WO2009081758A1 - 酸化物触媒の製造方法 - Google Patents
酸化物触媒の製造方法 Download PDFInfo
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- WO2009081758A1 WO2009081758A1 PCT/JP2008/072563 JP2008072563W WO2009081758A1 WO 2009081758 A1 WO2009081758 A1 WO 2009081758A1 JP 2008072563 W JP2008072563 W JP 2008072563W WO 2009081758 A1 WO2009081758 A1 WO 2009081758A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- oxide catalyst
- firing
- mass
- particles
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 224
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 216
- 238000010304 firing Methods 0.000 claims abstract description 113
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 239000001294 propane Substances 0.000 claims abstract description 54
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 52
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- 239000011261 inert gas Substances 0.000 claims abstract description 25
- 239000001282 iso-butane Substances 0.000 claims abstract description 21
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 113
- 239000002994 raw material Substances 0.000 claims description 101
- 239000012018 catalyst precursor Substances 0.000 claims description 81
- 238000001354 calcination Methods 0.000 claims description 66
- 238000004519 manufacturing process Methods 0.000 claims description 54
- 239000007789 gas Substances 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 25
- 238000001694 spray drying Methods 0.000 claims description 19
- 239000000470 constituent Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 100
- 239000000463 material Substances 0.000 abstract description 13
- 239000012808 vapor phase Substances 0.000 abstract 4
- 239000000843 powder Substances 0.000 description 91
- 230000009467 reduction Effects 0.000 description 67
- 239000010955 niobium Substances 0.000 description 64
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 50
- 238000002360 preparation method Methods 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 32
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 32
- 239000012071 phase Substances 0.000 description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- 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 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 229910021485 fumed silica Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000001133 acceleration Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000002822 niobium compounds Chemical class 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000007792 gaseous phase Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 150000002821 niobium Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- -1 inorganic acid salt Chemical class 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910018380 Mn(NO3)2.6H2 O Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 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
- 229940039748 oxalate Drugs 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
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-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
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/28—Molybdenum
-
- 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
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a method for producing an oxide catalyst used for gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane.
- Patent Document 1 describes a catalyst used in a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction of propane or isobutane, which has a specific reduction rate and specific surface area. It is described that the catalyst having this specific reduction rate and specific surface area shows moderate activity, good reaction results (selectivity and yield of the desired product), and little decrease in yield over time. Yes.
- a reaction method used for gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction heat removal from the reaction heat is easy and the temperature of the catalyst layer can be kept almost uniform, the catalyst is extracted from the reactor during operation, The fluidized bed reaction is preferred because it is easy to add.
- a catalyst used in the fluidized bed reaction a catalyst having a particle diameter adjusted to a certain range is disclosed in order to reduce the catalyst lost due to scattering during the reaction or to improve fluidity.
- Patent Document 2 discloses an example of an ammoxidation reaction using propylene or isobutylene as a raw material as an example focusing on the fluidity of a catalyst.
- the particle content in the range of 5 to 150 ⁇ m is 95% by mass or more and the particle content in the range of 20 to 30 ⁇ m is 3 to 30% by mass, It has been disclosed that a high nitrile yield can be obtained and that catalyst loss can be reduced.
- Patent Document 3 in the gas phase oxidation reaction in which the molybdenum compound released from the metal oxide catalyst is precipitated as needle-like crystals on the reactor surface, the proportion of catalyst particles having a particle size of 20 ⁇ m or less is 2% by weight or less.
- Patent Documents 4 and 5 dry particles obtained by spray drying are subjected to a classification operation to separate dry particles outside the desired particle diameter range, and the separated dry particles are pulverized to form a slurry before spray drying. A method of mixing and reusing is disclosed.
- the present inventor manufactured an oxide catalyst adjusted to a particle size within the range described in Patent Documents 2 to 5 in order to industrially carry out the gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane. did.
- the effects of improving fluidity in the fluidized bed reactor, preventing fouling in the reaction apparatus, and reducing catalyst loss described in this document are somewhat observed, the essential catalyst performance is completely satisfactory. It wasn't possible. Even if the fluidity is good, if the selectivity and yield of the target product are low, the gas phase catalytic oxidation or the gas phase catalytic ammoxidation cannot be put to practical use.
- Patent Document 1 describes that a catalyst containing Mo, V, and Nb was obtained at a desired reduction rate, and this prepared a catalyst with a relatively small scale for the calcination step and the like. For this reason, it is estimated that uneven adjustment of the reduction rate is difficult to occur.
- Patent Document 1 Although it is known that the reduction rate of the oxide can affect the catalyst performance, in particular, the calcination process is scaled up and a large amount is obtained by continuous calcination for a long time. In the case of production, a method for producing a catalyst that achieves a desired reduction rate has not been known.
- the problem to be solved by the present invention is a method for producing an oxide catalyst used for gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane, and a catalyst exhibiting a good yield. It is to provide a method of stably producing.
- a catalyst having excellent performance by a method for producing an oxide catalyst comprising a step of calcining particles having a rate of 20% by mass or less and an average particle size of 35 to 70 ⁇ m in an inert gas atmosphere.
- the present invention has been completed by finding that it can be manufactured satisfactorily and stably.
- a method for producing an oxide catalyst for use in a gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane (I) A catalyst raw material containing Mo, V and Nb and satisfying 0.1 ⁇ a ⁇ 1 and 0.01 ⁇ b ⁇ 1 when the atomic ratios of V and Nb to Mo1 atoms are a and b, respectively. Preparing a mixture, (Ii) a step of drying the catalyst raw material mixture; and (iii) particles having a particle size of 25 ⁇ m or less in a particle size of 20% by mass or less and an average particle size of 35 to 70 ⁇ m in an inert gas atmosphere.
- the step (iii) is a step of firing particles having a particle size of 25 ⁇ m or less and a particle content of 8% by mass or less and an average particle size of 45 to 65 ⁇ m in an inert gas atmosphere.
