gas as necessary.
以下に、実施例を挙げて本発明を具体的に説明するが、本発明はこれにより何ら限定されるものではない。なお、以下では、便宜上、「質量部」を単に「部」、と記すことがある。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Hereinafter, for convenience, “parts by mass” may be simply referred to as “parts”.
プロピレン転化率、アクリル酸収率は次式によって求めた。
プロピレン転化率［モル％］
＝（反応したプロピレンのモル数）／（供給したプロピレンのモル数）×１００
アクリル酸収率［モル％］
＝（生成したアクリル酸のモル数）／（供給したプロピレンのモル数）×１００
［触媒の比表面積測定］
ＢＥＴ比表面積計として株式会社マウンテック製 Ｍａｃｓｏｒｂ ｍｏｄｅｌ−１２１０を用いて触媒の比表面積を測定した。
〔触媒製造例１：第一工程触媒（１）の調製〕
イオン交換水１０００部に硝酸コバルト６８９部および硝酸第二鉄１９１部を溶解した。また、硝酸ビスマス２７５部を濃硝酸（６５ｗｔ％）３６部とイオン交換水２００部からなる硝酸水溶液に溶解した。別に、加熱したイオン交換水３０００部にパラモリブデン酸アンモニウム１０００部を添加し、撹拌しながら溶解した。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、次いで硝酸カリウム２．９部をイオン交換水５０部に溶解した水溶液および２０ｗｔ％のシリカゾル１４２部を順次添加した。この様にして得られた懸濁液を加熱攪拌し、蒸発乾固、乾燥した。次いで、得られた固形物を５００μｍ以下に粉砕した。得られた粉体１０００部に対して５０ｗｔ％の硝酸アンモニウム水溶液２２０部を加え、混練りした後、外径６ｍｍ、内径２ｍｍ、長さ６．５ｍｍのリング状に押し出し成型し、空気流通下４６０℃で８時間焼成して触媒（１）を得た。
この触媒（１）の酸素以外の金属元素の組成は原子比で次のとおりであった。
触媒（１） Ｍｏ１２Ｂｉ１．２Ｆｅ１Ｃｏ５Ｓｉ１Ｋ０．０６
触媒（１）の比表面積を測定したところ、１１．６ｍ２／ｇであった。
〔触媒製造例２〜４：第一工程触媒（２）〜（４）の調製〕
触媒製造例１において、粉体に添加する硝酸アンモニウム水溶液の濃度および量を表１のように変更した以外は、同様に調製した。それぞれの触媒の比表面積を測定した結果も表１に示す。
The propylene conversion rate and acrylic acid yield were determined by the following formulas.
Propylene conversion [mol%]
= (Number of moles of propylene reacted) / (number of moles of supplied propylene) × 100
Acrylic acid yield [mol%]
= (Mole number of acrylic acid produced) / (Mole number of supplied propylene) × 100
[Measurement of specific surface area of catalyst]
The specific surface area of the catalyst was measured using a Macsorb model-1210 manufactured by Mountec Co., Ltd. as a BET specific surface area meter.
[Catalyst Production Example 1: Preparation of First Step Catalyst (1)]
In 1000 parts of ion-exchanged water, 689 parts of cobalt nitrate and 191 parts of ferric nitrate were dissolved. Further, 275 parts of bismuth nitrate was dissolved in an aqueous nitric acid solution consisting of 36 parts of concentrated nitric acid (65 wt%) and 200 parts of ion-exchanged water. Separately, 1000 parts of ammonium paramolybdate was added to 3000 parts of heated ion-exchanged water and dissolved with stirring. Two aqueous solutions prepared separately were added dropwise to the obtained aqueous solution and mixed, and then an aqueous solution prepared by dissolving 2.9 parts of potassium nitrate in 50 parts of ion-exchanged water and 142 parts of 20 wt% silica sol were sequentially added. The suspension thus obtained was heated and stirred, evaporated to dryness and dried. Next, the obtained solid was pulverized to 500 μm or less. To 1000 parts of the obtained powder, 220 parts of a 50 wt% ammonium nitrate aqueous solution was added and kneaded, and then extruded into a ring shape having an outer diameter of 6 mm, an inner diameter of 2 mm, and a length of 6.5 mm, and 460 ° C. under air flow. And calcined for 8 hours to obtain catalyst (1).
The composition of metal elements other than oxygen in the catalyst (1) was as follows in terms of atomic ratio.
Catalyst (1) Mo 12 Bi 1.2 Fe 1 Co 5 Si 1 K 0.06
It was 11.6 m < 2 > / g when the specific surface area of the catalyst (1) was measured.
[Catalyst Production Examples 2 to 4: Preparation of First Step Catalysts (2) to (4)]
In Catalyst Production Example 1, the same procedure was performed except that the concentration and amount of the aqueous ammonium nitrate solution added to the powder were changed as shown in Table 1. The results of measuring the specific surface area of each catalyst are also shown in Table 1.
