JP6743391B2 - Method for producing complex oxide catalyst - Google Patents
Method for producing complex oxide catalyst Download PDFInfo
- Publication number
- JP6743391B2 JP6743391B2 JP2016006351A JP2016006351A JP6743391B2 JP 6743391 B2 JP6743391 B2 JP 6743391B2 JP 2016006351 A JP2016006351 A JP 2016006351A JP 2016006351 A JP2016006351 A JP 2016006351A JP 6743391 B2 JP6743391 B2 JP 6743391B2
- Authority
- JP
- Japan
- Prior art keywords
- producing
- catalytically active
- oxide catalyst
- active component
- source compound
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 69
- 239000000843 powder Substances 0.000 claims description 55
- 239000002245 particle Substances 0.000 claims description 49
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 48
- 229910052710 silicon Inorganic materials 0.000 claims description 48
- 239000010703 silicon Substances 0.000 claims description 48
- 239000002131 composite material Substances 0.000 claims description 47
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 44
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 40
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 40
- 238000007254 oxidation reaction Methods 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 230000003197 catalytic effect Effects 0.000 claims description 30
- 239000011734 sodium Substances 0.000 claims description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 229910052797 bismuth Inorganic materials 0.000 claims description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- -1 acryl Chemical group 0.000 claims description 9
- 150000001299 aldehydes Chemical class 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 7
- 229910052716 thallium Inorganic materials 0.000 claims description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 59
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 21
- 239000012071 phase Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 18
- 229910021485 fumed silica Inorganic materials 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 13
- 230000007423 decrease Effects 0.000 description 12
- 235000011187 glycerol Nutrition 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 6
- 229940036358 bismuth subcarbonate Drugs 0.000 description 6
- 230000010354 integration Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001622 bismuth compounds Chemical class 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 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 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- LVAMVZXECCXUGI-UHFFFAOYSA-N acetic acid;thallium Chemical compound [Tl].CC(O)=O LVAMVZXECCXUGI-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 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
- 230000006866 deterioration Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-BJUDXGSMSA-N oxygen-15 atom Chemical compound [15O] QVGXLLKOCUKJST-BJUDXGSMSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound 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=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- DASUJKKKKGHFBF-UHFFFAOYSA-L thallium(i) carbonate Chemical compound [Tl+].[Tl+].[O-]C([O-])=O DASUJKKKKGHFBF-UHFFFAOYSA-L 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 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 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、複合酸化物触媒の製造方法に関する。詳しくは、不飽和アルデヒド及び不飽和カルボン酸を製造する際に用いる複合酸化物触媒の製造方法に関する。 The present invention relates to a method for producing a composite oxide catalyst. Specifically, it relates to a method for producing a composite oxide catalyst used when producing an unsaturated aldehyde and an unsaturated carboxylic acid.
従来、プロピレン等を酸素含有ガスと気相接触酸化反応によりアクロレイン及びアクリル酸を製造するために用いる触媒、また、イソブチレン又はターシャリーブタノール等を酸素含有ガスと気相接触酸化反応することによりメタクロレイン及びメタクリル酸を製造するために用いる触媒の製造方法については種々提案されている。 Conventionally, a catalyst used for producing acrolein and acrylic acid by a gas phase catalytic oxidation reaction of propylene with an oxygen-containing gas, and methacrolein by a gas phase catalytic oxidation reaction of isobutylene or tertiary butanol with an oxygen-containing gas. Various methods for producing catalysts used for producing methacrylic acid have been proposed.
例えば、特許文献１には、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ための触媒として、モリブデンを必須成分とする複合金属酸化物を含有する触媒粉末を、特定の相対遠心加速度にて転動造粒法により不活性担体に担持することにより製造することが記載されている。 For example, in Patent Document 1, as a catalyst for producing acrolein and acrylic acid from propylene, a catalyst powder containing a complex metal oxide containing molybdenum as an essential component is rolling granulated at a specific relative centrifugal acceleration. It is described that it is produced by supporting it on an inert carrier by the method.
しかしながら、これら従前知られた複合酸化物触媒の製造方法により得られた複合酸化物触媒によるオレフィンの気相接触酸化反応では、とりわけ高負荷条件においては反応効率が十分ではなく、所望の酸化生成物を高収率で得るために、高温で気相接触酸化反応を行うか、又は、反応時間を延長するために触媒層の体積を大きくする等の方策をとる必要がある。しかしながら、該方策では所望の酸化生成物を得る気相接触酸化反応以外の副反応が生じる場合があり、転化率の低下や、選択率の低下を引き起こし、結果として収率が低下するという問題があった。 However, in the gas phase catalytic oxidation reaction of olefins by the composite oxide catalyst obtained by these previously known methods for producing a composite oxide catalyst, the reaction efficiency is not sufficient especially under high load conditions, and the desired oxidation product is obtained. In order to obtain a high yield, it is necessary to take measures such as performing a gas phase catalytic oxidation reaction at a high temperature or increasing the volume of the catalyst layer in order to extend the reaction time. However, in this method, a side reaction other than a gas phase catalytic oxidation reaction for obtaining a desired oxidation product may occur, which causes a decrease in conversion rate and a decrease in selectivity, resulting in a problem that the yield decreases. there were.
本発明は上記問題点を解決するためになされたものである。すなわち、オレフィンを原料として酸素含有ガスとの気相接触酸化反応により対応する不飽和アルデヒド及び不飽和カルボン酸を製造する際に用いる複合酸化物触媒として、原料が複合酸化物触媒と接触する時間が短い高負荷の条件下でも原料の転化率に優れ、且つ所望とする不飽和アルデヒド及び不飽和カルボン酸の選択率を高く維持し、収率の向上が可能となる複合酸化物触媒を提供することを目的とする。 The present invention has been made to solve the above problems. That is, as a composite oxide catalyst used when producing a corresponding unsaturated aldehyde and unsaturated carboxylic acid by a gas phase catalytic oxidation reaction of an olefin as a raw material with an oxygen-containing gas, the time during which the raw material contacts the composite oxide catalyst To provide a composite oxide catalyst which is excellent in the conversion rate of a raw material even under a short high load condition, maintains a high selectivity of an unsaturated aldehyde and an unsaturated carboxylic acid desired, and can improve a yield. With the goal.
本発明者らは上記課題を解決すべく鋭意研究を重ねた結果、オレフィンを酸素含有ガスにより気相接触酸化して対応する不飽和アルデヒド及び不飽和カルボン酸を製造する際に用いる、（ａ）モリブデン、ビスマス及びケイ素を含む触媒活性元素の各供給源化合物を水性系で一体化及び加熱し、触媒活性成分の粉体を得る工程、（ｂ）工程（ａ）で得られた触媒活性成分の粉体を、転動造粒法により、不活性担体に担持する工程を含む、複合酸化物触媒（以下「触媒」と称する場合がある。）を製造する方法であり、特定の比表面積、特定の体積平均粒径を有するケイ素の供給源化合物を用いることにより、製造された該複合酸化物触媒をプロピレンの気相接触酸化反応に使用した場合、酸化反応時間が短い条件下でも原料の転化率に優れ、生成するアクロレイン及びアクリル酸の選択率を高く維持することができ、収率の向上が可能となることを見いだし、本発明に至った。 The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, used for producing a corresponding unsaturated aldehyde and unsaturated carboxylic acid by gas-phase catalytic oxidation of an olefin with an oxygen-containing gas, (a) A step of integrating and heating each source compound of a catalytically active element containing molybdenum, bismuth and silicon in an aqueous system to obtain a powder of the catalytically active component, (b) the catalytically active component obtained in the step (a) A method for producing a composite oxide catalyst (hereinafter sometimes referred to as "catalyst"), which comprises a step of supporting a powder on an inert carrier by a tumbling granulation method. When the composite oxide catalyst produced by using a silicon source compound having a volume average particle size of is used for the gas phase catalytic oxidation reaction of propylene, the conversion rate of the raw material is reduced even under the condition that the oxidation reaction time is short. It was found that the present invention is excellent, that the selectivity of acrolein and acrylic acid to be produced can be kept high, and the yield can be improved, and the present invention has been completed.
すなわち、本発明は以下である。
［１］ （ａ）モリブデン、ビスマス及びケイ素を含む触媒活性元素の各供給源化合物を水性系で一体化及び加熱し、触媒活性成分の粉体を得る工程
（ｂ）工程（ａ）で得られた触媒活性成分の粉体を、転動造粒法により、不活性担体に担持する工程を含む、オレフィンを酸素含有ガスにより気相接触酸化して不飽和アルデヒド及び不飽和カルボン酸を製造するための複合酸化物触媒を製造する方法であり、
触媒活性成分が下記組成式（１）で表され、ケイ素の供給源化合物の比表面積が１２０ｍ２／ｇ〜３００ｍ２／ｇであり、かつ体積平均粒径が０．２μｍ〜３μｍであるオレフィンを原料として酸素含有ガスとの気相接触酸化反応により対応する不飽和アルデヒド及び不飽和カルボン酸を製造する際に用いる複合酸化物触媒の製造方法。
ＭｏａＢｉｂＣｏｃＮｉｄＦｅｅＸｆＹｇＳｉｈＯｉ （１）
（式中、Ｘはナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタリウム（Ｔｌ）からなる群から選ばれる少なくとも１種の元素であり、Ｙはホウ素（Ｂ）、リン（Ｐ）、砒素（Ａｓ）及びタングステン（Ｗ）からなる群から選ばれる少なくとも１種の元素である。また、ａ〜ｉはそれぞれの元素の原子比を表わし、ａ＝１２のとき、ｂ＝０．５〜７、ｃ＝０．１〜５．０、ｄ＝０．１〜１０、ｅ＝０．０５〜５、ｆ＝０〜２、ｇ＝０〜３、ｈ＝１〜４８の範囲にあり、またｉは他の元素の酸化状態を満足させる数値である。）
That is, the present invention is as follows.
[1] (a) A step of integrating and heating respective source compounds of catalytically active elements containing molybdenum, bismuth and silicon in an aqueous system to obtain powder of a catalytically active component (b) Obtained in step (a) In order to produce an unsaturated aldehyde and an unsaturated carboxylic acid by gas-phase catalytic oxidation of an olefin with an oxygen-containing gas, including a step of supporting a powder of a catalytically active component on an inert carrier by a tumbling granulation method. Which is a method for producing a composite oxide catalyst of
Catalytically active component is represented by the following composition formula (1), the specific surface area of the source compound of silicon is the 120m 2 / g~300m 2 / g, and volume average particle size of the olefin is 0.2μm~3μm A method for producing a composite oxide catalyst used in producing a corresponding unsaturated aldehyde and unsaturated carboxylic acid by a gas phase catalytic oxidation reaction with a gas containing oxygen as a raw material.
