WO2011142178A1 - 混合物触媒 - Google Patents
混合物触媒 Download PDFInfo
- Publication number
- WO2011142178A1 WO2011142178A1 PCT/JP2011/056941 JP2011056941W WO2011142178A1 WO 2011142178 A1 WO2011142178 A1 WO 2011142178A1 JP 2011056941 W JP2011056941 W JP 2011056941W WO 2011142178 A1 WO2011142178 A1 WO 2011142178A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composite oxide
- propane
- catalyst
- tungsten
- reaction
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 187
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 226
- 238000006243 chemical reaction Methods 0.000 claims abstract description 158
- 239000002131 composite material Substances 0.000 claims abstract description 122
- 239000001294 propane Substances 0.000 claims abstract description 113
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 68
- 239000010937 tungsten Substances 0.000 claims abstract description 67
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 64
- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 53
- 230000003197 catalytic effect Effects 0.000 claims abstract description 35
- 239000001282 iso-butane Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 23
- 150000002825 nitriles Chemical class 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 229910052788 barium Inorganic materials 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 239000000470 constituent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 210
- 239000007789 gas Substances 0.000 claims description 83
- 238000004519 manufacturing process Methods 0.000 claims description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 abstract description 8
- 239000010955 niobium Substances 0.000 description 66
- 238000010304 firing Methods 0.000 description 59
- 239000007788 liquid Substances 0.000 description 51
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 42
- 238000000034 method Methods 0.000 description 42
- 239000002994 raw material Substances 0.000 description 38
- 239000012071 phase Substances 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- 239000000843 powder Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 22
- 238000002156 mixing Methods 0.000 description 20
- 229910052758 niobium Inorganic materials 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000032683 aging Effects 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- -1 inorganic acid salt Chemical class 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 3
- 150000002821 niobium Chemical class 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910020015 Nb W Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 1
- JGHNXMHWDGTLQX-UHFFFAOYSA-N O.O.O.[Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound O.O.O.[Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JGHNXMHWDGTLQX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MAKKVCWGJXNRMD-UHFFFAOYSA-N niobium(5+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] MAKKVCWGJXNRMD-UHFFFAOYSA-N 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- LXXCECZPOWZKLC-UHFFFAOYSA-N praseodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LXXCECZPOWZKLC-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
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- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
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- C07C255/08—Acrylonitrile; Methacrylonitrile
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- C07C57/03—Monocarboxylic acids
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a mixture catalyst and a method for producing an unsaturated acid or an unsaturated nitrile using the mixture catalyst.
- Patent Document 1 discloses that Mo—V—Sb / Te-based catalysts include tungsten, molybdenum, chromium, zirconium, titanium, niobium, tantalum, vanadium, boron, bismuth, tellurium, palladium, cobalt, nickel, iron, phosphorus, silicon.
- Patent Document 2 discloses a method for producing a modified mixed metal oxide by bringing a mixed metal oxide catalyst into contact with water and optionally an aqueous metal oxide precursor, and firing the resulting modified mixed metal oxide.
- Patent Document 3 discloses a method of immersing tungsten and manganese in a Mo—V—Sb—Nb-based catalyst.
- Patent Document 4 a catalyst such as an antimony compound, a molybdenum compound, a tellurium compound, or a tungsten compound is mixed and used for the reaction, or the catalyst or catalyst precursor is mixed with a modifier and calcined, and then used for the reaction.
- a technique is disclosed.
- Patent Documents 1 to 3 when the present inventors used the oxide catalysts disclosed in Patent Documents 1 to 3 for the gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane, none of the catalysts still contained the target product. The rate was insufficient.
- Patent Documents 1 to 4 it is described that the performance is improved by impregnating or immersing tungsten in a Mo—V—Te / Sb-based composite oxide that is still active.
- the composite oxide before impregnation or immersion does not contain tungsten, and has not led to a catalyst with a high yield of the target product.
- the problem to be solved by the present invention is a catalyst for gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane, and the corresponding unsaturated acid or unsaturated nitrile from propane or isobutane Is provided in a high yield, and a process for producing an unsaturated acid or an unsaturated nitrile using the mixture catalyst is provided.
- the present invention is as follows.
- Mixture catalyst for gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction of propane or isobutane A mixed catalyst containing a composite oxide represented by the following composition formula (1) and a tungsten compound in a proportion of the following formula (2); Mo 1 V a Nb b Sb c W d Z e O n (1)
- Z is at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba, and a, b, c, d, e, and n are Mo1.
- a method for producing an unsaturated acid or an unsaturated nitrile comprising: A production method comprising a step of bringing propane or isobutane and oxygen, or propane or isobutane, oxygen and ammonia into contact with the mixture catalyst according to any one of [1] to [3] above.
- a production method comprising a step of bringing propane or isobutane and oxygen, or propane or isobutane, oxygen and ammonia into contact with the mixture catalyst according to any one of [1] to [3] above.
- a production method comprising a step of bringing propane or isobutane and oxygen, or propane or isobutane, oxygen and ammonia into contact with the mixture catalyst according to any one of [1] to [3] above.
- a manufacturing method according to the above [4] wherein the temperature of the contacting step is 400 ° C. or higher.
- the corresponding unsaturated acid or unsaturated nitrile can be produced in high yield from propane or isobutane.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
- the mixture catalyst of this embodiment is Mixture catalyst for gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction of propane or isobutane, A mixed catalyst containing a composite oxide represented by the following composition formula (1) and a tungsten compound in a proportion of the following formula (2); Mo 1 V a Nb b Sb c W d Z e O n (1)
- Z is at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba, and a, b, c, d, e, and n are Mo1.
- a is 0.01 ⁇ a ⁇ 1
- b is 0.01 ⁇ b ⁇ 1
- c is 0.01 ⁇ c ⁇ 1
- d is 0.001 ⁇ d ⁇ 1.
- E represents 0 ⁇ e ⁇ 1
- n represents a number determined by the valence of the constituent metal.
- w represents the atomic ratio of tungsten in the tungsten compound as the atomic ratio per Mo atom in the composite oxide).
- the method for producing the mixture catalyst of the present embodiment is not particularly limited, but an example thereof will be described below.
- the composite oxide contained in the mixture catalyst of the present embodiment can be produced, for example, by the following method.
- a complex oxide is produced by the following three steps. (1) Step for preparing raw material preparation liquid by preparing raw materials (2) Step for drying raw material preparation liquid obtained in step (1) to obtain dry powder (3) Drying obtained in step (2) Process of firing powder to obtain composite oxide
- Preparation in the above step (1) refers to dissolving or dispersing a raw material of the composite oxide in an aqueous solvent, and the raw material refers to a compound containing a constituent element of the composite oxide.
- ammonium heptamolybdate (NH 4) 6 Mo 7 O 24 ⁇ 4H 2 O] and ammonium metavanadate [NH 4 VO 3] suitably it can.
- Niobic acid is a compound represented by Nb 2 O 5 .nH 2 O and is also referred to as niobium hydroxide or niobium oxide hydrate.
- Nb raw material liquid having a dicarboxylic acid / niobium molar ratio of 1 to 4 as the Nb raw material.
- oxalic acid is preferable as the dicarboxylic acid.
- the raw material of Sb is not particularly limited, but diantimony trioxide [Sb 2 O 3 ] is preferable.
- the raw material of W is not particularly limited, and a compound containing W or a solution obtained by solubilizing W metal with an appropriate solvent can be used.
- the compound containing W include W ammonium salt, nitrate, carboxylate, ammonium carboxylate, peroxocarboxylate, ammonium peroxocarboxylate, ammonium halide salt, halide, acetylacetonate, alkoxide and the like.
- water-soluble raw materials such as W nitrate and carboxylate are preferably used.
- the raw material for component Z is not particularly limited as long as it is a substance containing at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba.
- a solution obtained by solubilizing the metal of the above element with an appropriate solvent can be used.
- the compound containing the above element include nitrates, carboxylates, ammonium carboxylates, peroxocarboxylates, ammonium peroxocarboxylates, ammonium halides, halides, acetylacetonates, alkoxides, and the like of the above metal elements.
- water-soluble raw materials such as nitrates and carboxylates are preferably used.
- silica sol can be used as the silica raw material, but powder silica can also be used for a part or all of the silica raw material.
- the powder silica is preferably produced by a high heat method.
- the powder silica can be easily added to and mixed in the slurry by being dispersed in water in advance.
- a general homogenizer, a homomixer, an ultrasonic vibrator, etc. can be disperse
- Step (1) Step of preparing raw materials
- Mo compound, V compound, Sb compound, W compound, component Z compound, and other ingredients as necessary are added to water and heated to prepare an aqueous mixture (I).
- the inside of the container for preparing the mixed liquid (I) may be a nitrogen atmosphere.
- the Nb compound and dicarboxylic acid are heated and stirred in water to prepare a mixed solution (B 0 ).
- hydrogen peroxide is added to the mixed solution (B 0 ) to prepare an aqueous mixed solution (II).
- H 2 O 2 / Nb (molar ratio) is preferably 0.5 to 20, and more preferably 1 to 10.
- the aqueous mixed liquid (I) and the aqueous mixed liquid (II) are suitably mixed according to the target composition to obtain the aqueous mixed liquid (III).
- the obtained aqueous mixed liquid (III) is aged in an air atmosphere to obtain a slurry-form raw material preparation liquid (hereinafter also simply referred to as “slurry”).
- the aging of the aqueous mixed liquid (III) means that the aqueous mixed liquid (III) is allowed to stand for a predetermined time or is stirred.
- the processing speed of the spray dryer is usually limited, and after a part of the aqueous mixed liquid (III) is spray dried, until the spray drying of all the mixed liquid is completed. Takes time. During this time, aging of the liquid mixture that has not been spray-dried is continued. Therefore, the aging time includes not only the aging time before spray drying but also the time from the start to the end of spray drying.
- the aging time is preferably 90 minutes or more and 50 hours or less, and more preferably 90 minutes or more and 6 hours or less from the viewpoint of the yield of the target product.