- the manufacturing method of the oxide catalyst of description is a manufacturing method of the oxide catalyst of the said [1] or [2] description which is a process of spray-drying the said catalyst raw material liquid mixture.
- [5] The method for producing an oxide catalyst according to the above [4], wherein the particle recovery rate in the classification operation is 75% by mass or more.
- [6] The oxide catalyst according to any one of [1] to [5], wherein the oxide catalyst is supported on silica in an amount of 10 to 80% by mass in terms of SiO 2 with respect to the total weight of the oxide of the catalyst constituent elements and silica.
- the method (iii) is a method for producing an oxide catalyst according to any one of the above [1] to [6], wherein the catalyst precursor particles calcined in the previous stage include a step of main calcination.
- a method for producing an unsaturated acid or an unsaturated nitrile comprising: A production method comprising a step of bringing propane or isobutane into contact with an oxide catalyst obtained by the production method according to any one of [1] to [11] above and subjecting the oxide catalyst to a gas phase catalytic oxidation or a gas phase catalytic ammoxidation reaction.
- the manufacturing method of the oxide catalyst used for the gaseous-phase catalytic oxidation of propane or isobutane or a gaseous-phase catalytic ammoxidation reaction Comprising: The method of manufacturing stably the catalyst which shows a favorable yield is provided. can do.
- a method for producing an oxide catalyst used for gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane includes (i) Mo, V, Nb, and V, Nb atoms relative to Mo1 atoms.
- the particles to be fired before the firing step of step (iii), have a particle content of 20 ⁇ % or less with a particle size of 25 ⁇ m or less and an average particle size of 35 to 70 ⁇ m. Adjust so that
- Step (i) includes Mo, V, and Nb, and 0.1 ⁇ a ⁇ 1 and 0.01 ⁇ b ⁇ 1 when the atomic ratios of V and Nb to Mo1 atoms are a and b, respectively. This is a step of preparing a catalyst raw material mixture to be filled.
- the catalyst raw material mixture of the present embodiment contains Mo, V, and Nb.
- the atomic ratios of V and Nb to Mo1 atoms are a and b, respectively, 0.1 ⁇ a ⁇ 1, 0.01 ⁇ b ⁇ 1, preferably 0.15 ⁇ a ⁇ 0.9 and 0.02 ⁇ b ⁇ 0.8.
- the raw material for the component metal used in step (i) is not particularly limited as long as it contains Mo, V, and Nb.
- the Mo material include molybdenum oxide, ammonium dimolybdate, ammonium heptamolybdate, phosphomolybdic acid, and silicomolybdic acid. Among these, ammonium heptamolybdate can be preferably used.
- the raw material for V include vanadium pentoxide, ammonium metavanadate, and vanadyl sulfate. Among them, ammonium metavanadate can be preferably used.
- Examples of the raw material of Nb include at least one selected from the group consisting of niobic acid, an inorganic acid salt of niobium, and an organic acid salt of niobium.
- niobic acid is preferable.
- Niobic acid is represented by Nb 2 O 5 .nH 2 O and is also referred to as niobium hydroxide or niobium oxide hydrate.
- Te telluric acid
- Sb when Sb is added, antimony oxide can be suitably used as a raw material for Sb.
- step (i) for example, a solution is prepared by dissolving each of the above-mentioned raw materials in a solvent such as water, and the resulting solution is mixed to obtain a catalyst raw material mixture.
- niobic acid and oxalic acid are added to water and stirred to obtain an aqueous solution or aqueous suspension.
- dissolution of the niobium compound can be promoted by adding a small amount of aqueous ammonia or heating.
- the aqueous solution or suspension is then cooled and filtered to obtain a niobium-containing liquid. Cooling can be carried out simply by ice-cooling, and filtration can be carried out simply by decantation or filtration.
- Oxalic acid can be appropriately added to the obtained niobium-containing liquid to prepare a suitable oxalic acid / niobium ratio.
- the molar ratio of oxalic acid / niobium is preferably 2 to 5, more preferably 2 to 4. Furthermore, hydrogen peroxide may be added to the obtained niobium mixed solution to prepare a mixed solution (B). At this time, the molar ratio of hydrogen peroxide / niobium is preferably 0.5 to 20, and more preferably 1 to 10.
- the mixed liquid (A) and the mixed liquid (B) are mixed according to the target composition to obtain a raw material mixed liquid.
- a compound containing W is suitably mixed to obtain a raw material mixture.
- the compound containing W for example, ammonium metatungstate is suitably used.
- a compound containing Mn for example, manganese nitrate is preferably used.
- the compound containing W or Mn can be added to the mixed liquid (A), or can be added simultaneously when the mixed liquid (A) and the mixed liquid (B) are mixed.
- the oxide catalyst is supported on a silica carrier, the raw material mixture is prepared so as to contain the silica sol, and in this case, the silica sol can be appropriately added.
- the metal component contained in the catalyst raw material mixture can have various oxidation numbers.
- each of the catalyst components in the step (i) of the catalyst has a maximum oxidation number or a state close thereto. Oxidation is preferred.
- the reason why it is preferable to prepare the catalyst raw material mixture in such a manner that the oxidation proceeds is that the catalyst having a preferable reduction rate is industrially stabilized by oxidizing in this step and proceeding the reduction in the firing step described later. This is because it is considered that it is easier to obtain.
- the method for oxidizing the catalyst raw material mixture so as to have the highest oxidation number or an oxidation number close thereto is not particularly limited.
- the mixed solution (A) or the mixed solution (A) The method of adding hydrogen peroxide to the liquid containing the component of) is mentioned.
- 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.
- the catalyst raw material mixture thus obtained may be a uniform solution, but is usually a slurry.
- Step (ii) is a step of drying the catalyst raw material mixture.
- a dry powder is obtained by drying the catalyst raw material mixture obtained in the above step (i). Drying can be performed by a known method, for example, spray drying or evaporation to dryness, but 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.
- 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.