Mo a Bi b Co c Ni d Fe e X f Y g Si h O i (1)
(In the formula, X is at least one element selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and thallium (Tl), and Y is boron (B). , At least one element selected from the group consisting of phosphorus (P), arsenic (As) and tungsten (W), and a to i represent the atomic ratio of each element, and when a=12, b=0.5-7, c=0.1-5.0, d=0.1-10, e=0.05-5, f=0-2, g=0-3, h=1- It is in the range of 48, and i is a numerical value that satisfies the oxidation states of other elements.)
［２］ 前記ケイ素の供給源化合物総体積の内、体積平均粒径の１．５倍以上の粒径を有する粒子の体積割合が１５％以下である［１］に記載の複合酸化物触媒の製造方法。
［３］ 前記触媒活性成分中、前記ケイ素に対する前記ビスマスの原子比が０．０４〜０．８０である［１］又は［２］に記載の複合酸化物触媒の製造方法。
[2] The composite oxide catalyst according to [1], wherein the volume ratio of particles having a particle size of 1.5 times or more the volume average particle size is 15% or less in the total volume of the silicon source compound. Production method.
[3] The method for producing a composite oxide catalyst according to [1] or [2], wherein in the catalytically active component, the atomic ratio of the bismuth to the silicon is 0.04 to 0.80.
［４］ プロピレンと酸素含有ガスを含む原料混合ガスを［１］乃至［３］のいずれかに
記載の複合酸化物触媒の製造方法により製造された複合酸化物触媒を用いて気相接触酸化
するアクロレイン及びアクリル酸の製造方法。
［５］ プロピレンの空間速度が８０ｈ−１〜３２０ｈ−１の範囲である［４］に記載の
アクロレイン及びアクリル酸の製造方法。
［６］ 前記原料混合ガス中のプロピレン含有量が７体積％〜１２体積％の範囲である［
４］又は［５］に記載のアクロレイン及びアクリル酸の製造方法。
[ 4 ] Gas-phase catalytic oxidation of a raw material mixed gas containing propylene and an oxygen-containing gas using the composite oxide catalyst produced by the method for producing a composite oxide catalyst according to any one of [1] to [ 3 ]. A method for producing acrolein and acrylic acid.
[5] acrolein and method for producing acrylic acid according to the space velocity of propylene is in the range of 80h -1 ~320h -1 [4].
[ 6 ] The propylene content in the raw material mixed gas is in the range of 7% by volume to 12% by volume [
4 ] or the production method of acrolein and acrylic acid according to [ 5 ].
本発明によれば、複合酸化物触媒のモリブデン、ビスマス等の各触媒活性元素の分散性を向上することが可能となり、活性種形成が促進されることにより、触媒性能が向上し、とりわけ、プロピレンの負荷が高い反応条件、すなわち、プロピレンの空間速度が高い条件で気相接触酸化反応を行っても、プロピレンの転化率に優れ、高選択率でアクロレイン及びアクリル酸を製造することができる。 According to the present invention, it becomes possible to improve the dispersibility of each catalytically active element such as molybdenum and bismuth in the composite oxide catalyst, and by promoting the formation of active species, the catalytic performance is improved, and in particular, propylene. Even if the gas-phase catalytic oxidation reaction is carried out under a reaction condition of a high load, that is, a condition in which the space velocity of propylene is high, the conversion rate of propylene is excellent and acrolein and acrylic acid can be produced with a high selectivity.
以下において、本発明について詳細に説明する。
尚、モリブデン（Ｍｏ）、ビスマス（Ｂｉ）、ケイ素（Ｓｉ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、鉄（Ｆｅ）、ナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）、タリウム（Ｔｌ）、ホウ素（Ｂ）、リン（Ｐ）、砒素（Ａｓ）、タングステン（Ｗ）の各元素は、それぞれカッコ内の元素記号を用いて表記した。
Hereinafter, the present invention will be described in detail.
In addition, molybdenum (Mo), bismuth (Bi), silicon (Si), cobalt (Co), nickel (Ni), iron (Fe), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs). ), thallium (Tl), boron (B), phosphorus (P), arsenic (As), and tungsten (W) are represented by using element symbols in parentheses.
本発明の製造方法はモリブデン、ビスマス及びケイ素を含む触媒活性元素の各供給源化合物を水性系で一体化及び加熱し、触媒活性成分の粉体を得る工程を含む（以下、「工程（ａ）」と称する場合がある）。
上記モリブデン、ビスマス及びケイ素を含む触媒活性元素の各供給源化合物を水性系で一体化とは、上記触媒活性元素の各供給源化合物の水溶液ないし水分散液を一括にあるいは段階的に混合又は熟成処理することを意味する。すなわち、（イ）上記の各供給源化合物を一括して混合する方法、（ロ）上記の各供給源化合物を一括して混合し、そして熟成処理する方法、（ハ）上記の各供給源化合物を段階的に混合する方法、（ニ）上記の各供給源化合物を段階的に混合・熟成処理を繰り返す方法、及び（イ）〜（ニ）を組み合わせた方法はいずれも上記触媒活性元素の各供給源化合物の水性系での一体化の概念に含まれる。ここで、上記熟成とは、「工業原料もしくは半製品を、一定時間、一定温度などの特定条件のもとに処理して、必要とする物理性、化学性の取得、上昇あるいは所定反応の進行などをはかる操作」（化学大辞典／共立出版）のことをいう。なお、この発明において、上記の一定時間とは、１０分〜２４時間の範囲をいい、上記の一定温度とは、室温から水溶液ないし水分散液の沸点までの範囲をいう。
The production method of the present invention includes a step of integrating and heating each source compound of a catalytically active element containing molybdenum, bismuth and silicon in an aqueous system to obtain a powder of a catalytically active component (hereinafter, referred to as “step (a) Sometimes referred to as ").
Integrating each source compound of catalytically active elements containing molybdenum, bismuth and silicon in an aqueous system means to collectively or stepwise mix or age an aqueous solution or aqueous dispersion of each source compound of catalytically active elements. Means to process. That is, (a) a method of collectively mixing the above-mentioned source compounds, (b) a method of collectively mixing the above-mentioned source compounds and aging treatment, and (c) a above-mentioned each source compound. The method of stepwise mixing, (d) the method of repeating stepwise mixing and aging treatment of the above-mentioned respective source compounds, and the method of combining (a) to (d) are all of the above-mentioned catalytically active elements. Included in the concept of integration of source compounds in an aqueous system. Here, the above-mentioned aging means that "industrial raw materials or semi-finished products are treated under a specific condition such as a constant time and a constant temperature to obtain necessary physical or chemical properties, increase or progress of a predetermined reaction. "Operation for measuring etc." (Kagaku University Dictionary/Kyoritsu Shuppan). In addition, in this invention, the above-mentioned fixed time means a range of 10 minutes to 24 hours, and the above-mentioned fixed temperature means a range from room temperature to the boiling point of the aqueous solution or the aqueous dispersion.
また、上記の加熱とは、上記の触媒活性元素の各供給源化合物個々の酸化物や複酸化物の形成、一体化により生じた複合化合物の酸化物や複酸化物の形成、生成最終複合酸化物の形成等のための熱処理をいう。そして、加熱は必ずしも１回に限らない。すなわち、この加熱は上記（イ）〜（ニ）で示される一体化の各段階で任意に行うことができ、また一体化後に必要に応じて追加して行っても構わない。上記の加熱温度は、通常２００℃〜６００℃の範囲である。
さらに、上記の一体化及び加熱においては、これら以外に、必要により乾燥、粉砕、成形等をその前後や途中に実施してもよい。
In addition, the above-mentioned heating means formation of individual oxides or complex oxides of each source compound of the above-mentioned catalytically active elements, formation of complex compound oxides or complex oxides formed by integration, and final complex oxidation of formation. A heat treatment for forming a product. And heating is not necessarily limited to once. That is, this heating can be arbitrarily performed at each stage of the integration shown in the above (A) to (D), and may be additionally performed after the integration if necessary. The above heating temperature is usually in the range of 200°C to 600°C.
Further, in the above integration and heating, in addition to these, drying, crushing, molding and the like may be performed before, after, or during the process, if necessary.
上記一体化工程中においてＳｉの供給源化合物を加えた水性系の凝集粒子に分散処理が施される。この処理を施すことによりＳｉ成分とともに一体化される触媒活性成分が微細に分散し、触媒性能、中でも原料転化率が向上する。
このようにして触媒活性成分の粉体を得ることができる。
In the integration step, the aqueous aggregated particles to which the Si source compound is added are subjected to a dispersion treatment. By performing this treatment, the catalytically active component integrated with the Si component is finely dispersed, and the catalytic performance, especially the raw material conversion rate is improved.
Thus, a powder of catalytically active component can be obtained.
本発明の製造方法は工程（ａ）で得られた触媒活性成分の粉体を、転動造粒法により、不活性担体に担持する工程を含む（以下、「工程（ｂ）」と称する場合がある）。
上記不活性担体とは、シリカ、炭化珪素、アルミナ、ムライト、アランダム等の直径が好ましくは２．５ｍｍ〜１０ｍｍ、更に好ましくは２．５ｍｍ〜６ｍｍの球形担体等が挙げられる。これらのうち気孔率が２０％〜６０％、吸水率が１０％〜６０％であることが触媒活性成分を容易に担持できることであることより好ましい。
The production method of the present invention includes a step of supporting the powder of the catalytically active component obtained in step (a) on an inert carrier by a tumbling granulation method (hereinafter, referred to as “step (b)”). There is).
Examples of the above-mentioned inert carrier include spherical carriers such as silica, silicon carbide, alumina, mullite, and alundum having a diameter of preferably 2.5 mm to 10 mm, more preferably 2.5 mm to 6 mm. Of these, a porosity of 20% to 60% and a water absorption rate of 10% to 60% are more preferable because the catalytically active component can be easily supported.