- the aging temperature is preferably 25 ° C. or higher from the viewpoint of preventing condensation of the Mo component and precipitation of V. Moreover, 65 degreeC or less is preferable from the viewpoint of preventing hydrolysis of the complex containing Nb and hydrogen peroxide from occurring too much and forming a slurry of a preferable form. Therefore, the aging temperature is preferably 25 ° C. or more and 65 ° C. or less, and more preferably 30 ° C. or more and 60 ° C. or less.
- the atmosphere in the container at the time of aging has a sufficient oxygen concentration. Insufficient oxygen may make it difficult for a substantial change in the aqueous mixture (III) to occur.
- the oxygen concentration in the gas phase portion in the container (hereinafter also referred to as “gas phase oxygen concentration”) is preferably 1 vol% or more.
- the gas phase oxygen concentration in the container can be measured by a general method, for example, using a zirconia oxygen analyzer.
- the place where the gas phase oxygen concentration is measured is preferably near the interface between the aqueous mixed liquid (III) and the gas phase.
- Nitrogen is preferable industrially.
- the gas for increasing the gas phase oxygen concentration is preferably pure oxygen or air with a high oxygen concentration.
- the redox potential of the aqueous mixture (III) is dominated by the potential 600 mV / AgCl of the aqueous raw material liquid (II), and the oxalic acid Nb peroxide and other metal components contained in the aqueous raw material liquid (II) are oxidized in some way. It is considered that the potential decreases with time due to the reduction reaction.
- the redox potential of the aqueous mixture (III) is preferably 450 to 530 mV / AgCl, and more preferably 470 to 510 mV / AgCl.
- the oxygen concentration inside is preferably 1 vol% or more.
- the oxygen concentration during the aging is preferably 25 vol% or less. In any case, since the gas phase oxygen affects the oxidation-reduction state of the slurry, it is necessary to maintain the oxygen concentration within an appropriate range, and the range is more preferably 5 to 23 vol%, and further 10 to 20 vol%. preferable.
- a raw material preparation liquid is prepared so as to include a silica sol.
- Silica sol can be added as appropriate.
- a part of the silica sol can be made into an aqueous dispersion of powdered silica.
- An aqueous dispersion of powdered silica can also be added as appropriate.
- H 2 O 2 / Sb (molar ratio) is preferably 0.01 to 5, and more preferably 0.05 to 4.
- stirring is preferably continued at 30 ° C. to 70 ° C. for 30 minutes to 2 hours.
- step (2) a dry powder is obtained by drying the slurry obtained in the raw material preparation step. Drying can be performed by a known method, for example, spray drying or evaporation to dryness. Among them, it is preferable to obtain a fine spherical dry powder by spray drying.
- the atomization in the spray drying method can be performed by a centrifugal method, a two-fluid nozzle method, or a high-pressure nozzle method.
- As the drying heat source air heated by steam, an electric heater or the like can be used.
- the dryer inlet temperature of the spray dryer is preferably 150 to 300 ° C, and the dryer outlet temperature is preferably 100 to 160 ° C.
- step (3) a composite oxide is obtained by subjecting the dry powder obtained in the drying step to firing.
- a rotary furnace rotary kiln
- the shape of the calciner is not particularly limited, but a tubular shape is preferable because continuous calcining can be performed.
- the shape of the firing tube is not particularly limited, but is preferably cylindrical.
- the heating method is preferably an external heating type, and for example, an electric furnace can be suitably used.
- the size, material, and the like of the firing tube can be selected appropriately according to the firing conditions and the production amount, but preferably have an inner diameter of 70 to 2000 mm, more preferably an inner diameter of 100 to 1200 mm.
- the length of the firing tube is preferably 200 to 10000 mm, more preferably 800 to 8000 mm.
- the thickness is preferably 2 mm or more, more preferably 4 mm or more from the viewpoint of having a sufficient thickness so as not to be damaged by the impact, and the impact is sufficiently transmitted to the inside of the firing tube. From the viewpoint, it is preferably 100 mm or less, more preferably 50 mm or less.
- the material of the fired tube is not particularly limited as long as it has heat resistance and has a strength that does not break due to impact, and SUS can be suitably used.
- a weir plate having a hole for the passage of powder in the center can be provided perpendicular to the flow of the powder to divide the firing tube into two or more areas. By installing the weir plate, it becomes easy to secure the residence time in the firing tube.
- the number of weir plates may be one or more.
- the material of the weir plate is preferably metal, and the same material as that of the firing tube can be suitably used. The height of the weir plate can be adjusted according to the residence time to be secured.
- the height of the weir plate is preferably 5 to 50 mm, more preferably 10 to It is 40 mm, more preferably 13 to 35 mm.
- the thickness of the weir plate is not particularly limited and is preferably adjusted according to the size of the firing tube.
- the thickness of the barrier plate is preferably 0.3 mm or more and 30 mm or less, more preferably 0.5 mm or more and 15 mm or less.
- the rotation speed of the firing tube is preferably 0.1 to 30 rpm, more preferably 0.5 to 20 rpm, and still more preferably 1 to 10 rpm.
- the heating temperature of the dry powder is started from a temperature lower than 400 ° C. and continuously or intermittently raised to a temperature in the range of 550 to 800 ° C. .
- the firing atmosphere may be an air atmosphere or an air circulation, but it is preferable to carry out at least a part of the firing while circulating an inert gas substantially free of oxygen such as nitrogen.
- the supply amount of the inert gas is preferably 50 N liters or more, more preferably 50 to 5000 N liters, more preferably 50 to 3000 N liters per 1 kg of the dry powder (N liter is a standard temperature / pressure condition, that is, Means liters measured at 0 ° C. and 1 atm).
- N liter is a standard temperature / pressure condition, that is, Means liters measured at 0 ° C. and 1 atm).
- the firing step can be carried out even in one stage, but the firing comprises pre-stage firing and main firing, the pre-stage firing is performed in a temperature range of 250 to 400 ° C., and the main firing is performed in a temperature range of 550 to 800 ° C. Preferably it is done.
- the pre-baking and the main baking may be performed continuously, or the main baking may be performed again after the pre-baking is once completed.
- each of pre-stage baking and main baking may be divided into several stages.
- the pre-stage calcination is preferably carried out in the range of a heating temperature of 250 ° C. to 400 ° C., preferably 300 ° C. to 400 ° C. under an inert gas flow.
- the pre-stage firing is preferably held at a constant temperature within a temperature range of 250 ° C. to 400 ° C., but the temperature may fluctuate within the range of 250 ° C. to 400 ° C., and the temperature may be gradually raised or lowered. Absent.
- the holding time of the heating temperature is preferably 30 minutes or more, more preferably 3 to 12 hours.
- the temperature rising pattern until reaching the pre-stage firing temperature may be increased linearly, or the temperature may be increased by drawing an upward or downward convex arc.
- the average rate of temperature increase during the temperature increase until reaching the pre-stage firing temperature is generally about 0.1 to 15 ° C./min, preferably 0.5 to 5 ° C./min, more preferably 1 to 2 ° C./min.
- the main calcination can be carried out preferably under an inert gas flow, preferably at 550 to 800 ° C., more preferably 580 to 750 ° C., further preferably 600 to 720 ° C., and particularly preferably 620 to 700 ° C.
- the main calcination is preferably held at a constant temperature within the temperature range of 620 to 700 ° C., but the temperature may fluctuate within the range of 620 to 700 ° C., or the temperature may be gradually increased or decreased.
- the firing time is preferably 0.5 to 20 hours, more preferably 1 to 15 hours.
- the dry powder and / or the composite oxide continuously pass through at least two, preferably 2 to 20, more preferably 4 to 15 areas.
- the temperature can be controlled by using one or more controllers, but in order to obtain the desired firing pattern, a heater and a controller should be installed and controlled for each area separated by these weirs. Is preferred.
- the set temperature is controlled by a heater and a controller in which eight areas are provided for each of the areas so that the temperature becomes the desired firing temperature pattern.
- an oxidizing component for example, oxygen
- a reducing component for example, ammonia
- the temperature rising pattern until reaching the main firing temperature may be increased linearly, or the temperature may be increased by drawing an upward or downward convex arc.
- the average rate of temperature increase during the temperature increase until reaching the main firing temperature is not particularly limited, but is generally 0.1 to 15 ° C./min, preferably 0.5 to 10 ° C./min, more preferably 1 to 8 ° C./min.
- the average temperature decreasing rate after the completion of the main firing is 0.01 to 1000 ° C./min, preferably 0.05 to 100 ° C./min, more preferably 0.1 to 50 ° C./min, particularly preferably 0.5 to 10 ° C./min.
- the holding temperature is a temperature that is 10 ° C. or more, preferably 50 ° C. or more, more preferably 100 ° C. or more lower than the main firing temperature.
- the holding time is 0.5 hours or more, preferably 1 hour or more, more preferably 3 hours or more, and particularly preferably 10 hours or more.
- the pre-baking is performed once after the pre-stage baking is completed, it is preferable to perform a low-temperature treatment in the main baking.
- the time required for low-temperature treatment is the size, thickness, material, catalyst of the calciner It is possible to adjust appropriately according to the production amount, a series of periods in which the dry powder and / or the composite oxide are continuously fired, the fixing speed, the fixing amount, and the like.
- a SUS calcining tube having an inner diameter of 500 mm, a length of 4500 mm, and a wall thickness of 20 mm, preferably within 30 days, more preferably within 15 days, Preferably within 3 days, particularly preferably within 2 days.
- dry powder is supplied at a rate of 35 kg / hr while rotating at 6 rpm by a rotary furnace having a SUS firing tube having an inner diameter of 500 mm, a length of 4500 mm, and a wall thickness of 20 mm, and the main firing is performed at a main firing temperature of 645 ° C.
- the step of raising the temperature to 645 ° C. can be performed in about one day.
- firing can be performed while maintaining the oxide layer temperature stably.