- the dry powder or catalyst precursor has a particle content of a particle size of 25 ⁇ m or less of 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and even more preferably. Prepare so that it may become 2 mass% or less.
- the term “catalyst precursor” refers to a compound that is generated in the middle of the firing step described later. For example, what is obtained after the pre-stage firing described later is called a catalyst precursor.
- the content of particles having a particle diameter of 25 ⁇ m or less exceeds 20% by mass, the performance of the resulting catalyst is deteriorated, and the yield of the target product in the fluidized bed reactor tends to decrease.
- the catalyst contains Mo, Sb, Te or the like, a low melting point compound is likely to be generated during firing. Since particles having a particle size of 25 ⁇ m or less have a larger surface ratio than particles having a particle size of more than 25 ⁇ m, it is considered that fixation is more likely to occur. If the amount of fixing becomes too large, problems such as a failure to obtain a sufficient firing temperature for the catalyst layer and an inability to secure the production amount occur. Therefore, it is preferable to reduce the proportion of particles having a particle size of 25 ⁇ m or less before firing.
- the dry powder or catalyst precursor is prepared to have an average particle size of 35 to 70 ⁇ m, preferably 40 to 65 ⁇ m, more preferably 42 to 65 ⁇ m, still more preferably 45 to 63 ⁇ m, and even more preferably 45 to 60 ⁇ m.
- the average particle size is less than 35 ⁇ m, the fluidity may deteriorate and the yield of the target product in the fluidized bed reaction may decrease, or it may be easily scattered from the fluidized bed reactor, resulting in a large amount of catalyst loss. If it exceeds 70 ⁇ m, the fluidity is deteriorated and the contact efficiency with the reaction gas is deteriorated, so that the yield of the target product in the fluidized bed reaction may be lowered.
- the reduction rate of the catalyst precursor can be adjusted to a preferred range.
- the dry powder usually contains an ammonium root, an organic acid, and an inorganic acid.
- the ammonium root evaporates to ammonia gas, and the catalyst precursor particles are reduced from the gas phase.
- the reduction rate of the catalyst precursor varies particularly depending on the firing time and firing temperature in the pre-stage firing described later.
- the reduction easily proceeds and the reduction rate becomes high.
- many precursors having a relatively small particle size are contained, typically, when the average particle size is less than 35 ⁇ m, or the content of particles having a particle size of 25 ⁇ m or less exceeds 20% by mass, it is accompanied by an inert gas or a calcined tube
- the small particles have many surfaces that come into contact with ammonia gas and are easily reduced.
- the average particle diameter exceeds 70 ⁇ m, the particles are large, so that the surface in contact with the ammonia gas is less likely to be reduced, and as a result, it is considered difficult to adjust the reduction rate to a preferable range.
- the particle content of a particle size of 25 ⁇ m or less is applied to a dry powder or catalyst precursor particles 20 g using a sieve having an opening of 25 ⁇ m and a diameter of 20 cm for 3 minutes by applying a vibrator (for example, National Panabrator), It is a value calculated by measuring the weight of the particles passing through the sieve and the weight of the particles remaining on the sieve and using the following equation.
- (Particle content of 25 ⁇ m or less) (mass of particles passing through a sieve) ⁇ ⁇ (mass of particles passing through a sieve) + (mass of particles remaining on the sieve) ⁇ ⁇ 100
- the average particle diameter is measured by using a LS230 manufactured by BECKMAN COULTER from a particle size distribution measuring apparatus BECKMAN by calcination of a part of the dry powder in air at 400 ° C. for 1 hour, and the obtained particles.
- the particle content of 25 ⁇ m or less and the average particle size are measured after the dry powder is “baked in air at 400 ° C. for 1 hour” in order to prevent the dry powder from being dissolved in water. That is, “calcination in air at 400 ° C. for 1 hour” is exclusively for measurement, and is not related to the later-described firing step. It may be considered that the particle diameter does not substantially change before and after the firing. Although the reduction rate of this calcined sample may be different from other dry powders, since the sample is usually very small, the whole catalyst can be used regardless of whether it is used in the calcining step described below or not. Almost no effect on performance.
- the measurement target of the average particle size is not necessarily a dry powder, and the average particle size of the calcined catalyst precursor may be measured as necessary.
- More specific measurement of the average particle diameter is performed as follows according to the manual attached to the LS230 manufactured by BECKMAN COULTER, a laser diffraction scattering method particle size distribution measuring apparatus. After background measurement (RunSpeed 60), 0.2 g of particles are weighed into an appropriately sized screw tube and 10 cc of water is added. Cap screw tube and shake well to disperse particles in water. Apply ultrasonic waves of the device for 30 watts, shake the screw tube well again, and inject the particles dispersed in water to an appropriate concentration (concentration 10, PIDS 60) with a dropper. When the concentration display is stable, the ultrasonic wave is turned off and measurement is started every 10 seconds (measurement time 90 seconds). The median diameter value of the measurement result is defined as the average particle diameter.
- spray drying conditions such as atomizer rotation speed, spray drying temperature, and raw material mixing
- a method for adjusting the supply amount of the liquid examples thereof include a method for adjusting the supply amount of the liquid and a method for classifying the dry powder or the catalyst precursor.
- the classification method is not particularly limited, and for example, general methods such as a centrifugal classifier, an air classifier, a gravity classifier, an inertia classifier, a sieve, and a cyclone can be used. If the type is dry or wet, a dry classifier can be preferably used.
- the recovery rate of the dry powder or catalyst precursor particles in the classification operation is preferably 75% by mass or more, more preferably 80% by mass or more, or It is preferable to select and use an apparatus that satisfies the conditions.
- the step of adjusting the dry powder or catalyst precursor particles so that the content of particles having a particle size of 25 ⁇ m or less is 20 mass% or less and the average particle size is 35 to 70 ⁇ m is not particularly limited as long as it is before the main firing.
- the pre-stage baking can be performed after completion.