上記転動造粒（以下「成型」と称する場合がある。）とは、例えば固定容器内の底部に、平らなあるいは凹凸のある円盤を有する装置中で、円盤を高速で回転することにより、容器内の不活性担体を自転運動と公転運動の繰り返しにより激しく撹拌させ、ここに触媒活性成分の粉体と必要によりバインダー、成型助剤並びに強度向上材の混合物を添加することにより該触媒活性成分の粉体を不活性担体に担持する方法である。バインダーは、（１）前記触媒活性成分の粉体等に予め混合したのちに添加、（２）触媒活性成分の粉体等を固定容器内に添加するのと同時に添加、（３）触媒活性成分の粉体等を添加した後に添加、（４）触媒活性成分の粉体等を添加する前に添加、（５）触媒活性成分の粉体等とバインダーをそれぞれ分割して添加、（１）〜（５）を適宜組み合わせて全量添加する等の方法が任意に採用しうる。このうち（５）においては、例えば触媒活性成分の粉体等の固定容器壁への付着、触媒活性成分の粉体同士の凝集がなく不活性担体上に所定量が担持されるようオートフィーダー等を用いて添加速度を調節して行うのが好ましい。
触媒活性成分の粉体量と不活性担体量の割合は通常、触媒活性成分の粉体量／（触媒活性成分の粉体量＋不活性担体量）＝１０重量％〜９０重量％ 、好ましくは３０重量％〜
８０重量％である。
前記成型により得られた成型品は、直径が３ｍｍ〜１２ｍｍであることが好ましく、３
ｍｍ〜７ｍｍであることが更に好ましい。
上記工程（ｂ）により触媒活性成分の粉体が担持された不活性担体は、次いで焼成を行うことにより複合酸化物触媒を得ることができる。
この場合の焼成温度は通常２５０℃〜５００℃、好ましくは３００℃〜４５０℃、焼成時間は１時間〜５０時間である。
The rolling granulation (hereinafter sometimes referred to as "molding") means, for example, by rotating the disc at a high speed in a device having a flat or uneven disc at the bottom of a fixed container, The inert carrier in the container is vigorously agitated by repeating the rotational movement and the revolution movement, and the powder of the catalytically active component and, if necessary, the mixture of the binder, the molding aid and the strength improving material are added to the catalytically active component. It is a method of supporting the powder of No. 1 on an inert carrier. The binder is (1) premixed with the powder or the like of the catalytically active component and then added, (2) simultaneously added with the powder or the like of the catalytically active component in the fixed container, and (3) the catalytically active component. (4) Add before the addition of the powder of the catalytically active component, (5) Add the powder of the catalytically active component and the binder separately in parts, (1)- A method of appropriately combining (5) and adding the whole amount can be arbitrarily adopted. Among them, in (5), for example, an auto feeder or the like is used so that a predetermined amount is supported on the inert carrier without adhesion of powder of the catalytic active component to the wall of the fixed container and aggregation of the powder of the catalytic active component. It is preferable to adjust the addition rate by using.
The ratio of the powder amount of the catalytically active component and the amount of the inert carrier is usually the powder amount of the catalytically active component/(the powder amount of the catalytically active component+the amount of the inert carrier)=10% by weight to 90% by weight, preferably 30% by weight
It is 80% by weight.
The molded product obtained by the molding preferably has a diameter of 3 mm to 12 mm.
More preferably, it is from mm to 7 mm.
The inactive support on which the powder of the catalytically active component is carried in the step (b) is then calcined to obtain a composite oxide catalyst.
In this case, the firing temperature is usually 250°C to 500°C, preferably 300°C to 450°C, and the firing time is 1 hour to 50 hours.
尚、バインダーとは転動造粒において触媒活性成分を担体に容易に担持するため、および、複合酸化物触媒の強度を向上するために用いられる。バインダーとしては、エタノール、グリセリン等の有機系バインダー、ポリビニールアルコール等の高分子系バインダーやシリカゾル水溶液等の無機系バインダーが挙げられるが、有機系バインダーが好ましく、エチレングリコールやグリセリン等のジオール類やトリオール類等のアルコール類が更に好ましく、グリセリンが特に好ましい。有機系バインダーはそのまま用いてもよいが、操作性の観点から、水溶液として用いることが好ましい。水溶液濃度は０．１重量％以上が好ましい。又、バインダーの使用量は、触媒活性成分の粉体１００重量部に対して通常０．１重量部〜５０重量部、好ましくは０．５重量部〜２０重量部である。
更に必要によりシリカゲル、珪藻土、アルミナ粉末等の成型助剤を用いてもよい。成型助剤の使用量は、触媒活性成分の粉体１００重量部に対して通常１重量部〜２０重量部である。また、更に必要によりセラミックス繊維、ウイスカー等の無機繊維等の強度向上材を用いる事は、触媒の機械的強度の向上に有用である。これら繊維の使用量は、触媒活性成分の粉体１００重量部に対して通常０．５重量部〜２０重量部である。
The binder is used for easily supporting the catalytically active component on the carrier in the rolling granulation and for improving the strength of the composite oxide catalyst. Examples of the binder include organic binders such as ethanol and glycerin, polymer binders such as polyvinyl alcohol, and inorganic binders such as silica sol aqueous solution. Organic binders are preferable, and diols such as ethylene glycol and glycerin are preferable. Alcohols such as triols are more preferable, and glycerin is particularly preferable. The organic binder may be used as it is, but it is preferably used as an aqueous solution from the viewpoint of operability. The concentration of the aqueous solution is preferably 0.1% by weight or more. The amount of the binder used is usually 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the powder of the catalytically active component.
Further, if necessary, a molding aid such as silica gel, diatomaceous earth, or alumina powder may be used. The amount of the molding aid used is usually 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the powder of the catalytically active component. Further, if necessary, it is useful to improve the mechanical strength of the catalyst by using a strength improving material such as ceramic fiber or inorganic fiber such as whisker. The amount of these fibers used is usually 0.5 to 20 parts by weight with respect to 100 parts by weight of the powder of the catalytically active component.
ケイ素（Ｓｉ）の供給源化合物としては、シリカ、粒状シリカ、コロイダルシリカ、ヒュームドシリカ等が挙げられるが、容易に触媒の比表面積、細孔容積、細孔容積の分布を制御できることから、熱分解シリカであるヒュームドシリカが好ましい。
ケイ素の供給源化合物を使用するに当たり、適度な比表面積を有する供給源化合物を選択することが重要である。該ケイ素の供給源化合物の比表面積は３０ｍ２／ｇ〜９００ｍ２／ｇである。８０ｍ２／ｇ〜７００ｍ２／ｇであることが好ましく、９０ｍ２／ｇ〜４００ｍ２／ｇであることがより好ましく、１２０ｍ２／ｇ〜３００ｍ２／ｇであることが更に好ましい。適度な比表面積を有するケイ素の供給源化合物を選択し、複合酸化物触媒を製造することにより、複合酸化物触媒の活性成分の分散性が向上した高活性な触媒にすることが可能となる。
更には、強度に優れた複合酸化物触媒とすることができ、長期間、気相接触酸化反応を行っても、差圧の上昇等の不具合が起こらず安定的な運転が可能となる。
なお、ここでいう比表面積はケイ素の供給源化合物単位重量あたりの表面積であり、窒素吸着によるＢＥＴ法により測定することができる。
Examples of the source compound of silicon (Si) include silica, granular silica, colloidal silica, fumed silica, and the like. Since the distribution of the specific surface area, pore volume, and pore volume of the catalyst can be easily controlled, Fumed silica, which is a fused silica, is preferred.
In using a silicon source compound, it is important to select a source compound having a suitable specific surface area. The specific surface area of the source compound of the silicon is 30m 2 / g~900m 2 / g. Is preferably 80m 2 / g~700m 2 / g, more preferably 90m 2 / g~400m 2 / g, and further preferably from 120m 2 / g~300m 2 / g. By selecting a silicon source compound having an appropriate specific surface area and producing a composite oxide catalyst, a highly active catalyst with improved dispersibility of the active component of the composite oxide catalyst can be obtained.
Furthermore, a composite oxide catalyst having excellent strength can be obtained, and stable operation can be performed without causing problems such as an increase in differential pressure even if a gas-phase catalytic oxidation reaction is performed for a long period of time.
The specific surface area mentioned here is the surface area per unit weight of the silicon source compound, and can be measured by the BET method by nitrogen adsorption.
ケイ素の供給源化合物を使用するに当たり、適度な体積平均粒径を有する供給源化合物を選択することが重要である。該ケイ素の供給源化合物の体積平均粒径は０．１μｍ〜３０μｍである。０．１μｍ〜１０μｍであることが好ましく、０．１μｍ〜５μｍであることがより好ましく、０．１５μｍ〜３μｍであることが更に好ましく、０．２μｍ〜２μｍであることが特に好ましい。適度な体積平均粒径を有するケイ素の供給源化合物を選択し、複合酸化物触媒を製造することにより、ケイ素上に効率よく活性種が分散され、高負荷条件において気相接触酸化反応を行っても活性種の劣化が防止でき、不飽和アルデヒド及び不飽和カルボン酸を高選択的に得ることが可能となる。 In using a silicon source compound, it is important to select a source compound that has a suitable volume average particle size. The volume average particle diameter of the silicon source compound is 0.1 μm to 30 μm. The thickness is preferably 0.1 μm to 10 μm, more preferably 0.1 μm to 5 μm, further preferably 0.15 μm to 3 μm, and particularly preferably 0.2 μm to 2 μm. By selecting a silicon source compound having an appropriate volume average particle size and producing a composite oxide catalyst, active species are efficiently dispersed on silicon, and a gas phase catalytic oxidation reaction is performed under high load conditions. Also, deterioration of active species can be prevented, and unsaturated aldehyde and unsaturated carboxylic acid can be obtained with high selectivity.
尚、前記ケイ素の供給源化合物の体積平均粒径はレーザー回折散乱式粒度分布測定法により測定することができ、体積基準５０％径を体積平均粒径とした。ケイ素の供給源化合物を分散液で使用する場合は該分散液を測定サンプルとして、体積平均粒径を測定し、ケイ素の供給源化合物を固体で使用する場合はケイ素の供給源化合物を水に投入後、均一なケイ素の供給源化合物の濃度とした液をサンプルとして体積平均粒径を測定する。 The volume average particle diameter of the silicon source compound can be measured by a laser diffraction/scattering particle size distribution measuring method, and the volume-based 50% diameter was taken as the volume average particle diameter. When the silicon source compound is used as a dispersion, the volume average particle diameter is measured using the dispersion as a measurement sample, and when the silicon source compound is used as a solid, the silicon source compound is added to water. After that, the volume average particle diameter is measured using a liquid having a uniform concentration of the silicon source compound as a sample.