〔触媒製造例５：第二工程触媒（５）の調製〕
イオン交換水２０００部を加熱撹拌しながら、この中にパラモリブデン酸アンモニウム３５０部、メタバナジン酸アンモニウム１１６部およびパラタングステン酸アンモニウム４４．６部を溶解した。別にイオン交換水２００部を加熱撹拌しながら、硝酸第二銅８７．８部および三酸化アンチモン１２部を添加した。得られた２つの液を混合し、懸濁液を得た。この懸濁液を蒸発乾固してケーキ状の固形物を得た。得られた固形物を乾燥後、５００μｍ以下に粉砕し、触媒前駆体粉体を得た。遠心流動コーティング装置に平均粒径５ｍｍのシリカ−アルミナからなる球状担体１，２００質量部を投入し、次いでバインダーとして１５質量％の硝酸アンモニウム水溶液と共に触媒前駆体粉体を９０℃の熱風を通しながら投入して担体に担持させた。得られた担持体を空気雰囲気下４００℃で６時間焼成して触媒（１）を調製した。この触媒（１）の担持率は約３２質量％であり、担体および酸素を除く金属元素の組成は原子比で次のとおりであった。
触媒（１） Ｍｏ１２Ｖ６Ｗ１Ｃｕ２．２Ｓｂ０．５
なお、担持率は下記式により求めた。
担持率（質量％）＝
［（焼成後の触媒の質量（ｇ）−用いた担体の質量）／用いた担体の質量（ｇ）］×１００
触媒（１）の比表面積を測定したところ、２．３ｍ２／ｇであった。
〔触媒製造例６〜８：触媒（６）〜（８）の調製〕
触媒製造例１において、担体の粒径を表２に示したように変更した以外は、同様に調製した。それぞれの触媒の比表面積を測定した結果も表２に示す。
[Catalyst Production Example 5: Preparation of second step catalyst (5)]
While heating and stirring 2000 parts of ion-exchanged water, 350 parts of ammonium paramolybdate, 116 parts of ammonium metavanadate, and 44.6 parts of ammonium paratungstate were dissolved therein. Separately, 87.8 parts of cupric nitrate and 12 parts of antimony trioxide were added while heating and stirring 200 parts of ion-exchanged water. The two liquids obtained were mixed to obtain a suspension. This suspension was evaporated to dryness to obtain a cake-like solid. The obtained solid was dried and pulverized to 500 μm or less to obtain catalyst precursor powder. 1,200 parts by mass of a spherical carrier made of silica-alumina with an average particle diameter of 5 mm is put into a centrifugal fluidized coating apparatus, and then a catalyst precursor powder together with a 15% by mass ammonium nitrate aqueous solution is fed as a binder while passing hot air at 90 ° C. And supported on a carrier. The obtained carrier was calcined at 400 ° C. for 6 hours in an air atmosphere to prepare a catalyst (1). The loading ratio of the catalyst (1) was about 32% by mass, and the composition of the metal elements excluding the carrier and oxygen was as follows in terms of atomic ratio.
Catalyst (1) Mo 12 V 6 W 1 Cu 2.2 Sb 0.5
The loading rate was determined by the following formula.
Loading rate (mass%) =
[(Mass of catalyst after calcination (g) −Mass of carrier used) / Mass of carrier used (g)] × 100
It was 2.3 m < 2 > / g when the specific surface area of the catalyst (1) was measured.
[Catalyst Production Examples 6 to 8: Preparation of Catalysts (6) to (8)]
The catalyst was prepared in the same manner as in Catalyst Production Example 1 except that the particle size of the support was changed as shown in Table 2. The results of measuring the specific surface area of each catalyst are also shown in Table 2.
＜実施例１〜４および比較例１〜３＞
〔酸化反応〕
全長５０００ｍｍ、内径２５ｍｍの鋼鉄製反応管およびこれを覆う熱媒体を流すためのシェルからなる反応器を鉛直方向に用意した。なお、シェルの下から２５００ｍｍの位置にシェルを上下に分割する厚さ３０ｍｍの仕切り板を設け、上方および下方の空間部のいずれにおいても熱媒体を下方から上方に流した。
<Examples 1-4 and Comparative Examples 1-3>
[Oxidation reaction]
A reactor comprising a steel reaction tube having a total length of 5000 mm and an inner diameter of 25 mm and a shell for flowing a heat medium covering the steel reaction tube was prepared in the vertical direction. A partition plate having a thickness of 30 mm for dividing the shell vertically was provided at a position of 2500 mm from the bottom of the shell, and the heat medium was allowed to flow from below to above in both the upper and lower space portions.