- some of the low melting point compounds in the oxide crystals may crystallize in a protruding shape on the surface of the composite oxide particles. Since the crystals of the low-melting-point compound ooze out on the surface of the catalyst, the fluidity may be hindered when the catalyst is used in a fluidized bed reaction. Therefore, in the case of a catalyst for fluidized bed reaction, it is preferable to physically remove the crystals of the low-melting-point compound derived from the protrusions prior to the use of the catalyst, from the viewpoint of preventing a decrease in fluidity. When removing the crystal of the low melting point compound from the surface of the catalyst, it may be removed before the tungsten source mixing step described later or after the mixing step.
- tungsten source tungsten compound supply source
- (B-1) Tungsten source examples include tungsten ammonium salt, nitrate salt, carboxylate salt, ammonium carboxylate salt, peroxocarboxylate salt, ammonium peroxocarboxylate salt, ammonium halide salt, halide, acetyl Acetonates, alkoxides, triphenyl compounds, polyoxometalates, polyoxometalate ammonium salts; powder raw materials such as tungsten oxide, tungstic acid, ammonium paratungstate, silicotungstic acid, silicotungsto molybdic acid, and cavernadotungstic acid; Examples thereof include liquid raw materials such as an aqueous solution of ammonium metatungstate and tungsten oxide sol.
- the kind of the tungsten source and whether it is mixed in a solid or liquid form can be selected depending on what mixing step is performed, the composition of the mixture catalyst to be prepared, and the like.
- the mixing step includes a method of supplying the tungsten source in a solid state and a method of supplying the tungsten source in a liquid state.
- a liquid supply method a commercially available product such as an ammonium metatungstate aqueous solution may be used.
- the above powder raw material is used by dissolving and / or dispersing in a solvent. Also good.
- an appropriate amount of powder raw material may be dissolved and / or dispersed in water, acetone, methanol, ethanol, or other polar / nonpolar solvent.
- water it is preferable to use water as a solvent and / or a dispersion medium from the viewpoint of ease of handling.
- tungsten oxide is preferable from the viewpoint of influence on the target product by the tungsten compound, more preferably tungsten oxide having a tungsten bronze structure, and further preferably tungsten trioxide.
- the mixture catalyst of this embodiment can be obtained by physically or chemically mixing the above-described composite oxide and a tungsten source at a predetermined ratio.
- B-2 Physical mixing method
- the physical mixing method of the composite oxide and the tungsten source is not particularly limited. For example, an appropriate amount of the tungsten source is added to the hopper that supplies the catalyst to the reactor by adding the composite oxide. A method is mentioned. Before the mixed oxide and the tungsten source are put into the hopper, they may be mixed in advance, but they are naturally mixed in the process of supplying the catalyst from the hopper to the reactor without mixing in advance. It is not essential to keep it.
- the order in which the composite oxide and the tungsten source are put into the hopper is not particularly limited, and may be appropriately determined so as to be in a sufficiently contacted state in the reactor from the viewpoint of the particle size of the both. If necessary, air and nitrogen can be circulated and mixed.
- the composite oxide and the tungsten source may be sequentially supplied into the reactor, instead of supplying from the hopper at a time. In this case, the composite oxide and the tungsten source are mixed while flowing in the reactor while the reaction proceeds.
- the tungsten compound contained in the mixture catalyst has the same structure as the tungsten source.
- the tungsten compound is chemically changed because heat is applied in a state of being in contact with the composite oxide or the reaction substrate.
- the mixture catalyst in the present embodiment is a catalyst with a view to affect the composite oxide by acting on the composite oxide by such a structural change during the progress of the reaction.
- the present embodiment is naturally applied to the case where it exists as a mixture before the reaction.
- This is a category of a mixture catalyst.
- the mixture catalyst does not exist before the reaction, but it can be said that the mixture catalyst is formed immediately after the supply of the tungsten source.
- the pores of the complex oxide are filled with air, inert gas, and other atmospheric gases that existed before the contact treatment of the complex oxide, which may hinder the diffusion of tungsten into the pores. There is. In that case, the gas in the pores can be removed under a reduced pressure atmosphere before or during the impregnation or immersion.
- the catalyst in which tungsten is incorporated into the complex oxide and the mixture catalyst are compared in terms of the performance of the catalyst, when the catalyst in which tungsten is incorporated is used for the production reaction of the unsaturated acid or unsaturated nitrile, the yield of the target product shows the maximum value at the initial stage of the reaction, and after that, even if the yield deteriorates, it does not improve. As the process proceeds, the yield of the target product tends to improve.
- the ion exchange in the liquid phase depends on the pH, the liquid temperature, the tungsten concentration in the solution, the contact time between the solution and the complex oxide, and the pH is, for example, 1.0 to 7.0, preferably 1.0.
- the pH is, for example, 1.0 to 7.0, preferably 1.0.
- ion exchange can be suppressed.
- the liquid temperature is preferably low.
- ion exchange can be suppressed.
- the contact time between the solution and the composite oxide is preferably shorter, and is within 1 hour, more preferably within 15 minutes.
- the mixture obtained by the impregnation and / or dipping process can be used as a mixture catalyst as it is, but may be used after firing.
- the tungsten compound contained in the mixture catalyst that has undergone the liquid phase treatment may have an aspect in which the tungsten source is changed (eg, oxidized, crystallized, or amorphous) in addition to an aspect having the same structure as the tungsten source. Even if it is an aspect, as long as it contains the tungsten compound which is not a part of complex oxide, it is the category of the mixture catalyst in this embodiment.
- (B-3-ii) Firing Step Even when ion exchange does not occur in the liquid phase, an exchange reaction may occur in the firing step, and the tungsten source may become a part of the composite oxide. As in the liquid phase treatment, this exchange reaction is expected to be in a non-mixed state due to progress of surface modification. The ease with which the exchange reaction occurs depends mainly on the firing temperature. If the firing temperature is too high, the exchange reaction tends to proceed.
- the firing temperature at which the exchange reaction hardly occurs is preferably 200 to 400 ° C., more preferably 250 to 350 ° C.
- the tungsten compound contained in the mixture catalyst that has undergone the calcination treatment generally has a structure different from that of the tungsten source, but as long as it contains a tungsten compound that is not a part of the composite oxide, similar to the one after the liquid phase treatment.
- the category of the mixture catalyst in the present embodiment is not a part of the composite oxide, similar to the one after the liquid phase treatment.
- the mixture catalyst in this embodiment is Mixture catalyst for gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction of propane or isobutane, A mixed catalyst containing a composite oxide represented by the following composition formula (1) and a tungsten compound in a proportion of the following formula (2); Mo 1 V a Nb b Sb c W d Z e O n (1)
- Z is at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba, and a, b, c, d, e, and n are Mo1.
- a is 0.01 ⁇ a ⁇ 1
- b is 0.01 ⁇ b ⁇ 1
- c is 0.01 ⁇ c ⁇ 1
- d is 0.001 ⁇ d ⁇ 1.
- E represents 0 ⁇ e ⁇ 1
- n represents a number determined by the valence of the constituent metal.
- w represents the atomic ratio of tungsten in the tungsten compound as the atomic ratio per Mo atom in the composite oxide).
- the mixture catalyst in the present embodiment is a mixture of a tungsten compound and a composite oxide.
- a tungsten compound as an essential component in the mixture catalyst, during the vapor phase catalytic oxidation reaction of propane or isobutane and oxygen, or during the vapor phase catalytic ammoxidation reaction of propane or isobutane, oxygen and ammonia, Based on the principle that tungsten element diffuses and is immobilized on the surface of the complex oxide, the yield of the target product can be dramatically improved.
- the composition of the composite oxide in the present embodiment is represented by the following formula (1).
- Mo 1 V a Nb b Sb c W d Z e O n
- Z is at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, Ba, a, b, c, d, e, n are Indicate the atomic ratio of each element per Mo atom, a is 0.01 ⁇ a ⁇ 1, b is 0.01 ⁇ b ⁇ 1, c is 0.01 ⁇ c ⁇ 1, d is 0.001 ⁇ d ⁇ 1 and e are 0 ⁇ e ⁇ 1, and n is a number determined by the valence of the constituent metal.
- a and b indicating the atomic ratio of V and Nb per Mo atom are preferably 0.1 to 0.4 and 0.02 to 0.2, respectively.
- C indicating the atomic ratio of Sb per Mo atom is preferably 0.01 to 0.6, more preferably 0.1 to 0.4. Further, as a result of intensive investigation of the atomic ratio of V and Sb, a / c is not clear, but from the viewpoint of improving yield, a / c is preferably in the range of 0.1 to 1. I understood that.
- D indicating the atomic ratio of W per Mo atom is 0.001 ⁇ d ⁇ 1, and preferably 0.001 ⁇ d ⁇ 0.3. It is presumed that tungsten in the composite oxide (hereinafter, tungsten present in the composite oxide is also referred to as “bulk tungsten”) is replaced with molybdenum or vanadium sites in the composite oxide.
- the melting points of the oxides are compared, for example, the melting points of molybdenum trioxide and tungsten trioxide are 795 ° C. and 1473 ° C., and the melting point of tungsten oxide is high. Therefore, molybdenum in the composite oxide is replaced with tungsten. It is estimated that the melting point of the composite oxide becomes high.
- the bulk tungsten dispersed in the composite oxide affects the crystal structure of the composite oxide and contributes to heat resistance and redox resistance.
- the composite oxide having bulk tungsten is The catalyst life tends to be long and tends to be advantageous for industrial long-term use.
- tungsten in the tungsten compound is presumed to have an effect of increasing the yield of unsaturated acid or unsaturated nitrile.
- an effect of bulk tungsten it is presumed that there is an effect of suppressing a decrease in the yield of the target product due to excessive diffusion of tungsten in the tungsten compound into the composite oxide.
- E indicating the atomic ratio of the component Z per Mo atom is 0 ⁇ e ⁇ 1, preferably 0.001 ⁇ e ⁇ 1, more preferably 0.001 ⁇ e ⁇ 0.1, and 0.002 ⁇ e. ⁇ 0.01 is more preferable.
- Component Z is preferably contained in a trace amount, as taught in JP-A-11-244702, which may cause an undesirable reaction in the slurry.
- the component Z is highly effective in improving the yield of the target product, it is preferable that the component Z is uniformly dispersed in the catalyst particles.