- the catalyst precursor is in a reduced state and may be oxidized by contact with air to change from an appropriate reduction rate. Therefore, it is preferable to store in an atmosphere substantially free of oxygen until the main baking is performed.
- the step of adjusting the particle content with a particle size of 25 ⁇ m or less to 20% by mass or less and the average particle size to be 35 to 70 ⁇ m is preferably performed before the pre-stage firing.
- the production method of the present embodiment further includes (iii) a particle content of a particle size of 25 ⁇ m or less is 20% by mass or less, and an average particle size is 35. Calcination of ⁇ 70 ⁇ m particles in an inert gas atmosphere.
- a rotary furnace (rotary kiln), a fluidized baking furnace, or the like can be used.
- the catalyst precursor particles are baked while standing, they are not uniformly baked and the performance is deteriorated, and cracks, cracks and the like are caused. Therefore, when performing continuous firing, it is preferable to use a rotary furnace (rotary kiln).
- the shape of the calciner is not particularly limited, but continuous firing can be performed when the shape is tubular.
- the shape of the firing tube is not particularly limited, but is preferably a cylinder.
- the heating method is preferably an external heating type, and an electric furnace can be suitably used.
- the size, material, etc. of the firing tube can be selected appropriately according to the firing conditions and production amount, but the inner diameter is preferably 70 to 2000 mm, more preferably 100 to 1200 mm, and the length is preferably 200-10000 mm, more preferably 800-8000 mm is used.
- a weir plate having a hole for the passage of dry powder or catalyst precursor particles in the center is provided in the calcining tube perpendicular to the flow of the catalyst precursor particles so that the calcining tube is divided into two or more areas. It can also be partitioned.
- 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 weir plate when supplying the catalyst precursor at 250 g / hr in a rotary furnace having a SUS calcining tube having an inner diameter of 150 mm and a length of 1150 mm, the weir plate is preferably 5 to 50 mm, more preferably 10 to 40 mm, and still 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.
- it 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 calciner In the calcination step, it is preferable to rotate the calciner in order to prevent cracking, cracks and the like of the catalyst precursor particles and to uniformly calcine.
- the rotation speed of the calciner 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 or catalyst precursor particles is continuously increased from a temperature lower than 400 ° C. to a temperature in the range of 550 to 800 ° C. It is preferable to increase the temperature intermittently or intermittently.
- the firing process is performed in an inert gas atmosphere. Firing is preferably carried out while circulating an inert gas that does not substantially contain oxygen such as nitrogen. As described above, it is preferable that the obtained catalyst has a specific reduction rate and specific surface area in order to obtain a catalyst that exhibits moderate activity and good reaction results (selectivity and yield of target product). Since the dry powder is prepared in such a manner that oxidation proceeds as described above, it is preferable to partially reduce at least one constituent element in the firing step. When calcination is performed in an inert gas atmosphere, there is an advantage that the reduction can be appropriately promoted by the ammonium root, organic acid, and inorganic acid contained in the dry powder.
- the atmosphere is not an inert gas
- the constituent elements are excessively oxidized by the air, so that it is difficult to adjust to a preferable reduction rate.
- firing is performed in an atmosphere in which constituent elements can be reduced, for example, ammonia exists excessively, it is excessively reduced, and similarly, it is difficult to adjust to a preferable reduction rate.
- the raw material mixed liquid is obtained by a process including oxidizing molybdenum and vanadium in the liquid to almost the maximum oxidation number.
- the above-mentioned advantage tends to become more prominent by firing the dry powder or catalyst precursor particles while circulating an inert gas substantially free of oxygen such as nitrogen.
- the dry powder or catalyst precursor particles usually contain ammonium root, organic acid, inorganic acid and the like in addition to moisture.
- the catalyst constituent elements are reduced when they are evaporated, decomposed or the like.
- the catalyst constituent element in the dry powder has almost the highest oxidation number, in order to bring the reduction rate of the catalyst precursor to the desired range, it is only necessary to carry out the reduction in the calcination step. is there.
- the supply amount of the inert gas is 50 N liter / hr or more, preferably 50 to 5000 N liter / hr, more preferably 50 to 3000 N liter / hr per kg of the catalyst precursor particles ( N liters means standard temperature and pressure conditions, that is, liters measured at 0 ° C. and 1 atm).
- N liters means standard temperature and pressure conditions, that is, liters measured at 0 ° C. and 1 atm).
- the supply amount of the inert gas is 50 N liters or more, preferably 50 to 5000 N liters, preferably 50 to 3000 N liters per kg of the catalyst precursor particles.
- the inert gas and the dry powder or catalyst precursor particles may be counter-current or co-current, but there is no problem with the gas components generated from the dry powder or catalyst precursor particles, or a small amount of air mixed with the catalyst precursor particles. Considering this, countercurrent contact is preferred.
- prior firing may be performed before performing the main firing.
- 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 catalyst precursor particles When the catalyst precursor particles are calcined at 550 to 800 ° C., they are calcined at a temperature higher than the melting point of the metal component contained in the oxide catalyst and / or catalyst precursor. Therefore, a metal component having a low melting point is melted during firing, and the oxide catalyst, the catalyst precursor, and the like are easily fixed or fused to the inner wall of the firing tube to easily form a lump. Particularly in continuous firing, this causes deterioration of heat transfer, a decrease in residence time, and unstable powder flow, making it difficult to stably fire at a desired temperature. In order to suppress such sticking to the inner wall of the firing tube and formation of lumps, it is preferable to apply an impact to the firing tube.
- the shape of the catalyst can be maintained better, so it is indirectly through the outer wall of the calcining tube. It is preferable to apply an impact to.
- the impact applied to the firing tube is the depth (powder depth) in which the catalyst precursor supplied in the firing tube has accumulated in the firing tube, the diameter, length, thickness and material of the firing tube, and the material and type of the device that applies the impact. Since it depends on the shape / position, the frequency of impact, etc., it is preferable to set appropriately.