その反応管上部から第一工程触媒、ＳＵＳ製ラシヒリングおよび第二工程触媒を下記表３に示す組み合わせで順に落下させ、反応管に下から順に第一工程触媒の層長２２００ｍｍ、ＳＵＳ製ラシヒリングの層長５００ｍｍおよび第二工程触媒の層長２２００ｍｍとなるように充填した。それぞれの触媒の充填密度および充填された触媒の単位容積当たりの表面積は表３に示す。この反応管にプロピレン７容量％、酸素１３容量％、水蒸気１０容量％および残部が窒素等からなる不活性ガスからなる混合ガスを第一工程触媒に対して空間速度１６００Ｈｒ−１にて導入し、酸化反応を行った。適宜反応温度を変更しながら、酸化反応を４０００時間継続させた。その結果も表３に示す。 The first step catalyst, the SUS Raschig ring and the second step catalyst are dropped sequentially from the upper part of the reaction tube in the combination shown in Table 3 below, and the layer length of the first step catalyst is 2200 mm and the SUS Raschig ring layer from the bottom in order. Packing was performed so that the length was 500 mm and the layer length of the second step catalyst was 2200 mm. The packing density of each catalyst and the surface area per unit volume of the packed catalyst are shown in Table 3. Into this reaction tube, a mixed gas composed of 7% by volume of propylene, 13% by volume of oxygen, 10% by volume of water vapor, and an inert gas composed of nitrogen or the like as the remainder was introduced at a space velocity of 1600 Hr −1 with respect to the first step catalyst. An oxidation reaction was performed. The oxidation reaction was continued for 4000 hours while appropriately changing the reaction temperature. The results are also shown in Table 3.
Claims (3)
Ｍｏ１２ＢｉａＦｅｂＡｃＢｄＣｅＤｆＯｘ （１）
（式中、Ｍｏはモリブデン、Ｂｉはビスマス、Ｆｅは鉄、Ａはコバルトおよびニッケルから選ばれる少なくとも１種の元素、Ｂはアルカリ金属、アルカリ土類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はタングステン、ケイ素、アルミニウム、ジルコニウムおよびチタン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、砒素および亜鉛から選ばれる少なくとも１種の元素、Ｏは酸素であり、ａ、ｂ、ｃ、ｄ、ｅ、ｆおよびｘはそれぞれＢｉ、Ｆｅ、Ａ、Ｂ、Ｃ、ＤおよびＯの原子比を表し、０＜ａ≦１０、０＜ｂ≦２０、２≦ｃ≦２０、０＜ｄ≦１０、０≦ｅ≦３０、０≦ｆ≦４であり、ｘはそれぞれの元素の酸化状態によって定まる数値である。） The method for producing acrolein and / or acrylic acid according to claim 1, wherein the catalyst having molybdenum, bismuth and iron as essential components is represented by the following general formula (1).
Mo 12 Bi a Fe b A c B d C e D f O x (1)
(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, A is at least one element selected from cobalt and nickel, B is at least one element selected from alkali metals, alkaline earth metals and thallium, C is at least one element selected from tungsten, silicon, aluminum, zirconium and titanium; D is at least one element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic and zinc; O is oxygen, and a, b, c, d, e, f and x represent the atomic ratio of Bi, Fe, A, B, C, D and O, respectively, and 0 <a ≦ 10, 0 <b ≦ (20, 2 ≦ c ≦ 20, 0 <d ≦ 10, 0 ≦ e ≦ 30, 0 ≦ f ≦ 4, and x is a numerical value determined by the oxidation state of each element.)
Ｍｏ１２ＶｐＡｑＢｒＣｓＤｔＯｚ （２）
（ここで、Ｍｏはモリブデン、Ｖはバナジウム、Ａはニオブおよび／またはタングステン、Ｂはクロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、およびビスマスからなる群より選ばれる少なくとも１種の元素、Ｃはスズ、アンチモン、テルルからなる群より選ばれる少なくとも１種の元素、Ｄはチタン、アルミニウム、ケイ素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ｐ、ｑ、ｒ、ｓ、ｔおよびｚはそれぞれＶ、Ａ、Ｂ、Ｃ、ＤおよびＯの原子比を表し、ｐ＝１〜１４、ｑ＝０〜１２、ｒ＝０〜１０、ｓ＝０〜６、ｔ＝０〜４０であり、ｚは各元素の酸化状態によって定まる数値である） The method for producing acrylic acid according to claim 1 or 2, wherein the catalyst containing molybdenum and vanadium as essential components is represented by the following general formula (2).
Mo 12 V p A q B r C s D t O z (2)
(Where Mo is molybdenum, V is vanadium, A is niobium and / or tungsten, B is at least one element selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, zinc, and bismuth, C represents at least one element selected from the group consisting of tin, antimony and tellurium, D represents at least one element selected from titanium, aluminum, silicon and zirconium, O represents oxygen, and p, q, r, s, t and z represent atomic ratios of V, A, B, C, D and O, respectively, p = 1 to 14, q = 0 to 12, r = 0 to 10, s = 0 to 6, t = 0 to 40, and z is a numerical value determined by the oxidation state of each element)
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