- Component Z is at least one element selected from the group consisting of La, Ce, Pr, Yb, Y, Sc, Sr, and Ba, and one or more elements selected from the group consisting of La, Ce, Pr, and Yb Ce is particularly preferable because the yield of the target product tends to be the highest.
- the composite oxide is preferably supported by a carrier mainly composed of silica.
- a carrier mainly composed of silica When the composite oxide is supported by a carrier containing silica as a main component, it has a high mechanical strength, and therefore is suitable for a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction using a fluidized bed reactor.
- the content of silica in the carrier mainly composed of silica is 20 to 70% by mass in terms of SiO 2 with respect to the total mass of the supported oxide composed of the oxide of the complex oxide constituting element and the carrier. Preferably, it is 30 to 60% by mass.
- the content of silica in the composite oxide is preferably 20% by mass or more from the viewpoint of strength and prevention of powdering. Further, when the silica content is less than 20% by mass, stable operation is difficult even when the composite oxide is industrially used, and it is necessary to replenish the lost composite oxide, which is economically preferable. Absent. On the contrary, when the content of silica exceeds 70% by mass, sufficient activity cannot be obtained, and the necessary amount of catalyst increases. Particularly in the case of a fluidized bed, if the silica content exceeds 70% by mass, the specific gravity of the silica-supported particles becomes too light, and it becomes difficult to obtain a good fluidized state.
- the mixture catalyst in the present embodiment is a catalyst containing the composite oxide represented by the composition formula (1) and the tungsten compound in the ratio of the following formula (2). 0.001 ⁇ w ⁇ 0.3 (2)
- w represents the atomic ratio of tungsten in the tungsten compound as the atomic ratio per Mo atom in the composite oxide.
- the atomic ratio of tungsten in the tungsten compound per Mo atom of the composite oxide, w is 0.001 ⁇ w ⁇ 0.3, preferably 0.01 ⁇ w ⁇ 0.2, more preferably 0. .015 ⁇ w ⁇ 0.18.
- w is 0.001 or less, the amount of tungsten is too small to improve the yield of the target product, and when it is 0.3 or more, there is too much tungsten and the catalyst surface is not reformed into a preferable form. Also, the yield improvement effect of the target product cannot be obtained.
- the composition of the mixture catalyst and the composite oxide are measured by fluorescent X-ray analysis and calculated from the following equation.
- w (W composition ratio in the mixture catalyst) ⁇ (W composition ratio in the composite oxide)
- a low melting point compound may crystallize in the shape of a protrusion on the surface of the composite oxide particle after the main firing. Even when the crystals are removed from the catalyst surface by contact between the catalysts, w is hardly affected. Therefore, the determination of w by composition analysis may be performed at any stage before and after the oxide crystal removal.
- the composite oxide and the tungsten compound are in contact with each other in the mixture catalyst.
- the contact may be contact between particles in the order of micrometers and millimeters, or contact between a tungsten compound and a composite oxide dispersed in nano-order within pores in the composite oxide particle.
- the former is obtained by physical mixing of composite oxide particles and a tungsten source, and the latter is obtained by liquid phase treatment using the composite oxide particles and a liquid tungsten source.
- the mixed catalyst of the present embodiment it is difficult to confirm the structural change before and after the mixing process even if the structural analysis by X-ray diffraction or the like is performed.
- the target product is produced using a mixture catalyst
- the unsaturated nitrile production reaction is carried out at 445 ° C.
- the reaction time elapses, a difference appears in the yields of both reactions. For example, after 240 hours, a yield improvement of 1% or more is observed in the reaction using the mixture catalyst as compared with the initial stage.
- the composite oxide there is almost no change from the initial yield.
- the present inventors combined tungsten in the tungsten compound by solid-phase reaction. It is presumed that this is because it diffuses on the oxide surface and undergoes an exchange reaction with a metal element such as Mo, whereby the catalyst surface is modified into a preferred form. Although the preferred form of the catalyst surface and the mechanism for improving the performance are not clear, it is presumed that the sequential decomposition of the target product or intermediate product is suppressed by placing tungsten at a specific site in the vicinity of the composite oxide surface.
- a method (makeup technique) in which a Mo compound is introduced into a reactor to suppress a decrease in activity associated with a decrease in Mo composition.
- this Mo compound make-up technology can be used in combination.
- the yield of the target product approaches the maximum value with the progress of the unsaturated acid or unsaturated nitrile production reaction.
- propane or isobutane and air are used.
- the solid phase reaction of tungsten in the tungsten compound proceeds moderately, and the mixture catalyst is activated.
- the preferable conditions for activation are not particularly limited, but are preferably 350 to 550 ° C., more preferably 400 to 500 ° C. in a state where propane or isobutane and oxygen, or propane or isobutane, oxygen and ammonia are brought into contact with each other. Heat to.
- the activation treatment time is preferably 1 to 1500 hours, more preferably 5 to 750 hours, and further preferably 50 to 500 hours.
- the feedstock for propane or isobutane and ammonia need not be highly pure, and industrial grade gases can be used.
- the supply oxygen source air, air enriched with oxygen, or pure oxygen can be used.
- helium, argon, carbon dioxide gas, water vapor, nitrogen or the like may be supplied as a dilution gas.
- the gas phase catalytic oxidation reaction of propane or isobutane can be carried out under the following conditions.
- the molar ratio of oxygen supplied to the reaction to propane or isobutane is 0.1 to 6, preferably 0.5 to 4.
- the reaction temperature is 300 to 500 ° C, preferably 350 to 450 ° C.
- the reaction pressure is 5 ⁇ 10 4 to 5 ⁇ 10 5 Pa, preferably 1 ⁇ 10 5 to 3 ⁇ 10 5 Pa.
- the contact time is 0.1 to 10 (sec ⁇ g / cc), preferably 0.5 to 5 (sec ⁇ g / cc). In the present embodiment, the contact time is determined by the following equation.
- W filled catalyst amount (g)
- F Raw material mixed gas flow rate (Ncc / sec) in standard state (0 ° C., 1.013 ⁇ 10 5 Pa)
- T reaction temperature (° C.)
- the gas phase catalytic ammoxidation reaction of propane or isobutane can be carried out under the following conditions.
- the molar ratio of oxygen supplied to the reaction to propane or isobutane is 0.1 to 6, preferably 0.5 to 4.
- the molar ratio of ammonia fed to the reaction to propane or isobutane is 0.3 to 1.5, preferably 0.7 to 1.2.
- the reaction temperature is 350 to 500 ° C, preferably 380 to 470 ° C.
- the reaction pressure is 5 ⁇ 10 4 to 5 ⁇ 10 5 Pa, preferably 1 ⁇ 10 5 to 3 ⁇ 10 5 Pa.
- the contact time is 0.1 to 10 (sec ⁇ g / cc), preferably 0.5 to 5 (sec ⁇ g / cc).
- reaction method a conventional method such as a fixed bed, a fluidized bed, or a moving bed can be adopted, but a fluidized bed reactor in which reaction heat can be easily removed is preferable.
- the gas phase catalytic oxidation or ammoxidation reaction may be a single flow type or a recycle type.
- propane conversion and the acrylonitrile yield follow the following definitions, respectively.
- Propane conversion (%) (moles of propane reacted) / (moles of propane fed) ⁇ 100
- Acrylonitrile (AN) yield (%) (Mole number of acrylonitrile produced) / (Mole number of supplied propane) ⁇ 100
- niobium mixed solution was prepared by the following method. Niobic acid 0.765 kg containing 80.0% by mass as Nb 2 O 5 and oxalic acid dihydrate [H 2 C 2 O 4 .2H 2 O] 2.633 kg were mixed in 10 kg of water. The molar ratio of charged oxalic acid / niobium was 5.0, and the concentration of charged niobium was 0.50 (mol-Nb / kg-solution). This solution was heated and stirred at 95 ° C. for 2 hours to obtain a mixed solution in which niobium was dissolved.
- the mixture was allowed to stand and ice-cooled, and then the solid was separated by suction filtration to obtain a uniform niobium mixture.
- the molar ratio of oxalic acid / niobium in this niobium mixed solution was 2.71 according to the following analysis. 10 g of this niobium mixed solution was precisely weighed in a crucible, dried overnight at 95 ° C., and then heat treated at 600 ° C. for 1 hour to obtain 0.771 g of Nb 2 O 5 . From this result, the niobium concentration was 0.580 (mol-Nb / kg-solution).
- niobium mixed solution was used as a niobium mixed solution (B 0 ) for catalyst preparation described below.
- Aqueous raw material liquid (II) is prepared by adding 54.5 g of hydrogen peroxide containing 30 wt% as H 2 O 2 to 414.3 g of niobium mixed liquid (B 0 ) and stirring and mixing at room temperature for 10 minutes. did. After cooling the obtained aqueous raw material liquid (I) to 70 ° C., 760.3 g of silica sol containing 34.0 wt% as SiO 2 was added, and hydrogen peroxide 102 containing 30 wt% as H 2 O 2 was further added. .2 g was added and stirring was continued at 55 ° C. for 30 minutes.
- an aqueous raw material liquid (II), a dispersion in which 33.4 g of a 50 wt% ammonium metatungstate aqueous solution as WO 3 and 211.5 g of powdered silica are dispersed in 2.750 kg of water are sequentially added to the aqueous mixture.
- (III) was obtained.
- the aqueous mixed liquid (III) was aged at 50 ° C. for 2 hours and 30 minutes after the addition of the aqueous raw material liquid (II) to obtain a slurry.
- the obtained slurry was supplied to a centrifugal spray dryer and dried to obtain a fine spherical dry powder.
- the dryer inlet temperature was 210 ° C and the outlet temperature was 120 ° C.
- the composition of the composite oxide is Mo 1 V 0.21 Nb 0.10 Sb 0.24 W 0.03 Ce 0.005 O n
- Aqueous raw material liquid (II) is prepared by adding 56.7 g of hydrogen peroxide containing 30 wt% as H 2 O 2 to 430.8 g of niobium mixed liquid (B 0 ) and stirring and mixing at room temperature for 10 minutes. did. After cooling the obtained aqueous raw material liquid (I) to 70 ° C., 760.3 g of silica sol containing 34.0 wt% as SiO 2 was added, and hydrogen peroxide 102 containing 30 wt% as H 2 O 2 was further added. 0.0 g was added and stirring was continued at 55 ° C. for 30 minutes.