- the vibration acceleration is preferably 0.1 m / s 2 or more, more preferably 1 m / s 2 or more, still more preferably 5 m / s 2 or more, particularly preferably from the viewpoint of sufficiently reducing adhesion to the inner wall of the fired tube. Is 10 m / s 2 or more.
- it is preferably 3000 m / s 2 or less, more preferably 1000 m / s 2 or less, More preferably, it is 500 m / s ⁇ 2 > or less, Most preferably, it is 300 m / s ⁇ 2 > or less.
- the “vibration acceleration” of the impact applied to the firing tube is a position at a distance of L / 4, 3L / 8, L / 2 from the firing tube powder inlet in parallel to the powder flow direction with respect to the overall length L of the firing tube. It means the average value of the values measured in.
- the measurement position is the same position as where the impact is applied in the firing tube cross-sectional direction.
- the vibration acceleration can be measured with a vibrometer attached to the firing tube.
- MD220 manufactured by Asahi Kasei Techno System Co., Ltd. can be used.
- the method for applying the impact is not particularly limited, and an air knocker, hammer, hammering device, or the like can be suitably used.
- the material of the portion directly in contact with the firing tube at the tip of the impact is not particularly limited as long as it is a material having sufficient heat resistance, for example, a general resin that can withstand impact, metal, etc. can be used, Of these, metals are preferred.
- the metal preferably has a hardness that does not damage or deform the fired tube, and copper or SUS metal can be suitably used.
- the location to which the impact is applied is not particularly limited and can be performed at a location convenient for operation. However, since the impact can be directly applied to the firing tube without waste, it is applied to the location where the firing tube is not covered with the heating furnace. It is preferable.
- the location where the impact is applied may be one location or multiple locations.
- the frequency at which the impact is applied is not particularly limited, but it is preferable that the impact is constantly applied to the calcining tube because adhesion in the calcining tube tends to be reduced more favorably.
- Constantly applying an impact refers to applying an impact at a certain frequency or more. Preferably it is 1 second to 1 hour, more preferably 1 second to 30 minutes, more preferably 1 second to 5 minutes, particularly preferably 1 second to 1 minute. Apply shock.
- the impacts need not always be applied at the same interval, and may be random.
- two or more impacts may be applied in 10 seconds, and the frequency may be returned to once in 10 seconds.
- the frequency at which the impact is applied is appropriately adjusted according to the vibration acceleration, the powder depth of the catalyst precursor supplied into the firing tube, the diameter / length / thickness / material of the firing tube, and the material / type / shape of the impacting device. It is preferable.
- the thickness of the fired tube is not particularly limited as long as it is a sufficient thickness that does not break due to impact, but is preferably 2 mm or more, more preferably 4 mm or more. Further, from the viewpoint of sufficiently transmitting the impact to the inside of the firing tube, it is preferably 100 mm or less, more preferably 50 mm or less.
- the material is not particularly limited as long as it has heat resistance and has a strength that is not damaged by an impact. For example, SUS can be suitably used.
- Pre-stage calcination is performed in a range of heating temperature of 250 ° C. to 400 ° C., preferably 300 ° C. to 400 ° C. under inert gas flow.
- the temperature is preferably maintained at a constant temperature within the range of 250 ° C. to 400 ° C., but the temperature may vary within the range of 250 ° C. to 400 ° C., or the temperature may be raised or lowered gradually.
- the holding time of the heating temperature is 30 minutes or 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 not particularly limited, but is preferably 0.1 to 15 ° C./min, more preferably 0.5 to 5 ° C./min, and still more preferably 1 ⁇ 2 ° C / min.
- the main calcination is performed at a heating temperature of 550 to 800 ° C., preferably 580 to 750 ° C., more preferably 600 to 720 ° C., and even more preferably 620 to 700 ° C. under an inert gas flow.
- the temperature is preferably maintained at a constant temperature within a temperature range of 620 to 700 ° C., but the temperature may vary within the range of 620 to 700 ° C., or the temperature may be gradually increased or decreased.
- the firing time is 0.5 to 20 hours, preferably 1 to 15 hours.
- the catalyst precursor particles continuously pass through at least two, preferably 2 to 20, more preferably 4 to 15 zones.
- 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 are installed and controlled in each section separated by these weirs. Is preferred.
- the temperature of the catalyst precursor particles is the desired temperature.
- the set temperature is controlled by a heater and a controller in which eight areas are set for each of the areas so as to obtain the firing temperature pattern.
- an oxidizing component for example, oxygen
- a reducing component for example, ammonia
- the catalyst raw material contains an ammonium salt
- ammonia can be generated in the calcination step, but according to the knowledge of the present inventor, in any case, calcination can be performed at an intended reduction rate.
- an oxidizing component or a reducing component it is not a preferable embodiment to add an oxidizing component or a reducing component, but it can be said that it does not affect the reduction rate of the calcined catalyst.
- the amount considered to have no substantial effect is 0.2 N liters or less for 1 kg of dry powder or catalyst precursor in the case of an oxidizing component (eg, oxygen), and dry in the case of a reducing component (eg, ammonia). It is 1.0 N liters or less with respect to 1 kg of powder or catalyst precursor.
- 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 preferably 0.1 to 15 ° C./min, more preferably 0.5 to 10 ° C./min, and still more preferably 1 ⁇ 8 ° C / min.
- the average temperature lowering 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, and further preferably 0.5 to 10 ° C./min.
- the temperature to be maintained is 10 ° C., preferably 50 ° C., more preferably 100 ° C. 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.
- an oxidizing component or a reducing component may be added to the firing atmosphere.
- the amount of organic components such as oxalic acid contained in the dry powder, the amount of ammonium root derived from the ammonium salt of the raw material, the rate of temperature rise at the start of firing, the temperature , Time, amount of inert gas, etc. have an effect.
- the temperature starts from a temperature lower than 400 ° C., decomposes the oxalate and ammonium radicals in the catalyst precursor particles, and generates gas. Is almost finished.