ケイ素の供給源化合物はその総体積の内、体積平均粒径の１．５倍以上の粒径を有する粒子の体積割合が１５％以下であることが好ましく、１２％以下がより好ましく、１０％以下がさらに好ましく、９％以下が特に好ましい。１．５倍以上の粒径を有する粒子の体積割合が多すぎると、高負荷条件では、気相接触酸化反応において局所的な温度ムラが発生しやすくなり、選択性が低下する場合がある。
前記ケイ素の供給源化合物の総体積の内、体積平均粒径の１．５倍以上の粒径を有する体積割合はレーザー回折散乱式粒度分布測定法により測定することがでる。尚、該体積平均粒径の測定方法は前記した方法に準ずる。
In the total volume of the silicon source compound, the volume ratio of particles having a particle size of 1.5 times or more the volume average particle size is preferably 15% or less, more preferably 12% or less, and more preferably 10%. The following is more preferable, and 9% or less is particularly preferable. If the volume ratio of the particles having a particle size of 1.5 times or more is too large, local temperature unevenness is likely to occur in the gas phase catalytic oxidation reaction under high load conditions, and the selectivity may decrease.
The volume ratio of the total volume of the silicon source compound having a particle size of 1.5 times or more the volume average particle size can be measured by a laser diffraction/scattering particle size distribution measuring method. The method for measuring the volume average particle diameter is in accordance with the method described above.
前記ケイ素の供給源化合物の水溶液ないし水分散液中のケイ素の供給源化合物濃度は１重量％〜５０重量％が好ましく、１０重量％〜３０重量％がより好ましい。１重量％より小さいと、水等の媒体量が多大となり、触媒活性成分の粉体とする際に経済的に不利となる場合がある。一方、５０重量％より大きいと、水溶液ないし水分散液の流動性は極めて悪くなり他触媒活性元素との混合操作が困難となる場合がある。 The concentration of the silicon source compound in the aqueous solution or dispersion of the silicon source compound is preferably 1% by weight to 50% by weight, more preferably 10% by weight to 30% by weight. If it is less than 1% by weight, the amount of a medium such as water becomes large, which may be economically disadvantageous when the powder of the catalytically active component is prepared. On the other hand, when it is more than 50% by weight, the fluidity of the aqueous solution or the aqueous dispersion becomes extremely poor, and the mixing operation with other catalytically active elements may become difficult.
本発明の製造方法において、前記触媒活性成分中、該ケイ素に対する該ビスマスの原子比（以下「Ｂｉ／Ｓｉ比」と称する場合がある。）が０．０４〜０．８０であることが好ましく、０．０５〜０．７０がより好ましく、０．０５〜０．６０がさらに好ましい。Ｂｉ／Ｓｉ比が小さすぎると製造された複合酸化物触媒を用いたプロピレンの気相接触酸化反応において、プロピレンの転化率、アクロレイン及びアクリル酸の選択率が低下する場合がある。Ｂｉ／Ｓｉ比が大きすぎると、特にプロピレンの負荷が高い条件で、気相接触酸化反応により発生する熱の除去が困難となり、時間の経過とともにアクロレイン及びアクリル酸の選択率が低下し、触媒が劣化し、触媒寿命が短くなる可能性がある。 In the production method of the present invention, the atomic ratio of the bismuth to the silicon (hereinafter sometimes referred to as “Bi/Si ratio”) in the catalytically active component is preferably 0.04 to 0.80, 0.05-0.70 is more preferable, and 0.05-0.60 is still more preferable. When the Bi/Si ratio is too small, the conversion rate of propylene and the selectivity of acrolein and acrylic acid may decrease in the gas phase catalytic oxidation reaction of propylene using the produced composite oxide catalyst. If the Bi/Si ratio is too large, it becomes difficult to remove the heat generated by the vapor phase catalytic oxidation reaction, especially under the condition that the load of propylene is high, and the selectivity of acrolein and acrylic acid decreases with the passage of time, and the catalyst becomes It may deteriorate and shorten the catalyst life.
更に本発明の製造方法において、触媒活性成分が下記組成式（１）で表されることが好ましい。
ＭｏａＢｉｂＣｏｃＮｉｄＦｅｅＸｆＹｇＳｉｈＯｉ （１）
（式中、Ｘはナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタリウム（Ｔｌ）からなる群から選ばれる少なくとも１種の元素であり、Ｙはホウ素（Ｂ）、リン（Ｐ）、砒素（Ａｓ）及びタングステン（Ｗ）からなる群から選ばれる少なくとも１種の元素である。また、ａ〜ｉはそれぞれの元素の原子比を表わし、ａ＝１２のとき、ｂ＝０．５〜７、ｃ＝０．１〜１０、ｄ＝０．１〜１０、ｅ＝０．０５〜５、ｆ＝０〜２、ｇ＝０〜３、ｈ＝１〜４８の範囲にあり、またｉは他の元素の酸化状態を満足させる数値である。）
上記組成式（１）の触媒活性成分により複合酸化物触媒を製造することにより、製造された触媒により気相接触酸化反応を行うと、より高収率でアクロレイン及びアクリル酸を製造することができる。
Further, in the production method of the present invention, the catalytically active component is preferably represented by the following composition formula (1).
Mo a Bi b Co c Ni d Fe e X f Y g Si h O i (1)
(In the formula, X is at least one element selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and thallium (Tl), and Y is boron (B). , At least one element selected from the group consisting of phosphorus (P), arsenic (As) and tungsten (W), and a to i represent the atomic ratio of each element, and when a=12, b=0.5-7, c=0.1-10, d=0.1-10, e=0.05-5, f=0-2, g=0-3, h=1-48 Within the range, i is a numerical value that satisfies the oxidation states of other elements.)
When a complex oxide catalyst is produced by using the catalytically active component of the above composition formula (1), and the gas-phase catalytic oxidation reaction is performed by the produced catalyst, acrolein and acrylic acid can be produced in higher yield. ..
本発明の複合酸化物触媒の製造にあたり、モリブデン（Ｍｏ）の供給源化合物としては、パラモリブデン酸アンモニウム、三酸化モリブデン、モリブデン酸、リンモリブデン酸アンモニウム、リンモリブデン酸等が挙げられる。
ビスマス（Ｂｉ）の供給源化合物としては、塩化ビスマス、硝酸ビスマス、酸化ビスマス、次炭酸ビスマス等が挙げられ、ビスマス添加量は、前記組成式（１）において、ａ＝１２のとき、ｂ＝０．５〜７となるように添加することが好ましく、より好ましくはｂ＝０．７〜５．０、更に好ましくはｂ＝１．０〜４．９となるように添加する。ｂが前記範囲内であることにより原料の転化率に優れ、高選択率で目的生成物を製造することができる複合酸化物触媒とすることができる。
In producing the composite oxide catalyst of the present invention, examples of the molybdenum (Mo) source compound include ammonium paramolybdate, molybdenum trioxide, molybdic acid, ammonium phosphomolybdate, phosphomolybdic acid and the like.
Examples of the bismuth (Bi) source compound include bismuth chloride, bismuth nitrate, bismuth oxide, and bismuth subcarbonate. The amount of bismuth added is b=0 when a=12 in the composition formula (1). It is preferable to add so as to be 0.5 to 7, more preferably b=0.7 to 5.0, and further preferably b=1.0 to 4.9. When b is in the above range, it is possible to obtain a composite oxide catalyst which is excellent in the conversion rate of the raw material and can produce the target product with high selectivity.
コバルト（Ｃｏ）の供給源化合物としては、硝酸コバルト、硫酸コバルト、塩化コバル
ト、炭酸コバルト、酢酸コバルト等が挙げられ、コバルト添加量は、前記組成式（１）において、ａ＝１２のとき、ｃ＝０．１〜１０となるように添加することが好ましく、より好ましくはｃ＝０．５〜８．０、更に好ましくはｃ＝１．０〜５．０となるように添加する。
Examples of the cobalt (Co) source compound include cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt carbonate, and cobalt acetate. The amount of cobalt added is c when a=12 in the composition formula (1). =0.1-10, more preferably c=0.5-8.0, still more preferably c=1.0-5.0.
ニッケル（Ｎｉ）の供給源化合物としては、硝酸ニッケル、硫酸ニッケル、塩化ニッケル、炭酸ニッケル、酢酸ニッケル等が挙げられ、ニッケル添加量は、前記組成式（１）において、ａ＝１２のとき、ｄ＝０．１〜１０なるように添加することが好ましく、より好ましくはｄ＝０．５〜８、更に好ましくはｄ＝１〜５となるように添加する。
鉄（Ｆｅ）の供給源化合物としては、硝酸第二鉄、硫酸第二鉄、塩化第二鉄、酢酸第二鉄等が挙げられ、鉄添加量は、前記組成式（１）において、ａ＝１２のとき、ｅ＝０．０５〜５となるように添加することが好ましく、より好ましくはｅ＝０．１〜４、更に好ましくはｅ＝０．３〜２となるように添加する。
Examples of the source compound of nickel (Ni) include nickel nitrate, nickel sulfate, nickel chloride, nickel carbonate, nickel acetate, and the like. The nickel addition amount is d when a=12 in the composition formula (1). =0.1-10, more preferably d=0.5-8, and even more preferably d=1-5.
Examples of the iron (Fe) source compound include ferric nitrate, ferric sulfate, ferric chloride, ferric acetate, etc., and the iron addition amount in the composition formula (1) is a= When it is 12, it is preferable to add so that e=0.05 to 5, more preferably e=0.1 to 4, and even more preferably e=0.3 to 2.
ケイ素（Ｓｉ）の供給源化合物としては、シリカ、粒状シリカ、コロイダルシリカ、ヒュームドシリカ等が挙げられるが、容易に触媒の比表面積、細孔容積、細孔容積の分布を制御できることから、熱分解シリカであるヒュームドシリカが好ましい。 Examples of the source compound of silicon (Si) include silica, granular silica, colloidal silica, fumed silica, and the like. Since the distribution of the specific surface area, pore volume, and pore volume of the catalyst can be easily controlled, Fumed silica, which is a fused silica, is preferred.
ケイ素の添加量は、前記組成式（１）において、ａ＝１２のとき、ｈ＝１〜４８となるように添加することが好ましく、より好ましくはｈ＝３〜３０、更に好ましくはｈ＝４〜２０となるように添加する。ｈが小さすぎると複合酸化物触媒の活性成分の分散性が低下する傾向にあり、ｈが大きすぎると複合酸化物触媒の活性成分の割合が少なくなり、十分な触媒性能が得られない可能性がある。 The amount of silicon added is preferably such that h=1 to 48 when a=12 in the composition formula (1), more preferably h=3 to 30, and further preferably h=4. Add ~20. If h is too small, the dispersibility of the active component of the composite oxide catalyst tends to decrease, and if h is too large, the ratio of the active component of the composite oxide catalyst decreases, and sufficient catalytic performance may not be obtained. There is.
Ｘはナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタリウム（Ｔｌ）からなる群から選ばれる少なくとも１種の元素であれば特に限定されないが、ナトリウム（Ｎａ）、カリウム（Ｋ）及びセシウム（Ｃｓ）からなる群から選ばれる少なくとも１種であることがより好ましく、ナトリウム（Ｎａ）及び／又はカリウム（Ｋ）であることが更に好ましい。Ｘを含むことで、目的生成物の選択性が向上することが可能となる。 X is not particularly limited as long as it is at least one element selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and thallium (Tl), but sodium (Na), At least one selected from the group consisting of potassium (K) and cesium (Cs) is more preferable, and sodium (Na) and/or potassium (K) is further preferable. By including X, the selectivity of the target product can be improved.
Ｘの添加量は、前記組成式（１）において、ａ＝１２のときに、ｆ＝０〜２となるように添加されることが好ましいが、より好ましくはｆ＝０．０５〜１．５、更に好ましくはｆ＝０．０５〜１．２となるように添加する。ｆが小さすぎると、目的生成物の選択率が低下する傾向にあり、ｆが大きすぎると触媒の活性が低下する可能性がある。
Ｙはホウ素（Ｂ）、リン（Ｐ）、砒素（Ａｓ）及びタングステン（Ｗ）からなる群から選ばれる少なくとも１種の元素であれば特に限定されないが、ホウ素（Ｂ）、リン（Ｐ）及び砒素（Ａｓ）からなる群から選ばれる少なくとも１種であることがより好ましく、ホウ素（Ｂ）であることが更に好ましい。
The addition amount of X is preferably such that f=0 to 2 when a=12 in the composition formula (1), and more preferably f=0.05 to 1.5. , And more preferably added so that f=0.05 to 1.2. If f is too small, the selectivity of the target product tends to decrease, and if f is too large, the activity of the catalyst may decrease.
Y is not particularly limited as long as it is at least one element selected from the group consisting of boron (B), phosphorus (P), arsenic (As) and tungsten (W), but boron (B), phosphorus (P) and At least one selected from the group consisting of arsenic (As) is more preferable, and boron (B) is further preferable.
Ｙの添加量は、前記組成式（１）において、ａ＝１２のときに、ｇ＝０〜３となるように添加されることが好ましいが、より好ましくはｇ＝０．０５〜２．０、更に好ましくはｇ＝０．１〜１．０となるように添加する。
上記成分元素の供給源化合物としては、成分元素の酸化物、硝酸塩、炭酸塩、アンモニウム塩、水酸化物、カルボン酸塩、カルボン酸アンモニウム塩、ハロゲン化アンモニウム塩、水素酸、アセチルアセテート、アルコキシド等が挙げられ、その具体例としては、下記のようなものが挙げられる。
The addition amount of Y is preferably such that g=0 to 3 when a=12 in the composition formula (1), and more preferably g=0.05 to 2.0. , And more preferably, g is added in an amount of 0.1 to 1.0.
Examples of the component element source compounds include oxides, nitrates, carbonates, ammonium salts, hydroxides, carboxylates, carboxylic acid ammonium salts, ammonium halide salts, hydrolic acid, acetyl acetate, alkoxides, etc. of the component elements. The following are mentioned as specific examples.
また、Ｘ成分（Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｔｌの１種又は２種以上）を固溶させた、ビスマス（Ｂｉ）とＸ成分との複合炭酸塩化合物として供給することもできる。Ｘ成分の供給
量は、前記組成式（１）において、ａ＝１２のときに、ｆ＝０〜２となるように供給される。
例えば、Ｘ成分としてナトリウム（Ｎａ）を用いた場合、ビスマス（Ｂｉ）とＮａとを複合炭酸塩化合物は、炭酸ナトリウム又は重炭酸ナトリウムの水溶液等に、硝酸ビスマス等の水溶性ビスマス化合物の水溶液を滴下混合し、得られた沈殿を水洗、乾燥することによって製造することができる。
It is also possible to supply it as a complex carbonate compound of bismuth (Bi) and the X component, which is a solid solution of the X component (one or more of Na, K, Rb, Cs, and Tl). The supply amount of the X component is supplied so that f=0 to 2 when a=12 in the composition formula (1).
For example, when sodium (Na) is used as the X component, the complex carbonate compound of bismuth (Bi) and Na is an aqueous solution of sodium carbonate or sodium bicarbonate, or an aqueous solution of a water-soluble bismuth compound such as bismuth nitrate. It can be produced by dropping and mixing, and washing the resulting precipitate with water and drying.
その他の成分元素の供給源化合物としては、下記のものが挙げられる。
カリウム（Ｋ）の供給源化合物としては、硝酸カリウム、硫酸カリウム、塩化カリウム、炭酸カリウム、酢酸カリウム等が挙げられる。
ルビジウム（Ｒｂ）の供給源化合物としては、硝酸ルビジウム、硫酸ルビジウム、塩化ルビジウム、炭酸ルビジウム、酢酸ルビジウム等が挙げられる。
Examples of the source compound of the other component elements include the following.
Examples of the source compound of potassium (K) include potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate, potassium acetate and the like.
Examples of the source compound of rubidium (Rb) include rubidium nitrate, rubidium sulfate, rubidium chloride, rubidium carbonate and rubidium acetate.
タリウム（Ｔｌ）の供給源化合物としては、硝酸第一タリウム、塩化第一タリウム、炭酸タリウム、酢酸第一タリウム等が挙げられる。
ホウ素（Ｂ）の供給源化合物としては、ホウ砂、ホウ酸アンモニウム、ホウ酸等が挙げられる。
リン（Ｐ）の供給源化合物としては、リンモリブデン酸アンモニウム、リン酸アンモニウム、リン酸、五酸化リン等が挙げられる。
Examples of the thallium (Tl) source compound include thallium nitrate, thallium chloride, thallium carbonate, thallium acetate, and the like.
Examples of the source compound of boron (B) include borax, ammonium borate, boric acid and the like.
Examples of the phosphorus (P) source compound include ammonium phosphomolybdate, ammonium phosphate, phosphoric acid, phosphorus pentoxide, and the like.
砒素（Ａｓ）の供給源化合物としては、ジアルセノ十八モリブデン酸アンモニウム、ジアルセノ十八タングステン酸アンモニウム等が挙げられる。
タングステン（Ｗ）の供給源化合物としては、パラタングステン酸アンモニウム、メタタングステン酸アンモニウム、三酸化タングステン、タングステン酸、リンタングステン酸等が挙げられる。
Examples of the arsenic (As) supply source compound include ammonium dialcseno octamolybdate and ammonium dialcseno octatungstate.
Examples of the tungsten (W) source compound include ammonium paratungstate, ammonium metatungstate, tungsten trioxide, tungstic acid, phosphotungstic acid, and the like.
複合酸化物触媒を製造する場合の各元素の供給源化合物とは、各元素のそれぞれについてのそれぞれの化合物のみを意味するのではなく、複数の元素を共に含む化合物（たとえばＭｏとＰとについてのリンモリブデン酸アンモンなど）を包含するものである。
また、上記のようにして複合酸化物触媒を製造する場合、ケイ素成分の供給源化合物として、熱分解シリカが好ましく、ビスマス成分の供給源化合物として、（１）酸化ビスマスまたは次炭酸ビスマスのいずれか一方、（２）所要のＮａの少なくとも一部を固溶した次炭酸ビスマス、（３）成分の少なくとも一部を含むＢｉとＸ成分との複合炭酸塩化合物、あるいは（４）所要のＮａおよびＸ成分のそれぞれ少なくとも一部を含むＢｉとＮａとＸとの複合炭酸塩化合物を組み合わせて用いることにより、容易に工業的に優れた触媒を製造できる。上記複合酸化物触媒は、触媒活性元素の各供給源化合物の水性系での一体化及び加熱し、触媒活性成分の粉体を得る工程を経て製造するが、その一部としてモリブデン、鉄、ニッケル又はコバルトの少なくとも一つ、及びシリカを一部として含む原料塩水溶液を乾燥して得た乾燥物を加熱処理して触媒活性成分の前駆体粉末を製造する前工程を経た後、該触媒活性成分の前駆体粉末とビスマス化合物とを水性溶媒とともに一体化し、乾燥、焼成する後工程を経て触媒活性成分の粉末を調製することが好ましい。
The source compound of each element in the case of producing a composite oxide catalyst does not mean only each compound for each element, but a compound containing a plurality of elements together (for example, for Mo and P). Ammonium phosphomolybdate, etc.) are included.
Further, in the case of producing the composite oxide catalyst as described above, pyrolytic silica is preferable as the source compound of the silicon component, and (1) either bismuth oxide or bismuth subcarbonate as the source compound of the bismuth component. On the other hand, (2) bismuth subcarbonate in which at least a part of required Na is dissolved, (3) complex carbonate compound of Bi and X component containing at least a part of component, or (4) required Na and X By using a complex carbonate compound of Bi, Na and X containing at least a part of each of the components in combination, an industrially excellent catalyst can be easily produced. The composite oxide catalyst is produced by a process of integrating and heating each source compound of the catalytically active element in an aqueous system to obtain a powder of the catalytically active component, and as a part thereof, molybdenum, iron, nickel. Alternatively, the raw material salt aqueous solution containing at least one of cobalt and silica as a part is dried to obtain a precursor powder of the catalytically active component by heat treatment of the dried product, and then the catalytically active component is subjected to the pretreatment. It is preferable that the precursor powder and the bismuth compound are integrated with an aqueous solvent, and the powder of the catalytically active component is prepared through a post-process of drying and firing.
上記の原料塩水溶液又はこれを乾燥して得た顆粒あるいはケーキ状のものは空気中で２００℃〜４００℃、好ましくは２５０℃〜３５０℃の温度域で短時間の熱処理を行う。その際の炉の形式及びその方法については特に限定はなく、例えば、通常の箱型加熱炉、トンネル型加熱炉等を用いて乾燥物を固定した状態で加熱してもよいし、また、ロータリーキルン等を用いて乾燥物を流動させながら加熱してもよい。 The raw salt solution or the granular or cake-like product obtained by drying the raw salt solution is subjected to heat treatment in air at a temperature range of 200°C to 400°C, preferably 250°C to 350°C for a short time. The type and method of the furnace at that time are not particularly limited, and for example, the dried product may be heated in a fixed state by using an ordinary box-type heating furnace, tunnel-type heating furnace, or the like, or a rotary kiln. Alternatively, the dried product may be heated while flowing.