- an aqueous raw material liquid (II) and a dispersion obtained by dispersing 211.5 g of powdered silica in 2.750 kg of water were sequentially added to obtain an aqueous mixed liquid (III).
- the aqueous mixed liquid (III) was aged at 50 ° C. for 2 hours and 30 minutes after the addition of the aqueous raw material liquid (II) to obtain a slurry.
- the obtained slurry was supplied to a centrifugal spray dryer and dried to obtain a fine spherical dry powder.
- the dryer inlet temperature was 210 ° C and the outlet temperature was 120 ° C.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst.
- the propane conversion after 5 hours from the start of the mixed gas supply was 87.3%, and the AN yield was 52.2%. Thereafter, the reaction was continued under the same conditions.
- the propane conversion after 240 Hr after starting the supply of the mixed gas was 86.3%, and the AN yield was 51.8%.
- Example 3 (Production of mixture catalyst) An aqueous solution obtained by diluting 500 g of an aqueous ammonium metatungstate solution with 500 g of water was prepared, and the obtained aqueous solution was supplied to a centrifugal spray dryer and dried to obtain a fine spherical dry powder.
- the dryer inlet temperature was 210 ° C and the outlet temperature was 120 ° C.
- 100 g of the obtained tungsten-containing spray-dried product was fired at 500 ° C. for 2 hours in an air atmosphere to obtain a powdery tungsten compound.
- the tungsten compound was confirmed to be tungsten trioxide by X-ray diffraction measurement.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst. After 5 hours from the start of supplying the mixed gas, the propane conversion was 88.7% and the AN yield was 52.6%. Thereafter, the reaction was continued under the same conditions, and the propane conversion after 240 hours after starting the mixed gas supply was 89.2%, and the AN yield was 54.0%.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst.
- the propane conversion after 5 hours from the start of the mixed gas supply was 88.6%, and the AN yield was 52.5%. Thereafter, the reaction was continued under the same conditions.
- the propane conversion after 240 Hr after starting the supply of the mixed gas was 89.0%, and the AN yield was 53.6%.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst.
- the propane conversion after 5 hours from the start of the mixed gas supply was 88.6%, and the AN yield was 52.5%. Thereafter, the reaction was continued under the same conditions, and the propane conversion after 240 hours after starting the mixed gas supply was 87.6%, and the AN yield was 52.1%.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst. After 5 hours from the start of supplying the mixed gas, the propane conversion was 88.5% and the AN yield was 52.4%. Thereafter, the reaction was continued under the same conditions, and the propane conversion after 240 hours after starting the supply of the mixed gas was 86.3%, and the AN yield was 50.9%.
- Example 5 (Preparation of complex oxide) The composition formula Mo 1 V 0.21 Nb 0.10 Sb 0.24 W 0.12 Ce 0 was obtained in the same manner as in Example 1 except that the addition amount of the ammonium metatungstate aqueous solution was changed to 133.6 g. A composite oxide represented by 0.005 O n /47.0 wt% -SiO 2 was produced.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst. After 5 hours from the start of supplying the mixed gas, the propane conversion was 87.6% and the AN yield was 52.1%. Thereafter, the reaction was continued under the same conditions. The propane conversion after 240 Hr after starting the supply of the mixed gas was 87.7%, and the AN yield was 54.1%.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst.
- the propane conversion after 5 hours from the start of the mixed gas supply was 87.5%, and the AN yield was 52.0%. Thereafter, the reaction was continued under the same conditions.
- the propane conversion after 240 Hr after starting the supply of the mixed gas was 87.6%, and the AN yield was 53.6%.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst.
- the propane conversion after 5 hours from the start of the mixed gas supply was 88.3%, and the AN yield was 52.3%. Thereafter, the reaction was continued under the same conditions.
- the propane conversion after 240 Hr after starting the supply of the mixed gas was 88.9%, and the AN yield was 55.1%.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst. After 5 hours from the start of supplying the mixed gas, the propane conversion was 88.4% and the AN yield was 52.4%. Thereafter, the reaction was continued under the same conditions. The propane conversion after 240 Hr after starting the supply of the mixed gas was 89.2%, and the AN yield was 55.2%.
- Example 9 (Preparation of complex oxide) The composition formula Mo 1 V 0.21 Nb 0.10 Sb 0.24 W 0.03 O n / in the same manner as in Example 1 except that 5.22 g of cerium nitrate hexahydrate was not added. A composite oxide represented by 47.0 wt% -SiO 2 was produced. (Production of mixture catalyst) A mixed catalyst was produced in the same manner as in Example 7 using the obtained composite oxide.
- composition of the composite oxide be a Mo 1 V 0.21 Nb 0.10 Sb 0.24 W 0.03 O n
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst.
- the propane conversion after 5 hours from the start of the mixed gas supply was 85.8%, and the AN yield was 51.0%. Thereafter, the reaction was continued under the same conditions.
- the propane conversion after 240 Hr after starting the supply of the mixed gas was 86.3%, and the AN yield was 53.1%.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst.
- the propane conversion after 5 hours from the start of the mixed gas supply was 87.9%, and the AN yield was 52.4%. Thereafter, the reaction was continued under the same conditions.