- the value of (n 0 -n) in the above formula (1) can be obtained by oxidation-reduction titration of the sample with KMnO 4 .
- An example of the measurement method is shown below. Precisely weigh about 200 mg of sample into a beaker. Further, an excessive amount of a KMnO 4 aqueous solution having a known concentration is added. Further, after adding 150 mL of purified water and 2 mL of 1: 1 sulfuric acid (ie, sulfuric acid aqueous solution obtained by mixing concentrated sulfuric acid and purified water at a volume ratio of 1/1), the beaker was capped with a watch glass and 70 ° C.
- the sample is oxidized by stirring for 1 hour in a water bath at ⁇ 2 ° C. At this time, KMnO 4 is excessively present, and since unreacted KMnO 4 is present in the liquid, it is confirmed that the liquid color is purple.
- the solution is filtered with a filter paper to collect the entire amount of the filtrate.
- a sodium oxalate aqueous solution having a known concentration is added in excess to the KMnO 4 present in the filtrate, and the mixture is heated and stirred so that the liquid temperature becomes 70 ° C.
- 2 mL of 1: 1 sulfuric acid is added. Stirring is continued while maintaining the liquid temperature at 70 ° C.
- the reduction rate of any of the catalyst precursor before the completion of calcination and the catalyst after the completion of calcination can be measured as follows.
- the sample is heated to a temperature higher than the calcination temperature at which the catalyst precursor or catalyst was calcined under the condition that the constituent elements of the sample do not volatilize or escape, and complete oxidation with oxygen is performed to determine the increased weight (amount of bound oxygen). From this, the value of (n 0 -n) is obtained, and the reduction rate is obtained based on this value.
- [Oxide catalyst] An example of a preferable oxide catalyst of the present embodiment is represented by the following composition formula (2). Mo1VaNbbXcYdOn (2) (In the formula, component X represents at least one element selected from Te and Sb, and Y represents one or more elements selected from Mn, W, B, Ti, Al, Ta, alkali metal, and alkaline earth metal. A, b, c, d, and n represent the atomic ratio of vanadium (V), niobium (Nb), element X, element Y, and oxygen (O) to 1 atom of molybdenum (Mo), respectively.
- n is the number of oxygen atoms determined by the valence of a constituent element other than oxygen.
- the atomic ratios a, b, c, and d per Mo atom are preferably 0.1 ⁇ a ⁇ 1, 0.01 ⁇ b ⁇ 1, 0.01 ⁇ c ⁇ 1, and 0 ⁇ d ⁇ 1, respectively. More preferably, 0.1 ⁇ a ⁇ 0.5, 0.01 ⁇ b ⁇ 0.5, 0.1 ⁇ c ⁇ 0.5, 0.0001 ⁇ d ⁇ 0.5, and even more preferably. Are 0.2 ⁇ a ⁇ 0.3, 0.05 ⁇ b ⁇ 0.2, 0.2 ⁇ c ⁇ 0.3, and 0.0002 ⁇ d ⁇ 0.4.
- the oxide catalyst is preferably supported on a silica support.
- the oxide catalyst is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and still more preferably 30 to 55% by mass in terms of SiO 2 with respect to the total weight of the oxides of the catalyst constituent elements and silica. Supported on silica.
- the amount of silica supporting the oxide catalyst is determined from the viewpoints of strength and prevention of pulverization, ease of stable operation when using the catalyst, and reduction of replenishment of the lost catalyst. From the viewpoint of achieving sufficient catalytic activity, it is preferably 80% by mass or less based on the total weight of the oxides of the catalyst constituent elements and silica. In particular, when the catalyst is used in a fluidized bed, if the amount of silica is 80% by mass or less, the specific gravity of the catalyst supported on silica is appropriate, and it is easy to create a good fluidized state.
- the feedstock for propane or isobutane and ammonia does not necessarily have to be highly pure, and industrial grade gas can be used.
- As the supply oxygen source air, pure oxygen, or air enriched with pure oxygen can be used.
- helium, neon, argon, carbon dioxide gas, water vapor, nitrogen or the like may be supplied as a dilution gas.
- the molar ratio of ammonia supplied to the reaction system to propane or isobutane is 0.3 to 1.5, preferably 0.8 to 1.2.
- the molar ratio of molecular oxygen supplied to the reaction system to propane or isobutane is 0.1 to 6, preferably 0.1 to 4.
- the reaction pressure is 0.5 to 5 atm, preferably 1 to 3 atm
- the reaction temperature is 350 ° C. to 500 ° C., preferably 380 ° C. to 470 ° C.
- the time is 0.1 to 10 (sec ⁇ g / cc), preferably 0.5 to 5 (sec ⁇ g / cc).
- reaction systems such as a fixed bed, fluidized bed, and moving bed can be adopted as the reaction system, but the heat of reaction can be easily removed and the temperature of the catalyst layer can be maintained almost uniformly, and the catalyst is extracted from the reactor during operation.
- a fluidized bed reaction is preferable because a catalyst can be added.
- propane conversion and the acrylonitrile yield follow the following definitions, respectively.
- Propane conversion (Pn conversion) (%) (number of moles of reacted propane) / (number of moles of supplied propane) ⁇ 100
- Acrylonitrile yield (AN yield) (%) (Mole number of acrylonitrile produced) / (Mole number of supplied propane) ⁇ 100
- niobium raw material liquid A niobium raw material solution was prepared by the following method. Niobic acid 76.33 kg containing 80.2 mass% as Nb 2 O 5 and oxalic acid dihydrate [H 2 C 2 O 4 .2H 2 O] 29.02 g were mixed in 500 kg of water. The molar ratio of charged oxalic acid / niobium was 5.0, and the concentration of charged niobium was 0.532 (mol-Nb / kg-solution). This solution was heated and stirred at 95 ° C. for 1 hour to obtain an aqueous solution in which the niobium compound was dissolved.