ケイ素の供給源化合物の分散液の調製方法は、例えば、ケイ素の供給源化合物を水等の媒体に添加・混合し、懸濁状態とした後に、媒体の流動、衝突、圧力差、超音波等の分散
原理を利用し、ケイ素の供給源化合物を媒体中に微分散し、分散液とする方法が挙げられる。ケイ素の供給源化合物を媒体中に微分散し、分散液とする分散装置としては、例えばホモジナイザー、ホモミキサー、高剪断ブレンダー、ビーズミル、超音波分散装置が挙げられ、中でも、微分散したケイ素の供給源化合物の粒径分布がシャープとなることより、ホモジナイザー、ホモミキサーが好ましく、ホモジナイザーがより好ましい。
The method for preparing the dispersion liquid of the silicon source compound is, for example, adding/mixing the silicon source compound into a medium such as water to form a suspension, and then flowing, collision, pressure difference, ultrasonic wave, etc. of the medium. A method in which a silicon source compound is finely dispersed in a medium to obtain a dispersion liquid by utilizing the dispersion principle of No. As a dispersion device for finely dispersing a source compound of silicon in a medium to obtain a dispersion liquid, for example, a homogenizer, a homomixer, a high shear blender, a bead mill, an ultrasonic dispersion device, and the like, among them, supply of finely dispersed silicon Since the particle size distribution of the source compound becomes sharp, a homogenizer and a homomixer are preferable, and a homogenizer is more preferable.
以上のようにして、高い転化率条件で、かつ目的とする酸化生成物を高い収率で与える複合酸化物触媒が得られる。このようにして製造された複合酸化物触媒は、例えば、プロピレンからアクロレイン及びアクリル酸を製造する反応に使用される。プロピレンからアクロレイン及びアクリル酸を製造する気相接触酸化反応は、原料混合ガス組成として５容量％〜１５容量％のプロピレン、５容量％〜１８容量％の分子状酸素、０〜４０容量％の水蒸気及び２０容量％〜７０容量％の不活性ガス、例えば窒素、炭酸ガスなどからなる混合ガスを前記のようにして製造した複合酸化物触媒上に３００℃〜４５０℃の温度範囲及び常圧〜１５０ｋＰａの圧力下、そして０．５秒〜４秒の接触時間で導入することによって遂行される。 As described above, a composite oxide catalyst that gives a desired oxidation product in a high yield under high conversion conditions can be obtained. The composite oxide catalyst thus produced is used, for example, in a reaction for producing acrolein and acrylic acid from propylene. The gas-phase catalytic oxidation reaction for producing acrolein and acrylic acid from propylene is carried out by using a raw material mixed gas composition of 5 vol% to 15 vol% propylene, 5 vol% to 18 vol% molecular oxygen, and 0 to 40 vol% steam. And a mixed gas consisting of 20% by volume to 70% by volume of an inert gas, for example, nitrogen, carbon dioxide, etc., on the composite oxide catalyst produced as described above, in the temperature range of 300° C. to 450° C. and normal pressure to 150 kPa. Under pressure and with a contact time of 0.5 seconds to 4 seconds.
上記、原料混合ガス中のプロピレンの含有量は７体積％〜１２体積％の範囲が好ましく、また、プロピレンの空間速度は８０ｈ−１〜３２０ｈ−１の範囲が好ましく、１００ｈ−１〜３２０ｈ−１の範囲がより好ましい。空間速度が低い条件、すなわち、プロピレンの負荷が低い条件では副生成物が多くなり、生成目的物の収率が低下する原因になる。又、空間速度が高い条件、すなわち、プロピレンの負荷が高い条件では転化率が８０％より低くなって、原料であるプロピレンの未反応量が多くなり生産量が低下する可能性がある。工業的な観点からプロピレン転化率は８９．５％以上になることが好ましい。 The content of propylene raw material mixed gas is preferably from 7 vol% to 12 vol%, and a space velocity of propylene is preferably in the range of 80h -1 ~320h -1, 100h -1 ~320h -1 Is more preferable. Under the condition that the space velocity is low, that is, the condition that the load of propylene is low, the amount of by-products increases, which causes a decrease in the yield of the target product. Further, under the condition that the space velocity is high, that is, the condition that the load of propylene is high, the conversion rate becomes lower than 80%, the unreacted amount of propylene as a raw material increases, and the production amount may decrease. From an industrial viewpoint, the propylene conversion rate is preferably 89.5% or more.
尚、空間速度とは次式で示される値である。
・空間速度ＳＶ（ｈ−１）＝反応器に供給するオレフィンガスの体積流量（０℃、１気圧条件）／反応器に充填された複合金属酸化物触媒の体積（反応性の無い固形物は含まない）
The space velocity is a value represented by the following equation.
Space velocity SV(h −1 )=Volume flow rate of olefin gas supplied to reactor (0° C., 1 atmospheric pressure condition)/Volume of complex metal oxide catalyst filled in reactor (solid matter having no reactivity is Not included)
（１）シリカの比表面積の測定
シリカの比表面積は、窒素吸着によるＢＥＴ１点法により触媒単位重量あたりの表面積を測定した。複合酸化物触媒を２５０℃で１５分間、窒素ガス送風状態で処理したサンプルを、測定装置：マックソーブHM Model-1201（株式会社マウンテック製）を用いて、Ｂ
ＥＴ1 点法（吸着ガス：窒素）にて比表面積を測定した。
(1) Measurement of specific surface area of silica As the specific surface area of silica, the surface area per unit weight of catalyst was measured by the BET one-point method by nitrogen adsorption. A sample obtained by treating the composite oxide catalyst at 250° C. for 15 minutes in a nitrogen gas blowing state was measured using a measuring device: Macsorb HM Model-1201 (manufactured by Mountech Co., Ltd.)
The specific surface area was measured by the ET1 point method (adsorption gas: nitrogen).
（２）シリカの体積平均粒径、粒径分布の測定
サンプルをレーザー回折散乱式粒度分布測定器であるＷｅｔ ｕｎｉｔ ＬＭＳ-２０
００s、（株式会社セイシン企業製）により、シリカの体積基準粒径分布を測定した。又
、５０％粒径を測定し、シリカの体積平均粒径とした。尚、湿式法により測定したものである。
体積平均粒径の１．５倍以上の粒径を有する粒子の体積割合は該体積基準粒径分布より計算して求めた。
(2) Measurement of volume average particle size and particle size distribution of silica A sample is Wet unit LMS-20 which is a laser diffraction/scattering particle size distribution analyzer.
00s, manufactured by Seishin Enterprise Co., Ltd., was used to measure the volume-based particle size distribution of silica. Further, the 50% particle size was measured and used as the volume average particle size of silica. In addition, it was measured by a wet method.
The volume ratio of particles having a particle size of 1.5 times or more the volume average particle size was calculated from the volume standard particle size distribution.
（実施例１）
＜複合酸化物触媒の調製＞
容器に温水１５００ｍｌを入れ、更にパラモリブデン酸アンモニウム２３８ｇを加えて溶解させ、溶液とした。次いで、該溶液にヒュームドシリカの水分散液４６０ｇを加えて、撹拌し、懸濁液とした（以下、「懸濁液Ａ」と称する）。該ヒュームドシリカ水分散液は、ヒュームドシリカ５ｋｇ（比表面積１５０ｍ２／ｇ）をイオン交換水２２．５Ｌに加
えてヒュームドシリカ懸濁液とした後に、該ヒュームドシリカ懸濁液を、ホモジナイザーであるULTRA-TURRAX T115KT（ＩＫＡ社製）により、３０分間分散処理を行い、ヒューム
ドシリカ水分散液としたものであり、ケイ素の供給源化合物とした。尚、ヒュームドシリカ水分散液中のシリカの体積平均粒径は１．３０７μｍであり、体積平均粒径の１．５倍以上の粒径の粒子の体積割合は８．３％であった。
(Example 1)
<Preparation of complex oxide catalyst>
1500 ml of warm water was placed in a container, and 238 g of ammonium paramolybdate was further added and dissolved to obtain a solution. Then, 460 g of an aqueous dispersion of fumed silica was added to the solution and stirred to obtain a suspension (hereinafter referred to as "suspension A"). The fumed silica aqueous dispersion was prepared by adding 5 kg of fumed silica (specific surface area 150 m 2 /g) to 22.5 L of ion-exchanged water to prepare a fumed silica suspension, A homogenizer ULTRA-TURRAX T115KT (manufactured by IKA) was used for dispersion treatment for 30 minutes to prepare a fumed silica aqueous dispersion, which was used as a silicon source compound. The volume average particle size of silica in the fumed silica aqueous dispersion was 1.307 μm, and the volume ratio of particles having a particle size of 1.5 times or more the volume average particle size was 8.3%.
別の容器に純水４０８ｍｌを入れ、更に硝酸第二鉄６１．０ｇ、硝酸コバルト１８６．０ｇ及び硝酸ニッケル２００．０ｇを加えて、加温して溶解させた（以下、「溶液Ｂ」と称する）。溶液Ｂを懸濁液Ａに添加し、均一になるように攪拌し、加熱乾燥し、固形物を得た。次いで該固形物を空気雰囲気で３００℃、１時間熱処理した。
更に、別の容器に純水９３ｍｌ、アンモニア水１４．３ｍｌを入れ、パラモリブデン酸アンモニウム２８．４ｇを加えて溶解し、「溶液Ｃ」とした。次いで、溶液Ｃにホウ砂０．９ｇ及び硝酸カリウム０．７ｇを加えて溶解し、「溶液Ｄ」とした。前記熱処理した固形物１６７ｇを溶液Ｄに添加し、均一になるように混合した。次いでＮａを０．５３％固溶した次炭酸ビスマス１４．６ｇを加えて３０分間混合し、触媒活性成分とした。該触媒活性成分を加熱して水分を除去し、乾燥品とし、次いで該乾燥品を粉砕し、触媒活性成分の粉体を得た（以下、「粉体Ａ」と称する）。
粉体Ａ、グリセリンの１６．７重量％水溶液、アルミナ及びシリカを主成分とする不活性担体を用いて、転動造粒法により、複合酸化物触媒前駆体を調製した。転動造粒装置に直径４．０ｍｍの球状の不活性担体（気孔率４０％、吸水率２０％）を投入し、次いで該粉体Ａとグリセリン水溶液を交互に添加することにより粉体Ａを不活性担体に担持させ、担持成型体を得た（粉体Ａ／（粉体Ａ＋不活性担体）＝４０重量％）。担持成型体の直径は５．０ｍｍであった。このときグリセリンを用いた有機系バインダー量は、触媒活性成分の粉体１００重量部に対して、２重量部であった。
該担持成型体を空気雰囲気下、５１５℃で２時間、焼成を行い、複合酸化物触媒を得た。ケイ素の供給源化合物であるシリカの比表面積および体積平均粒径を表１に示した。触媒活性成分の組成比並びに該触媒活性成分中のケイ素に対するビスマスの原子比を表２に示した。
Put 408 ml of pure water in another container, and further add 61.0 g of ferric nitrate, 186.0 g of cobalt nitrate and 200.0 g of nickel nitrate and heat to dissolve them (hereinafter, referred to as "solution B"). ). Solution B was added to suspension A, stirred to be uniform, and dried by heating to obtain a solid. Then, the solid matter was heat-treated in an air atmosphere at 300° C. for 1 hour.