- the propane conversion after 240 Hr after starting the supply of the mixed gas was 88.5%, and the AN yield was 54.4%.
- the ammoxidation reaction of propane was performed in the same manner as in Example 1 using the obtained mixture catalyst. After 5 hours from the start of supplying the mixed gas, the propane conversion was 87.7% and the AN yield was 52.4%. Thereafter, the reaction was continued under the same conditions. The propane conversion after 240 Hr after starting the supply of the mixed gas was 88.2%, and the AN yield was 54.3%.
- the mixture catalyst of the present invention can be usefully used in an industrial production process for producing a corresponding unsaturated acid or unsaturated nitrile by subjecting propane or isobutane to a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction.
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Abstract
Description
これまで、気相接触アンモ酸化に用いる触媒として、種々の酸化物触媒が提案されている。一般的にはモリブデン、バナジウム等を、必要に応じて混合、焼成して得られる酸化物をそのまま触媒として使用するが、不飽和カルボン酸又は不飽和ニトリルを製造するにあたり、焼成後の触媒にさらに後処理する手法も研究されてきた。
例えば特許文献1には、Mo-V-Sb/Te系触媒にタングステン、モリブデン、クロム、ジルコニウム、チタン、ニオブ、タンタル、バナジウム、硼素、ビスマス、テルル、パラジウム、コバルト、ニッケル、鉄、リン、ケイ素、希土類元素、アルカリ金属、アルカリ土類金属からなる群より選ばれる1つ以上の元素を含む溶液を含浸する手法が開示されている。
特許文献2には、混合金属酸化物触媒を水、及び任意に水性金属酸化物前駆体と接触させて修飾混合金属酸化物を製造し、得られた修飾混合金属酸化物を焼成する手法が開示されている。
特許文献3には、Mo-V-Sb-Nb系触媒にタングステン、マンガンを浸漬する手法が開示されている。
特許文献4には、触媒にアンチモン化合物、モリブデン化合物、テルル化合物、タングステン化合物等の修飾剤を混合して反応に供するか、触媒や触媒前駆体に修飾剤を混合して焼成した後に反応に供する手法が開示されている。
特許文献1~4に記載された製造方法では、そのままでも活性を有するMo-V-Te/Sb系複合酸化物に、タングステンを含浸又は浸漬することで性能が向上することが記載されている。しかしながら、含浸又は浸漬の前の複合酸化物がタングステンを含有しておらず、目的物の収率が高い触媒を得ることには至っていない。
上記事情に鑑み、本発明が解決しようとする課題は、プロパン若しくはイソブタンの気相接触酸化又は気相接触アンモ酸化反応用の触媒であって、プロパン若しくはイソブタンから対応する不飽和酸又は不飽和ニトリルを高収率で得ることのできる混合物触媒を提供すること、及びその混合物触媒を用いた不飽和酸又は不飽和ニトリルの製造方法を提供することである。
プロパン若しくはイソブタンの気相接触酸化反応又は気相接触アンモ酸化反応用の混合物触媒であって、
下記組成式(1)で表される複合酸化物と、タングステン化合物と、を下記式(2)の割合で含有した混合物触媒;
Mo1VaNbbSbcWdZeOn (1)
(式(1)中、ZはLa、Ce、Pr、Yb、Y、Sc、Sr、Baからなる群から選ばれる少なくとも1種以上の元素、a、b、c、d、e、nはMo1原子当たりの各元素の原子比を示し、aは0.01≦a≦1、bは0.01≦b≦1、cは0.01≦c≦1、dは0.001≦d≦1、eは0≦e≦1であり、nは構成金属の原子価によって決まる数を示す。)
0.001<w<0.3 (2)
(式(2)中、wはタングステン化合物中のタングステンの原子比を、複合酸化物中のMo1原子当たりの原子比として表したものである。)。
[2]
前記タングステン化合物が、酸化タングステンを含む、上記[1]記載の混合物触媒。
[3]
流動床反応に用いられる、上記[1]又は[2]記載の混合物触媒。
[4]
不飽和酸又は不飽和ニトリルの製造方法であって、
上記[1]~[3]のいずれか記載の混合物触媒に、プロパン若しくはイソブタンと酸素を、又は、プロパン若しくはイソブタンと酸素とアンモニアを、接触させる工程を含む製造方法。
[5]
前記接触させる工程の温度を400℃以上にする、上記[4]記載の製造方法。
プロパン若しくはイソブタンの気相接触酸化反応又は気相接触アンモ酸化反応用の混合物触媒であって、
下記組成式(1)で表される複合酸化物と、タングステン化合物と、を下記式(2)の割合で含有した混合物触媒である;
Mo1VaNbbSbcWdZeOn (1)
(式(1)中、ZはLa、Ce、Pr、Yb、Y、Sc、Sr、Baからなる群から選ばれる少なくとも1種以上の元素、a、b、c、d、e、nはMo1原子当たりの各元素の原子比を示し、aは0.01≦a≦1、bは0.01≦b≦1、cは0.01≦c≦1、dは0.001≦d≦1、eは0≦e≦1であり、nは構成金属の原子価によって決まる数を示す。)
0.001<w<0.3 (2)
(式(2)中、wはタングステン化合物中のタングステンの原子比を、複合酸化物中のMo1原子当たりの原子比として表したものである。)。
本実施形態の混合物触媒に含まれる複合酸化物は、例えば、以下の方法により製造することができる。
(a)複合酸化物の製造
複合酸化物は、次の3つの工程により製造される。
(1)原料を調合して原料調合液を得る工程
(2)工程(1)で得られた原料調合液を乾燥し、乾燥粉体を得る工程
(3)工程(2)で得られた乾燥粉体を焼成し、複合酸化物を得る工程
MoとVの原料としては、特に限定されないが、それぞれ、ヘプタモリブデン酸アンモニウム[(NH4)6Mo7O24・4H2O]とメタバナジン酸アンモニウム[NH4VO3]を好適に用いることができる。
(工程(1):原料を調合する工程)
工程(1)においては、Mo化合物、V化合物、Sb化合物、W化合物、成分Z化合物、必要によりその他原料となる成分を水に添加し、加熱して水性混合液(I)を調製する。この時、混合液(I)を調製する容器内は窒素雰囲気でもよい。次に、Nb化合物とジカルボン酸を水中で加熱撹拌して混合液(B0)を調製する。更に、混合液(B0)に、過酸化水素を添加し、水性混合液(II)を調製する。この時、H2O2/Nb(モル比)は0.5~20であることが好ましく、1~10であることがより好ましい。
熟成時間は、目的物の収率の観点から、90分以上50時間以内が好ましく、90分以上6時間以内がより好ましい。
熟成温度は、Mo成分の縮合やVの析出を防ぐ観点から、25℃以上が好ましい。また、Nbと過酸化水素を含む錯体の加水分解が起こりすぎないようにし、好ましい形態のスラリーを形成する観点から、65℃以下が好ましい。従って、熟成温度は、25℃以上65℃以下が好ましく、30℃以上60℃以下がより好ましい。
工程(2)においては、原料調合工程で得られたスラリーを乾燥することによって、乾燥粉体を得る。乾燥は公知の方法で行うことができ、例えば、噴霧乾燥又は蒸発乾固によって行うことができ、中でも、噴霧乾燥により微小球状の乾燥粉体を得ることが好ましい。噴霧乾燥法における噴霧化は、遠心方式、二流体ノズル方式、又は高圧ノズル方式によって行うことができる。乾燥熱源としては、スチーム、電気ヒーター等によって加熱された空気を用いることができる。噴霧乾燥装置の乾燥機入口温度は150~300℃が好ましく、乾燥機出口温度は100~160℃が好ましい。
工程(3)においては、乾燥工程で得られた乾燥粉体を焼成に供することによって複合酸化物を得る。焼成装置としては、例えば、回転炉(ロータリーキルン)を使用することができる。焼成器の形状としては特に限定されないが、管状であると、連続的な焼成を実施することができるため好ましい。焼成管の形状としては特に限定されないが、円筒状であるのが好ましい。
本実施形態における複合酸化物は、そのままでも触媒活性を有するものであるが、タングステン化合物を複合酸化物と特定の割合で含有する混合物触媒にすることで、目的物の収率が向上する。
タングステン源としては、例えば、タングステンのアンモニウム塩、硝酸塩、カルボン酸塩、カルボン酸アンモニウム塩、ペルオキソカルボン酸塩、ペルオキソカルボン酸アンモニウム塩、ハロゲン化アンモニウム塩、ハロゲン化物、アセチルアセトナート、アルコキシド、トリフェニル化合物、ポリオキソメタレート、ポリオキソメタレートアンモニウム塩;酸化タングステン、タングステン酸、パラタングステン酸アンモニウム、ケイタングステン酸、ケイタングストモリブデン酸、ケイバナドタングステン酸等の粉末原料;メタタングステン酸アンモニウム水溶液や酸化タングステンゾル等の液状原料が挙げられる。
(b-2)物理混合方法
複合酸化物とタングステン源との物理混合方法としては特に限定されないが、例えば、反応器に触媒を供給するホッパー中に複合酸化物を加えてタングステン源を適量添加する方法が挙げられる。複合酸化物とタングステン源をホッパーに入れる前に、予め両者を混合しておいてもよいが、予め混合しなくてもホッパーから反応器に触媒を供給する工程で自然に混ざりあうので、予め混合しておくことは必須ではない。複合酸化物とタングステン源をホッパーに入れる順序も特に限定されず、両者の粒径等の観点から反応器中で十分に接触した状態になるように適宜決めればよい。必要に応じて、空気や窒素を流通させて混合することも可能である。流動床反応の場合、ホッパーから一度に供給するのでなく、複合酸化物とタングステン源を反応器内に順に供給してもよい。この場合、反応進行中に複合酸化物とタングステン源が反応器内で流動しながら混合される。
(b-3-i)液相工程
本実施形態においては、複合酸化物にタングステン源を溶解した溶液を滴下する方法を含浸と呼ぶ。一方、タングステン源を溶解した溶液に複合酸化物を添加し、攪拌等により一定時間接触させる方法を浸漬と呼ぶ。いずれの場合も、不要な溶液はろ過又は蒸発させることにより除去することができる。蒸発は、30~300℃程度、好ましくは40~250℃で実施する。その後、必要に応じて、焼成処理を施し、タングステン源の一部又は全量を酸化物にすることもできる。複合酸化物の細孔内には空気、不活性ガス等、複合酸化物が接触処理前に存在していた雰囲気ガスが充満されており、細孔内部へのタングステンの拡散が阻害される可能性がある。その場合は、含浸、浸漬をする前、若しくは含浸、浸漬をしている間、減圧雰囲気下にして、細孔内のガスを除去することもできる。
液相でイオン交換が生じていない場合も、焼成工程で交換反応が生じてタングステン源が複合酸化物の一部になってしまう場合がありうる。この交換反応も液相処理と同様に、表面改質が進行して混合物でない状態になっていると予想される。交換反応の生じ易さは主として焼成温度に依存し、焼成温度が高すぎると交換反応が進行し易い。交換反応が生じ難い焼成温度としては、好ましくは200~400℃、より好ましくは250~350℃である。焼成処理を経た混合物触媒に含まれるタングステン化合物は、一般的にはタングステン源とは異なる構造を有するが、液相処理後のものと同様に、複合酸化物の一部でないタングステン化合物を含有する限り、本実施形態における混合物触媒の範疇である。
本実施形態における混合物触媒は、
プロパン若しくはイソブタンの気相接触酸化反応又は気相接触アンモ酸化反応用の混合物触媒であって、
下記組成式(1)で表される複合酸化物と、タングステン化合物と、を下記式(2)の割合で含有した混合物触媒;
Mo1VaNbbSbcWdZeOn (1)
(式(1)中、ZはLa、Ce、Pr、Yb、Y、Sc、Sr、Baからなる群から選ばれる少なくとも1種以上の元素、a、b、c、d、e、nはMo1原子当たりの各元素の原子比を示し、aは0.01≦a≦1、bは0.01≦b≦1、cは0.01≦c≦1、dは0.001≦d≦1、eは0≦e≦1であり、nは構成金属の原子価によって決まる数を示す。)
0.001<w<0.3 (2)
(式(2)中、wはタングステン化合物中のタングステンの原子比を、複合酸化物中のMo1原子当たりの原子比として表したものである。)。
Mo1VaNbbSbcWdZeOn (1)