- the aqueous solution was allowed to stand and ice-cooled, and then the solid was separated by suction filtration to obtain a uniform aqueous niobium compound solution. The same operation was repeated several times, and the obtained niobium compound aqueous solution was combined into one niobium raw material solution.
- the molar ratio of oxalic acid / niobium in this niobium raw material liquid was 2.60 according to the following analysis. In a crucible, 10 g of this niobium raw material solution was precisely weighed, dried overnight at 95 ° C., and then heat treated at 600 ° C. for 1 hour to obtain 0.7868 g of Nb 2 O 5 .
- the niobium concentration was 0.5920 (mol-Nb / kg-solution).
- 3 g of this niobium raw material solution was precisely weighed into a 300 mL glass beaker, 200 mL of hot water at about 80 ° C. was added, and then 10 mL of 1: 1 sulfuric acid was added.
- the obtained solution was titrated with 1 / 4N KMnO 4 under stirring while maintaining the liquid temperature at 70 ° C. on a hot stirrer. The end point was a point where a faint pale pink color by KMnO 4 lasted for about 30 seconds or more.
- the concentration of oxalic acid was 1.54 (mol-oxalic acid / kg) as a result of calculation according to the following formula from titration. 2KMnO 4 + 3H 2 SO 4 + 5H 2 C 2 O 4 ⁇ K 2 SO 4 + 2MnSO 4 + 10CO 2 + 8H 2 O
- the obtained niobium raw material liquid was used as a niobium raw material liquid in the production of the following oxide catalyst.
- Example 1 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Sb 0.26 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) To 18.07 kg of water, 3.69 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.58 kg of ammonium metavanadate [NH 4 VO 3 ], antimony trioxide [Sb 2 0.73 kg of O 3 ] was added, and the mixture was heated at 90 ° C. for 2.5 hours with stirring to obtain an aqueous mixture A-1.
- aqueous liquid B-1 was added to 3.23 kg of the niobium raw material liquid.
- 0.43 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added.
- the liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1.
- the obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and 6.95 kg of silica sol containing 30.4% by mass as SiO 2 was added.
- 0.92 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added and stirred and mixed at 50 ° C. for 1 hour.
- aqueous liquid B-1 was added.
- a turbo classifier TC-25M manufactured by Nisshin Engineering Co., Ltd. was used as a classifier.
- the amount of powder supplied to the classifier was 40 kg / hr, the air volume was 7 m 3 / min, and the rotor rotation speed was 1250 rpm.
- the dry powder particles obtained had a particle content of 25 ⁇ m or less of 1.8% by mass and an average particle size of 55 ⁇ m.
- the average particle diameter was measured by LS230 manufactured by BECKMAN COULTER. (Baking) Seven dam plates having a height of 35 mm were placed on a SUS-fired tube having an inner diameter of 200 mm and a length of 1500 mm so that the length of the heating furnace portion was equally divided into eight.
- the dry powder obtained by the classification operation was circulated at a speed of 550 g / hr, and increased to 360 ° C. over about 6 hours under a nitrogen gas flow of 8.2 N liter / min.
- the temperature of the heating furnace was set so that the temperature profile was maintained at 360 ° C. for 2 hours, and pre-stage continuous firing was performed.
- the reduction rate of the catalyst precursor at this time was 10.23%.
- the temperature was raised to 650 ° C. at 2 ° C./min under a nitrogen gas flow of 8.0 N liters / min while the firing tube was rotated at 5 rpm, fired at 650 ° C. for 2 hours, and 1 ° C. /
- the temperature of the heating furnace was set so as to obtain a temperature profile in which the temperature was lowered in min, and the main firing was carried out continuously.
- a hammering device in which a hammer with a 3 kg mass made of SUS is installed on the powder introduction side of the firing tube (the part not covered with the heating furnace), firing in the direction perpendicular to the rotation axis The impact was applied once every 15 seconds from the height of 40 mm above the tube.
- Example 2 An oxide catalyst was obtained in the same manner as in Example 1 except that the rotor rotation speed to the classifier was 1400 rpm.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 4.1% by mass and an average particle size of 52 ⁇ m. Further, the reduction rate of the catalyst precursor was 9.98%.
- the propane conversion was 88.2% and the acrylonitrile yield was 51.8%.
- Example 3 An oxide catalyst was obtained in the same manner as in Example 1 except that the rotor rotation speed to the classifier was 1500 rpm.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 6.0% by mass and an average particle size of 51 ⁇ m.
- the reduction rate of the catalyst precursor was 10.10%.
- the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 87.9% and the acrylonitrile yield was 51.0%.
- Example 4 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Sb 0.26 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) Ammonium heptamolybdate in water 4.52kg [(NH 4) 6 Mo 7 O 24 ⁇ 4H 2 O ] was 0.93 kg, the ammonium metavanadate [NH 4 VO 3] 0.15 kg, diantimony trioxide [Sb 2 0.20 kg of O 3 ] was added, and the mixture was heated at 90 ° C. for 2.5 hours with stirring to obtain an aqueous mixture A-1.
- aqueous liquid B-1 0.11 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 0.81 kg of the niobium raw material liquid. The liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1. The obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and 1.74 kg of silica sol containing 30.4% by mass as SiO 2 was added. Next, 0.23 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added, and the mixture was stirred and mixed at 50 ° C. for 1 hour. Next, aqueous liquid B-1 was added.
- a liquid in which 0.35 kg of fumed silica was dispersed in 4.93 kg of water was added to obtain a raw material mixture.
- the obtained raw material mixture 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.
- Classification operation 200 g of the obtained dry powder was sieved by applying a vibrator for 2 minutes using a sieve having an opening of 25 ⁇ m and a diameter of 20 cm, and classification was performed. After classification, the dry powder particles obtained had a particle content of 25 ⁇ m or less of 0.2% by mass and an average particle size of 56 ⁇ m.