Further, 93 ml of pure water and 14.3 ml of ammonia water were placed in another container, and 28.4 g of ammonium paramolybdate was added and dissolved to obtain "solution C". Next, 0.9 g of borax and 0.7 g of potassium nitrate were added to and dissolved in the solution C to obtain a “solution D”. The heat-treated solid material (167 g) was added to the solution D and mixed so as to be uniform. Next, 14.6 g of bismuth subcarbonate containing 0.53% of Na dissolved therein was added and mixed for 30 minutes to obtain a catalytically active component. The catalytically active component was heated to remove water to obtain a dry product, and then the dried product was pulverized to obtain a powder of the catalytically active component (hereinafter referred to as "powder A").
A composite oxide catalyst precursor was prepared by a tumbling granulation method using powder A, a 16.7 wt% aqueous solution of glycerin, and an inert carrier containing alumina and silica as main components. A spherical inert carrier having a diameter of 4.0 mm (porosity 40%, water absorption 20%) was put into a tumbling granulator, and then the powder A and the glycerin aqueous solution were alternately added to obtain the powder A. It was supported on an inert carrier to obtain a supported molding (powder A/(powder A+inert carrier)=40% by weight). The diameter of the support molding was 5.0 mm. At this time, the amount of the organic binder using glycerin was 2 parts by weight with respect to 100 parts by weight of the powder of the catalytically active component.
The supported molded body was calcined in an air atmosphere at 515° C. for 2 hours to obtain a composite oxide catalyst. Table 1 shows the specific surface area and volume average particle diameter of silica, which is a source compound of silicon. Table 2 shows the composition ratio of the catalytically active component and the atomic ratio of bismuth to silicon in the catalytically active component.
＜プロピレンの気相接触酸化反応＞
該複合酸化物触媒４０ｍｌをムライトボール５２ｍｌと混合し、ステンレス鋼製ナイタージャケット付反応管に充填し、プロピレン１０％、スチーム１７％、酸素１５％、窒素５８％の原料混合ガスを圧力７０ｋＰａで反応管内に導入し、プロピレンの酸化反応を実施した。この時、プロピレンの空間速度は１００ｈ−１であった。結果は表３にまとめた。
<Propylene gas-phase catalytic oxidation reaction>
40 ml of the complex oxide catalyst was mixed with 52 ml of mullite ball, and the mixture was filled in a reaction tube with a stainless steel niter jacket, and a raw material mixed gas of propylene 10%, steam 17%, oxygen 15% and nitrogen 58% was reacted at a pressure of 70 kPa. It was introduced into the tube to carry out an oxidation reaction of propylene. At this time, the space velocity of propylene was 100 h −1 . The results are summarized in Table 3.
ここで、プロピレン転化率、アクロレイン選択率、アクリル酸選択率、アクロレイン収率、アクリル酸収率、合計収率の定義は、下記の通りである。
・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
・アクロレイン選択率（モル％）＝（生成したアクロレインのモル数／反応したプロピレンのモル数）×１００
・アクリル酸選択率（モル％）＝（生成したアクリル酸のモル数／反応したプロピレンのモル数）×１００
・アクロレイン収率（モル％）＝（生成したアクロレインのモル数／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
・合計収率（モル％）＝アクロレイン収率（モル％）＋アクリル酸収率（モル％）
Here, the definitions of propylene conversion rate, acrolein selectivity, acrylic acid selectivity, acrolein yield, acrylic acid yield, and total yield are as follows.
Propylene conversion rate (mol %)=(mol number of reacted propylene/mol number of supplied propylene)×100
Acrolein selectivity (mol %)=(mol number of acrolein produced/mol number of reacted propylene)×100
Acrylic acid selectivity (mol %)=(mol of generated acrylic acid/mol of reacted propylene)×100
-Acrolein yield (mol %) = (moles of acrolein produced/moles of propylene fed) x 100
Acrylic acid yield (mol %)=(mol number of acrylic acid produced/mol number of propylene supplied)×100
-Total yield (mol%) = acrolein yield (mol%) + acrylic acid yield (mol%)
（参考例１）
容器に温水１６７０ｍｌを入れ、更にパラモリブデン酸アンモニウム２６５ｇを加えて
溶解させ、溶液とした。次いで、該溶液にヒュームドシリカの水分散液２５６ｇを加えて
、撹拌し、懸濁液とした（以下、「懸濁液Ａ」と称する）。該ヒュームドシリカ水分散液
は、ヒュームドシリカ５ｋｇ（比表面積９３ｍ２／ｇ）をイオン交換水２２．５Ｌに加え
てヒュームドシリカ懸濁液とした後に、該ヒュームドシリカ懸濁液を、ホモジナイザーで
あるULTRA-TURRAX T115KT（ＩＫＡ社製）により、３０分間分散処理を行い、ヒュームド
シリカ水分散液としたものであり、ケイ素の供給源化合物とした。尚、ヒュームドシリカ
水分散液中のシリカの体積平均粒径は０．２４７μｍであり、体積平均粒径の１．５倍以
上の粒径の粒子の体積割合は７．６％であった。
( Reference example 1 )
1670 ml of warm water was placed in a container, and 265 g of ammonium paramolybdate was further added and dissolved to obtain a solution. Then, 256 g of an aqueous dispersion of fumed silica was added to the solution and stirred to obtain a suspension (hereinafter referred to as "suspension A"). The fumed silica aqueous dispersion was prepared by adding 5 kg of fumed silica (specific surface area: 93 m2/g) to 22.5 L of ion-exchanged water to prepare a fumed silica suspension, and then using the homogenizer for the fumed silica suspension. ULTRA-TURRAX T115KT (manufactured by IKA Co., Ltd.) for 30 minutes to obtain a fumed silica aqueous dispersion, which was used as a silicon source compound. The volume average particle diameter of silica in the fumed silica aqueous dispersion was 0.247 μm, and the volume ratio of particles having a particle diameter of 1.5 times or more the volume average particle diameter was 7.6%.
別の容器に純水４５４ｍｌを入れ、更に硝酸第二鉄６８．０ｇ、硝酸コバルト２０７．２ｇ及び硝酸ニッケル２２３．０ｇを加えて、加温して溶解させた（以下、「溶液Ｂ」と称する）。溶液Ｂを懸濁液Ａに添加し、均一になるように攪拌し、加熱乾燥し、固形物を得た。次いで該固形物を空気雰囲気で３００℃、１時間熱処理した。
更に、別の容器に純水９３ｍｌ、アンモニア水１４．３ｍｌを入れ、パラモリブデン酸アンモニウム３１．７ｇを加えて溶解し、「溶液Ｃ」とした。次いで、溶液Ｃにホウ砂１．０ｇ及び硝酸カリウム０．８ｇを加えて溶解し、「溶液Ｄ」とした。前記熱処理した固形物１６３ｇを溶液Ｄに添加し、均一になるように混合した。次いでＮａを０．５３％固溶した次炭酸ビスマス１６．２ｇを加えて３０分間混合し、触媒活性成分とした。該触媒活性成分を加熱して水分を除去し、乾燥品とし、次いで該乾燥品を粉砕し、触媒活性成分の粉体を得た（以下、「粉体Ｃ」と称する）。
粉体Ｃ、グリセリンの１６．７重量％水溶液、アルミナ及びシリカを主成分とする不活性担体を用いて、転動造粒法により、複合酸化物触媒前駆体を調製した。転動造粒装置に直径４．０ｍｍの球状の不活性担体（気孔率４０％、吸水率２０％）を投入し、次いで該粉体Ａとグリセリン水溶液を交互に添加することにより粉体Ａを不活性担体に担持させ、担持成型体を得た（粉体Ａ／（粉体Ａ＋不活性担体）＝４０重量％）。担持成型体の直径は５．０ｍｍであった。このときグリセリンを用いた有機系バインダー量は、触媒活性成分の粉体１００重量部に対して、２重量部であった。
該担持成型体を空気雰囲気下、５１５℃で２時間、焼成を行い、複合酸化物触媒を得た。ケイ素の供給源化合物であるシリカの比表面積および体積平均粒径を表１に示した。触媒活性成分の組成比並びに該触媒活性成分中のケイ素に対するビスマスの原子比を表２に示した。
該複合酸化物触媒を用いて実施例１と同様の条件でプロピレンの酸化反応を行った。結果は表３にまとめた。
Pure water (454 ml) was placed in another container, and ferric nitrate (68.0 g), cobalt nitrate (207.2 g) and nickel nitrate (223.0 g) were added, and the mixture was heated and dissolved (hereinafter referred to as “solution B”). ). Solution B was added to suspension A, stirred to be uniform, and dried by heating to obtain a solid. Then, the solid matter was heat-treated in an air atmosphere at 300° C. for 1 hour.
Further, 93 ml of pure water and 14.3 ml of ammonia water were placed in another container, and 31.7 g of ammonium paramolybdate was added and dissolved to obtain "solution C". Next, 1.0 g of borax and 0.8 g of potassium nitrate were added to and dissolved in the solution C to obtain a “solution D”. The heat-treated solid material (163 g) was added to the solution D and mixed so as to be uniform. Next, 16.2 g of bismuth subcarbonate containing 0.53% solid solution of Na was added and mixed for 30 minutes to obtain a catalytically active component. The catalytically active component was heated to remove water to obtain a dry product, and then the dried product was pulverized to obtain a powder of the catalytically active component (hereinafter referred to as "powder C").
A composite oxide catalyst precursor was prepared by a tumbling granulation method using powder C, a 16.7 wt% aqueous solution of glycerin, and an inert carrier containing alumina and silica as main components. A spherical inert carrier having a diameter of 4.0 mm (porosity 40%, water absorption 20%) was put into a tumbling granulator, and then the powder A and the glycerin aqueous solution were alternately added to obtain the powder A. It was supported on an inert carrier to obtain a supported molding (powder A/(powder A+inert carrier)=40% by weight). The diameter of the support molding was 5.0 mm. At this time, the amount of the organic binder using glycerin was 2 parts by weight with respect to 100 parts by weight of the powder of the catalytically active component.