(式(1)中、Zは、La、Ce、Pr、Yb、Y、Sc、Sr、Baからなる群から選ばれる少なくとも1種以上の元素、a、b、c、d、e、nはMo1原子当たりの各元素の原子比を示し、aは0.01≦a≦1、bは0.01≦b≦1、cは0.01≦c≦1、dは0.001≦d≦1、eは0≦e≦1であり、nは構成金属の原子価によって決まる数を示す。)
0.001<w<0.3 (2)
式(2)中、wはタングステン化合物中のタングステンの原子比を、複合酸化物中のMo1原子当たりの原子比として表したものである。
wを定量するには、蛍光X線分析により、混合物触媒の組成と複合酸化物の組成を測定し、次の式から算出する。
w=(混合物触媒中のW組成比)-(複合酸化物中のW組成比)
なお、本焼成後、複合酸化物粒子の表面に低融点の化合物が突起状に結晶化する場合がある。その結晶を触媒同士の接触等によって触媒表面から除去した場合であっても、wにほとんど影響を与えない。そのため、組成分析によるwの定量は、酸化物の結晶除去前後のいずれの段階でもよい。
本実施形態における混合物触媒の存在下、プロパン若しくはイソブタンを気相接触酸化又は気相接触アンモ酸化反応させて、対応する不飽和酸又は不飽和ニトリルを製造することができる。
即ち、本実施形態における不飽和酸又は不飽和ニトリルの製造方法は、
上述した混合物触媒に、プロパン若しくはイソブタンと酸素を、又は、プロパン若しくはイソブタンと酸素とアンモニアを、接触させる工程を含む製造方法である。
供給酸素源としては、空気、酸素を富化した空気又は純酸素を用いることができる。更に、希釈ガスとしてヘリウム、アルゴン、炭酸ガス、水蒸気、窒素等を供給してもよい。
反応に供給する酸素のプロパン若しくはイソブタンに対するモル比は0.1~6、好ましくは0.5~4である。
反応温度は300~500℃、好ましくは350~450℃である。
反応圧力は5×104~5×105Pa、好ましくは1×105~3×105Paである。
接触時間は0.1~10(sec・g/cc)、好ましくは0.5~5(sec・g/cc)である。本実施形態において、接触時間は次式で決定される。
接触時間(sec・g/cc)=(W/F)×273/(273+T)
ここで、W、F及びTは次のように定義される。
W=充填触媒量(g)
F=標準状態(0℃、1.013×105Pa)での原料混合ガス流量(Ncc/sec)
T=反応温度(℃)
反応に供給する酸素のプロパン若しくはイソブタンに対するモル比は0.1~6、好ましくは0.5~4である。
反応に供給するアンモニアのプロパン若しくはイソブタンに対するモル比は0.3~1.5、好ましくは0.7~1.2である。
反応温度は350~500℃、好ましくは380~470℃である。
反応圧力は5×104~5×105Pa、好ましくは1×105~3×105Paである。
接触時間は0.1~10(sec・g/cc)、好ましくは0.5~5(sec・g/cc)である。
実施例と比較例においては、プロパン転化率、アクリロニトリル収率は、それぞれ次の定義に従う。
プロパン転化率(%)=(反応したプロパンのモル数)/(供給したプロパンのモル数)×100
アクリロニトリル(AN)収率(%)=(生成したアクリロニトリルのモル数)/(供給したプロパンのモル数)×100
以下の方法でニオブ混合液を調製した。
水10kgにNb2O5として80.0質量%を含有するニオブ酸0.765kgとシュウ酸二水和物〔H2C2O4・2H2O〕2.633kgを混合した。仕込みのシュウ酸/ニオブのモル比は5.0、仕込みのニオブ濃度は0.50(mol-Nb/kg-液)であった。この液を95℃で2時間加熱撹拌することによって、ニオブが溶解した混合液を得た。この混合液を静置、氷冷後、固体を吸引濾過によって濾別し、均一なニオブ混合液を得た。このニオブ混合液のシュウ酸/ニオブのモル比は下記の分析により2.71であった。
るつぼにこのニオブ混合液10gを精秤し、95℃で一夜乾燥後、600℃で1時間熱処理し、Nb2O50.771gを得た。この結果から、ニオブ濃度は0.580(mol-Nb/kg-液)であった。
300mLのガラスビーカーにこのニオブ混合液3gを精秤し、約80℃の熱水200mLを加え、続いて1:1硫酸10mLを加えた。得られた混合液をホットスターラー上で液温70℃に保ちながら、攪拌下、1/4規定KMnO4を用いて滴定した。KMnO4によるかすかな淡桃色が約30秒以上続く点を終点とした。シュウ酸の濃度は、滴定量から次式に従って計算した結果、1.570(mol-シュウ酸/kg)であった。
2KMnO4+3H2SO4+5H2C2O4→K2SO4+2MnSO4+10CO2+8H2O
得られたニオブ混合液は、下記の触媒調製のニオブ混合液(B0)として用いた。
(複合酸化物の調製)
仕込み組成式がMo1V0.21Nb0.10Sb0.24W0.03Ce0.005On/47.0wt%-SiO2で示される複合酸化物を次のようにして製造した。
水1.902kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を424.3g、メタバナジン酸アンモニウム〔NH4VO3〕を59.0g、硝酸セリウム6水和物5.22g及び三酸化二アンチモン〔Sb2O3〕を87.6g加え、攪拌しながら95℃で1時間加熱して水性原料液(I)を得た。
ニオブ混合液(B0)414.3gに、H2O2として30wt%を含有する過酸化水素水を54.5g添加し、室温で10分間攪拌混合して、水性原料液(II)を調製した。
得られた水性原料液(I)を70℃に冷却した後にSiO2として34.0wt%を含有するシリカゾル760.3gを添加し、更に、H2O2として30wt%含有する過酸化水素水102.2gを添加し、55℃で30分間撹拌を続けた。次に、水性原料液(II)、WO3として50wt%のメタタングステン酸アンモニウム水溶液33.4g、粉体シリカ211.5gを水2.750kgに分散させた分散液を順次添加して水性混合液(III)を得た。水性混合液(III)は水性原料液(II)を添加後から2時間30分、50℃で熟成し、スラリーを得た。
得られたスラリーを、遠心式噴霧乾燥器に供給して乾燥し、微小球状の乾燥粉体を得た。乾燥機の入口温度は210℃、そして出口温度は120℃であった。
得られた乾燥粉体800gを直径3インチのSUS製焼成管に充填し、8.0NL/minの窒素ガス流通下、管を回転させながら、680℃で2時間焼成して複合酸化物を得た。
メタタングステン酸アンモニウム水溶液46.2gを水453.8gで希釈した水溶液(Wとして濃度0.7mol/kg)に得られた複合酸化物100gを攪拌しながら添加・混合した。得られた混合液をアスピレーター容器内に移動し、100kPaで10分間減圧処理した。その後、アスピレーター内の混合液を濾過し、乾燥器内で50℃12Hr乾燥処理し、タングステン化合物との混合物を得た。得られた複合酸化物と混合物触媒に対して組成分析を行った。組成分析には蛍光X線分析装置(理学電器製、RIX1000)を使用した。
複合酸化物の組成は、Mo1V0.21Nb0.10Sb0.24W0.03Ce0.005Onであり、混合物触媒の組成は、Mo1V0.21Nb0.10Sb0.24W0.10Ce0.005Onであった。両者のW組成比の差から、w=0.07であることを確認した。
得られた混合物触媒35gを内径25mmのバイコールガラス流動床型反応管に充填し、反応温度445℃、反応圧力0.05Mpa下にプロパン:アンモニア:酸素:ヘリウム=1:1:3:18のモル比の混合ガスを接触時間3.4(sec・g/cc)で供給した。混合ガス供給開始後、5時間後のプロパン転化率は88.3%、AN収率は52.4%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は88.8%、AN収率は54.4%であった。
(混合物触媒の製造)
実施例1で得られた複合酸化物を用いて、混合物触媒の製造を行った。希釈後のタングステン酸アンモニウム水溶液濃度をWとして1.5mol/kgに変更したこと以外は、実施例1と同様に行った。
得られた混合物触媒の組成を実施例1と同様に測定した結果、Mo1V0.21Nb0.10Sb0.24W0.18Ce0.005Onであり、w=0.15であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は88.2%、AN収率は52.3%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は88.6%、AN収率は53.8%であった。
(複合酸化物の調製)
仕込み組成式がMo1V0.21Nb0.10Sb0.24Ce0.005On/47.0wt%-SiO2で示される複合酸化物を次のようにして製造した。
水1.964kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を441.1g、メタバナジン酸アンモニウム〔NH4VO3〕を61.4g、硝酸セリウム6水和物5.42g及び三酸化二アンチモン〔Sb2O3〕を87.4g加え、攪拌しながら95℃で1時間加熱して水性原料液(I)を得た。
ニオブ混合液(B0)430.8gに、H2O2として30wt%を含有する過酸化水素水を56.7g添加し、室温で10分間攪拌混合して、水性原料液(II)を調製した。
得られた水性原料液(I)を70℃に冷却した後にSiO2として34.0wt%を含有するシリカゾル760.3gを添加し、更に、H2O2として30wt%含有する過酸化水素水102.0gを添加し、55℃で30分間撹拌を続けた。次に、水性原料液(II)、粉体シリカ211.5gを水2.750kgに分散させた分散液を順次添加して水性混合液(III)を得た。水性混合液(III)は、水性原料液(II)を添加後から2時間30分、50℃で熟成し、スラリーを得た。
得られたスラリーを、遠心式噴霧乾燥器に供給して乾燥し、微小球状の乾燥粉体を得た。乾燥機の入口温度は210℃、そして出口温度は120℃であった。
得られた乾燥粉体800gを直径3インチのSUS製焼成管に充填し、8.0NL/minの窒素ガス流通下、管を回転させながら、680℃で2時間焼成して複合酸化物を得た。
WO3として50.0wt%含有するメタタングステン酸アンモニウム水溶液231.0gを水453.8gで希釈した水溶液(Wとして濃度1.0mol/kg)に得られた複合酸化物100gを攪拌しながら添加・混合した。得られた混合液をアスピレーター容器内に移動し、100kPaで10分間減圧処理した。その後、アスピレーター内の混合液を濾過し、乾燥器内で50℃12Hr乾燥処理し、タングステン化合物との混合物を得た。得られた複合酸化物と混合物触媒に対して組成分析を行った。組成分析には蛍光X線分析装置(理学電器製、RIX1000)を使用した。
得られた複合酸化物の組成は、Mo1V0.21Nb0.10Sb0.24Ce0.005Onであり、混合物触媒の組成は、Mo1V0.21Nb0.10Sb0.24W0.10Ce0.005Onであった。両者のW組成比の差から、w=0.10であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は87.3%、AN収率は52.2%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は86.3%、AN収率は51.8%であった。
(混合物触媒の製造)
希釈後のタングステン酸アンモニウム水溶液濃度をWとして1.5mol/kgに変更したこと以外は、比較例1と同様に混合物触媒の製造を行った。
得られた混合物触媒の組成を比較例1と同様に測定した結果、Mo1V0.21Nb0.10Sb0.24W0.15Ce0.005Onであり、w=0.15であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は86.9%、AN収率は51.8%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は85.2%、AN収率は50.3%であった。
(混合物触媒の製造)
メタタングステン酸アンモニウム水溶液500gを水500gで希釈した水溶液を調製し、得られた水溶液を遠心式噴霧乾燥器に供給して乾燥し、微小球状の乾燥粉体を得た。乾燥機の入口温度は210℃、そして出口温度は120℃であった。得られたタングステン含有噴霧乾燥品100gを空気雰囲気下500℃で2時間焼成し、粉状のタングステン化合物を得た。タングステン化合物はX線回折測定により、三酸化タングステンであることを確認した。
実施例1で得られた複合酸化物100gと得られたタングステン化合物3.37gを粉のまま混合し、混合物触媒を得た。得られた混合物触媒に対して組成分析を行った。組成分析には蛍光X線分析装置(理学電器製、RIX1000)を使用した。
得られた混合物触媒の組成は、Mo1V0.21Nb0.10Sb0.24W0.09Ce0.005Onであり、w=0.06であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は88.7%、AN収率は52.6%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は89.2%、AN収率は54.0%であった。
(混合物触媒の製造)
混合するタングステン化合物の質量を10.1gに変更したこと以外は、実施例3と同様にして混合物触媒を得た。得られた混合物触媒に対して実施例1と同様に組成分析を行った。組成分析には蛍光X線分析装置(理学電器製、RIX1000)を使用した。
得られた混合物触媒の組成は、Mo1V0.21Nb0.10Sb0.24W0.18Ce0.005Onであり、w=0.15であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は88.6%、AN収率は52.5%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は89.0%、AN収率は53.6%であった。
(混合物触媒の製造)
比較例1で得られた複合酸化物を用い、混合するタングステン化合物の質量を6.74gに変更したこと以外は、実施例3と同様にして混合物触媒の製造を行った。
得られた混合物触媒の組成を実施例1と同様に測定した結果、Mo1V0.21Nb0.10Sb0.24W0.10Ce0.005Onであり、w=0.10であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は88.6%、AN収率は52.5%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は87.6%、AN収率は52.1%であった。
(混合物触媒の製造)
比較例1で得られた複合酸化物を用い、混合するタングステン化合物の質量を10.1gに変更したこと以外は、実施例3と同様にして混合物触媒の調製を行った。
得られた混合物触媒の組成を実施例1と同様に測定した結果、Mo1V0.21Nb0.10Sb0.24W0.15Ce0.005Onであり、w=0.15であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は88.5%、AN収率は52.4%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は86.3%、AN収率は50.9%であった。
(プロパンのアンモ酸化反応)
混合物触媒を製造することなく実施例1で得られた複合酸化物をそのまま用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は88.4%、AN収率は52.2%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は88.3%、AN収率は52.1%であった。
(複合酸化物の調製)
メタタングステン酸アンモニウム水溶液の添加量を133.6gに変更したこと以外は、実施例1と同様の方法により仕込み組成式Mo1V0.21Nb0.10Sb0.24W0.12Ce0.005On/47.0wt%-SiO2で示される複合酸化物を製造した。
得られた複合酸化物を用いて、実施例1と同様にして混合物触媒の製造を行った。実施例1と同様の方法で複合酸化物及び混合物触媒の組成を測定した結果、複合酸化物の組成は、Mo1V0.21Nb0.10Sb0.24W0.12Ce0.005Onであり、混合物触媒の組成は、Mo1V0.21Nb0.10Sb0.24W0.19Ce0.005Onであった。両者のW組成比から、w=0.07であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は87.6%、AN収率は52.1%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は87.7%、AN収率は54.1%であった。
実施例5で得られた複合酸化物を用いて、実施例2と同様にして混合物触媒の製造を行った。
得られた混合物触媒の組成を実施例1と同様に測定した結果、Mo1V0.21Nb0.10Sb0.24W0.27Ce0.005Onであり、w=0.15であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は87.5%、AN収率は52.0%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は87.6%、AN収率は53.6%であった。
(混合物触媒の製造)
実施例1で得られた複合酸化物を用いて、混合物触媒の製造を行った。希釈後のタングステン酸アンモニウム水溶液濃度をWとして0.2mol/kgに変更したこと以外は、実施例1と同様に行った。
得られた混合物触媒の組成を実施例1と同様に測定した結果、Mo1V0.21Nb0.10Sb0.24W0.05Ce0.005Onであり、w=0.02であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は88.3%、AN収率は52.3%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は88.9%、AN収率は55.1%であった。
(混合物触媒の製造)
実施例1で得られた複合酸化物を用いて、混合物触媒の製造を行った。希釈後のタングステン酸アンモニウム水溶液濃度をWとして0.3mol/kgに変更したこと以外は、実施例1と同様に行った。
得られた混合物触媒の組成を実施例1と同様に測定した結果、Mo1V0.21Nb0.10Sb0.24W0.06Ce0.005Onであり、w=0.03であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は88.4%、AN収率は52.4%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は89.2%、AN収率は55.2%であった。
(混合物触媒の製造)
比較例1で得られた複合酸化物を用いて、混合物触媒の製造を行った。希釈後のタングステン酸アンモニウム水溶液濃度をWとして0.05mol/kgに変更したこと以外は、比較例1と同様に行った。
得られた混合物触媒の組成を比較例1と同様に測定した結果、Mo1V0.21Nb0.10Sb0.24W0.005Ce0.005Onであり、w=0.005であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は88.3%、AN収率は52.1%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は88.2%、AN収率は52.0%であった。
[比較例7]
(混合物触媒の製造)
実施例1で得られた複合酸化物を用いて、混合物触媒の製造を行った。混合するタングステン化合物の質量を44.9gに変更したこと以外は、実施例3と同様にして混合物触媒を得た。
得られた混合物触媒の組成を実施例1と同様に測定した結果、Mo1V0.21Nb0.10Sb0.24W0.43Ce0.005Onであり、w=0.40であることを確認した。
(プロパンのアンモ酸化反応)
得られた混合物触媒を使用して、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は86.2%、AN収率は51.9%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は83.5%、AN収率は49.3%であった。
(複合酸化物の調製)
硝酸セリウム6水和物5.22gを添加しなかったこと以外は、実施例1と同様の方法により仕込み組成式Mo1V0.21Nb0.10Sb0.24W0.03On/47.0wt%-SiO2で示される複合酸化物を製造した。
(混合物触媒の製造)
得られた複合酸化物を用いて、実施例7と同様にして混合物触媒の製造を行った。実施例1と同様の方法で複合酸化物及び混合物触媒の組成を測定した結果、複合酸化物の組成は、Mo1V0.21Nb0.10Sb0.24W0.03Onであり、混合物触媒の組成は、Mo1V0.21Nb0.10Sb0.24W0.05Onであった。両者のW組成比から、w=0.02であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は85.8%、AN収率は51.0%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は86.3%、AN収率は53.1%であった。
(複合酸化物の調製)
硝酸セリウム6水和物5.22gの代わりに硝酸ランタン6水和物5.21gを添加したこと以外は、実施例1と同様の方法により仕込み組成式Mo1V0.21Nb0.10Sb0.24W0.03La0.005On/47.0wt%-SiO2で示される複合酸化物を製造した。
(混合物触媒の製造)
得られた複合酸化物を用いて、実施例7と同様にして混合物触媒の製造を行った。実施例1と同様の方法で複合酸化物及び混合物触媒の組成を測定した結果、複合酸化物の組成は、Mo1V0.21Nb0.10Sb0.24W0.03La0.005Onであり、混合物触媒の組成は、Mo1V0.21Nb0.10Sb0.24W0.05La0.005Onであった。両者のW組成比から、w=0.02であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は87.6%、AN収率は51.8%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は87.9%、AN収率は53.6%であった。
(複合酸化物の調製)
硝酸セリウム6水和物5.22gの代わりに硝酸プラセオジム6水和物5.23gを添加したこと以外は、実施例1と同様の方法により仕込み組成式Mo1V0.21Nb0.10Sb0.24W0.03Pr0.005On/47.0wt%-SiO2で示される複合酸化物を製造した。
(混合物触媒の製造)
得られた複合酸化物を用いて、実施例7と同様にして混合物触媒の製造を行った。実施例1と同様の方法で複合酸化物及び混合物触媒の組成を測定した結果、複合酸化物の組成は、Mo1V0.21Nb0.10Sb0.24W0.03Pr0.005Onであり、混合物触媒の組成は、Mo1V0.21Nb0.10Sb0.24W0.05Pr0.005Onであった。両者のW組成比から、w=0.02であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は87.9%、AN収率は52.4%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は88.5%、AN収率は54.4%であった。
(複合酸化物の調製)
硝酸セリウム6水和物5.22gの代わりに硝酸イッテルビウム3水和物4.97gを添加したこと以外は、実施例1と同様の方法により仕込み組成式Mo1V0.21Nb0.10Sb0.24W0.03Yb0.005On/47.0wt%-SiO2で示される複合酸化物を製造した。
(混合物触媒の製造)
得られた複合酸化物を用いて、実施例7と同様にして混合物触媒の製造を行った。実施例1と同様の方法で複合酸化物及び混合物触媒の組成を測定した結果、複合酸化物の組成は、Mo1V0.21Nb0.10Sb0.24W0.03Yb0.005Onであり、混合物触媒の組成は、Mo1V0.21Nb0.10Sb0.24W0.05Yb0.005Onであった。両者のW組成比から、w=0.02であることを確認した。
得られた混合物触媒を用いて、プロパンのアンモ酸化反応を実施例1と同様に行った。混合ガス供給開始後、5時間後のプロパン転化率は87.7%、AN収率は52.4%であった。
その後、同条件で反応を継続し、混合ガス供給開始後240Hr後のプロパン転化率は88.2%、AN収率は54.3%であった。
Claims (5)
- プロパン若しくはイソブタンの気相接触酸化反応又は気相接触アンモ酸化反応用の混合物触媒であって、
下記組成式(1)で表される複合酸化物と、タングステン化合物と、を下記式(2)の割合で含有した混合物触媒;
Mo1VaNbbSbcWdZeOn (1)
(式(1)中、ZはLa、Ce、Pr、Yb、Y、Sc、Sr、Baからなる群から選ばれる少なくとも1種以上の元素、a、b、c、d、e、nはMo1原子当たりの各元素の原子比を示し、aは0.01≦a≦1、bは0.01≦b≦1、cは0.01≦c≦1、dは0.001≦d≦1、eは0≦e≦1であり、nは構成金属の原子価によって決まる数を示す。)
0.001<w<0.3 (2)
(式(2)中、wはタングステン化合物中のタングステンの原子比を、複合酸化物中のMo1原子当たりの原子比として表したものである。)。 - 前記タングステン化合物が、酸化タングステンを含む、請求項1記載の混合物触媒。
- 流動床反応に用いられる、請求項1又は2記載の混合物触媒。
- 不飽和酸又は不飽和ニトリルの製造方法であって、
請求項1~3のいずれか1項記載の混合物触媒に、プロパン若しくはイソブタンと酸素を、又は、プロパン若しくはイソブタンと酸素とアンモニアを、接触させる工程を含む製造方法。 - 前記接触させる工程の温度を400℃以上にする、請求項4記載の製造方法。
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