The supported molded body was calcined in an air atmosphere at 515° C. for 2 hours to obtain a composite oxide catalyst. Table 1 shows the specific surface area and volume average particle diameter of silica, which is a source compound of silicon. Table 2 shows the composition ratio of the catalytically active component and the atomic ratio of bismuth to silicon in the catalytically active component.
Oxidation reaction of propylene was performed under the same conditions as in Example 1 using the composite oxide catalyst. The results are summarized in Table 3.
（比較例１）
容器に温水１８８５ｍｌを入れ、更にパラモリブデン酸アンモニウム２９９ｇを加えて溶解させ、溶液とした（以下、「溶液Ａ」と称する）。
(Comparative Example 1)
1885 ml of warm water was placed in a container, and 299 g of ammonium paramolybdate was further added and dissolved to obtain a solution (hereinafter referred to as "solution A").
別の容器に純水５１２ｍｌを入れ、更に硝酸第二鉄７６．８ｇ、硝酸コバルト２３３．８ｇ及び硝酸ニッケル２５１．７ｇを加えて、加温して溶解させた（以下、「溶液Ｂ」と称する）。溶液Ｂを、加熱乾燥し、固形物を得た。次いで該固形物を空気雰囲気で３００℃、１時間熱処理した。
更に、別の容器に純水５０ｍｌ、アンモニア水８．５ｍｌを入れ、パラモリブデン酸アンモニウム１７．０ｇを加えて溶解し、「溶液Ｃ」とした。次いで、溶液Ｃにホウ砂０．５ｇ及び硝酸カリウム０．４ｇを加えて溶解し、「溶液Ｄ」とした。前記熱処理した固形物１００ｇを溶液Ｄに添加し、均一になるように混合した。次いでＮａを０．５３％固溶した次炭酸ビスマス８．７ｇを加えて３０分間混合し、触媒活性成分とした。該触媒活性成分を加熱して水分を除去し、乾燥品とし、次いで該乾燥品を粉砕し、触媒活性成分の粉
体を得た（以下、「粉体Ｂ」と称する）。
粉体Ｂ、グリセリンの１６．７重量％水溶液、アルミナ及びシリカを主成分とする不活性担体を用いて、転動造粒法により、複合酸化物触媒前駆体を調製した。転動造粒装置に直径４．０ｍｍの球状の不活性担体（気孔率４０％、吸水率２０％）を投入し、次いで該粉体Ａとグリセリン水溶液を交互に添加することにより粉体Ａを不活性担体に担持させ、担持成型体を得た（粉体Ａ／（粉体Ａ＋不活性担体）＝４０重量％）。担持成型体の直径は５．０ｍｍであった。このときグリセリンを用いた有機系バインダー量は、触媒活性成分の粉体１００重量部に対して、２重量部であった。
該担持成型体を空気雰囲気下、５１５℃で２時間、焼成を行い、複合酸化物触媒を得た。ケイ素の供給源化合物であるシリカの比表面積および体積平均粒径を表１に示した。触媒活性成分の組成比並びに該触媒活性成分中のケイ素に対するビスマスの原子比を表２に示した。
該複合酸化物触媒を用いて実施例１と同様の条件でプロピレンの酸化反応を行った。結果は表３にまとめた。
Pure water (512 ml) was placed in another container, and ferric nitrate (76.8 g), cobalt nitrate (233.8 g) and nickel nitrate (251.7 g) were added, and the mixture was heated and dissolved (hereinafter, referred to as “solution B”). ). Solution B was dried by heating to obtain a solid. Then, the solid matter was heat-treated in an air atmosphere at 300° C. for 1 hour.
Further, 50 ml of pure water and 8.5 ml of ammonia water were placed in another container, and 17.0 g of ammonium paramolybdate was added and dissolved to obtain “solution C”. Next, 0.5 g of borax and 0.4 g of potassium nitrate were added to and dissolved in the solution C to obtain a “solution D”. 100 g of the heat-treated solid was added to the solution D and mixed so as to be uniform. Next, 8.7 g of bismuth subcarbonate containing 0.53% of solid solution of Na was added and mixed for 30 minutes to obtain a catalytically active component. The catalytically active component was heated to remove water to obtain a dry product, and then the dried product was pulverized to obtain a powder of the catalytically active component (hereinafter referred to as "powder B").
A composite oxide catalyst precursor was prepared by a tumbling granulation method using powder B, a 16.7 wt% aqueous solution of glycerin, and an inert carrier containing alumina and silica as main components. A spherical inert carrier having a diameter of 4.0 mm (porosity 40%, water absorption 20%) was put into a tumbling granulator, and then the powder A and the glycerin aqueous solution were alternately added to obtain the powder A. It was supported on an inert carrier to obtain a supported molding (powder A/(powder A+inert carrier)=40% by weight). The diameter of the support molding was 5.0 mm. At this time, the amount of the organic binder using glycerin was 2 parts by weight with respect to 100 parts by weight of the powder of the catalytically active component.
The supported molded body was calcined in an air atmosphere at 515° C. for 2 hours to obtain a composite oxide catalyst. Table 1 shows the specific surface area and volume average particle diameter of silica, which is a source compound of silicon. Table 2 shows the composition ratio of the catalytically active component and the atomic ratio of bismuth to silicon in the catalytically active component.
Oxidation reaction of propylene was performed under the same conditions as in Example 1 using the composite oxide catalyst. The results are summarized in Table 3.
本発明の製造方法により製造された複合酸化物触媒は実施例において示されているように、高負荷条件でプロピレンの気相接触酸化反応に用いた場合、プロピレンの転化率に優れ、且つ所望とするアクロレイン及びアクリル酸の選択率が高く維持し、収率の向上が可能となっている。 As shown in the examples, the composite oxide catalyst produced by the production method of the present invention is excellent in the conversion rate of propylene when used in the gas phase catalytic oxidation reaction of propylene under high load conditions, and has a desired value. The selectivity of acrolein and acrylic acid to be used is kept high, and the yield can be improved.
Claims (6)
（ｂ）工程（ａ）で得られた触媒活性成分の粉体を、転動造粒法により、不活性担体に担持する工程を含む、オレフィンを酸素含有ガスにより気相接触酸化して不飽和アルデヒド及び不飽和カルボン酸を製造するための複合酸化物触媒を製造する方法であり、
触媒活性成分が下記組成式（１）で表され、ケイ素の供給源化合物の比表面積が１２０ｍ２／ｇ〜３００ｍ２／ｇであり、かつ体積平均粒径が０．２μｍ〜３μｍであるオレフィンを原料として酸素含有ガスとの気相接触酸化反応により対応する不飽和アルデヒド及び不飽和カルボン酸を製造する際に用いる複合酸化物触媒の製造方法。
ＭｏａＢｉｂＣｏｃＮｉｄＦｅｅＸｆＹｇＳｉｈＯｉ （１）
（式中、Ｘはナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）及びタリウム（Ｔｌ）からなる群から選ばれる少なくとも１種の元素であり、Ｙはホウ素（Ｂ）、リン（Ｐ）、砒素（Ａｓ）及びタングステン（Ｗ）からなる群から選ばれる少なくとも１種の元素である。また、ａ〜ｉはそれぞれの元素の原子比を表わし、ａ＝１２のとき、ｂ＝０．５〜７、ｃ＝０．１〜５．０、ｄ＝０．１〜１０、ｅ＝０．０５〜５、ｆ＝０〜２、ｇ＝０〜３、ｈ＝１〜４８の範囲にあり、またｉは他の元素の酸化状態を満足させる数値である。） (A) A step of integrating and heating each source compound of a catalytically active element containing molybdenum, bismuth and silicon in an aqueous system to obtain powder of a catalytically active component (b) Catalytic activity obtained in step (a) Composite oxidation for producing unsaturated aldehyde and unsaturated carboxylic acid by gas-phase catalytic oxidation of olefin with oxygen-containing gas, including the step of supporting the powder of the component on an inert carrier by tumbling granulation method Is a method for producing a physical catalyst,
Catalytically active component is represented by the following composition formula (1), the specific surface area of the source compound of silicon is the 120m 2 / g~300m 2 / g, and volume average particle size of the olefin is 0.2μm~3μm A method for producing a composite oxide catalyst used in producing a corresponding unsaturated aldehyde and unsaturated carboxylic acid by a gas phase catalytic oxidation reaction with a gas containing oxygen as a raw material.
Mo a Bi b Co c Ni d Fe e X f Y g Si h O i (1)
(In the formula, X is at least one element selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and thallium (Tl), and Y is boron (B). , At least one element selected from the group consisting of phosphorus (P), arsenic (As) and tungsten (W), and a to i represent the atomic ratio of each element, and when a=12, b=0.5-7, c=0.1-5.0, d=0.1-10, e=0.05-5, f=0-2, g=0-3, h=1- It is in the range of 48, and i is a numerical value that satisfies the oxidation states of other elements.)
又は５に記載のアクロレイン及びアクリル酸の製造方法。 The propylene content in the raw material mixed gas is in the range of 7% by volume to 12% by volume.
Or the method for producing acrolein and acrylic acid according to item 5.
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| CN112691680B (en) * | 2019-10-23 | 2023-05-02 | 中国石油化工股份有限公司 | Composite catalyst for acrolein synthesis and preparation method and application thereof |
| JP7347282B2 (en) * | 2020-03-18 | 2023-09-20 | 三菱ケミカル株式会社 | Method for producing catalyst for unsaturated carboxylic acid synthesis |
| JP7347283B2 (en) * | 2020-03-18 | 2023-09-20 | 三菱ケミカル株式会社 | Method for producing catalyst for unsaturated carboxylic acid synthesis |
| JP7480671B2 (en) * | 2020-10-20 | 2024-05-10 | 三菱ケミカル株式会社 | Method for producing catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids |
| JP7480672B2 (en) * | 2020-10-20 | 2024-05-10 | 三菱ケミカル株式会社 | Method for producing catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids |
| JP7237268B1 (en) * | 2021-10-14 | 2023-03-10 | 日本化薬株式会社 | Catalyst for producing unsaturated carboxylic acid, method for producing the same, and method for producing unsaturated carboxylic acid |
| WO2023063349A1 (en) * | 2021-10-14 | 2023-04-20 | 日本化薬株式会社 | Catalyst for production of unsaturated carboxylic acid, method for producing same, and method for producing unsaturated carboxylic acid |
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