- the average particle diameter was measured by LS230 manufactured by BECKMAN COULTER. (Baking) 100 g of dry powder particles obtained by the classification operation are filled in a glass firing tube having a diameter of 50 mm, and the firing tube is rotated under a nitrogen gas flow of 0.25 N liter / min. The temperature was raised and held at 360 ° C. for 2 hours. The reduction rate at this time was 9.93%. Then, it heated up to 650 degreeC in 2 hours, and baked at 650 degreeC for 2 hours, and obtained the catalyst. When the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 88.8% and the acrylonitrile yield was 52.8%.
- Example 5 Example 1 with the exception that a hammering device having a hammer of 2 kg in mass at the tip of the hitting part was placed once in 15 seconds from a height of 35 mm above the firing tube in a direction perpendicular to the rotation axis. An oxide catalyst was obtained in the same manner. The vibration acceleration was measured by a vibration meter (MD-220 manufactured by Asahi Kasei Techno System Co., Ltd.) and found to be 14 m / s 2 . When the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 88.3% and the acrylonitrile yield was 52.1%.
- MD-220 manufactured by Asahi Kasei Techno System Co., Ltd.
- Example 6 Example 1 with the exception that a hammering device having a hammer of 13 kg in mass at the tip of the hammering part was hit once every 15 seconds from a height of 50 mm above the firing tube in a direction perpendicular to the rotation axis.
- An oxide catalyst was obtained in the same manner.
- the vibration acceleration was measured with a vibration meter (MD-220 manufactured by Asahi Kasei Techno System Co., Ltd.) and found to be 210 m / s 2 .
- the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 88.4% and the acrylonitrile yield was 52.4%.
- Example 7 After obtaining a dry powder by the same method as in Example 1, the previous-stage continuous firing was performed in the same manner as in Example 1 without performing the classification operation. 200 g of the catalyst precursor particles obtained by the pre-stage calcination were sieved by applying a vibrator for 2 minutes using a sieve with an opening of 25 ⁇ m and a diameter of 20 cm, and classification operation was performed. After classification, the obtained catalyst precursor particles had a particle content of 25 ⁇ m or less of 0.4% by mass and an average particle size of 54 ⁇ m. The average particle diameter was measured by LS230 manufactured by BECKMAN COULTER. At this time, the reduction rate of the catalyst precursor was 10.18%.
- Example 1 An oxide catalyst was obtained in the same manner as in Example 1 except that the classification operation was not performed after spray drying.
- the dry powder particles had a particle content of 25 ⁇ m or less of 25% by mass and an average particle size of 34 ⁇ m.
- the reduction rate of the catalyst precursor at this time was 10.21%. Further, the reduction rate of particles of 25 ⁇ m or less was 10.54%, and the reduction rate of particles of 25 ⁇ m or more was 10.10%.
- the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 86% and the acrylonitrile yield was 47.5%.
- Example 2 An oxide catalyst was obtained by the same method as in Example 1 except that the rotation speed of the classifier was 3000 rpm.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 22% by mass and an average particle size of 46 ⁇ m.
- the reduction rate of the catalyst precursor at this time was 10.15%. Further, the reduction rate of particles of 25 ⁇ m or more was 10.11%, and the reduction rate of particles of 25 ⁇ m or less was 10.30%.
- the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 86.8% and the acrylonitrile yield was 49.5%.
- Example 3 An oxide catalyst was obtained by the same method as in Example 1 except that the rotation speed of the classifier was 2500 rpm.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 18% by mass and an average particle size of 34 ⁇ m.
- the reduction rate of the catalyst precursor at this time was 10.0%. Further, the reduction rate of particles of 25 ⁇ m or more was 9.93%, and the reduction rate of particles of 25 ⁇ m or less was 10.32%.
- the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 85.0% and the acrylonitrile yield was 48.8%.
- Example 4 An oxide catalyst was obtained by the same method as in Example 1 except that the classification operation was performed with a sieve having an opening of 53 ⁇ m.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 0% by mass and an average particle size of 71 ⁇ m.
- the reduction rate of the catalyst precursor at this time was 10.08%.
- the propane conversion was 87.1% and the acrylonitrile yield was 49.4%.
- Example 5 An oxide catalyst was obtained by the same method as in Example 1 except that the catalyst precursor particles were not classified and the catalyst was classified under the same conditions as in Example 1 after the main calcination.
- the content of particles of 25 ⁇ m or less in the classified catalyst was 2% by mass, and the average particle size was 53 ⁇ m.
- the reduction rate of the catalyst precursor at this time was 10.19%.
- the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 87.6% and the acrylonitrile yield was 49.9%.
- Example 6 An oxide catalyst was obtained by the same method as in Example 1 except that the calcination step was performed under air flow. The reduction rate of the catalyst precursor at this time was 4.2%. When the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 38.7% and the acrylonitrile yield was 6.5%.
- Example 8 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Sb 0.26 W 0.025 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) 17.6 kg of water, 3.59 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.57 kg of ammonium metavanadate [NH 4 VO 3 ], antimony trioxide [Sb 2 0.73 kg of O 3 ] was added, and the mixture was heated at 90 ° C. for 2.5 hours with stirring to obtain an aqueous mixture A-1.
- aqueous liquid B-1 0.42 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 3.14 kg of the niobium raw material liquid. The liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1. The obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and 6.95 kg of silica sol containing 30.4% by mass as SiO 2 was added. Next, 0.89 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added and stirred and mixed at 50 ° C. for 1 hour. Next, aqueous liquid B-1 was added.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 1.7% by mass and an average particle size of 52 ⁇ m.
- (Baking) Firing was performed in the same manner as in Example 1 to obtain an oxide catalyst. At this time, the reduction rate of the catalyst precursor was 10.19%.
- (Catalyst performance evaluation) When the performance of the oxide catalyst in the ammoxidation reaction was evaluated in the same manner as in Example 1, the propane conversion was 88.8% and the acrylonitrile yield was 53.0%.
- Example 9 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Sb 0.26 W 0.04 Ce 0.008 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) 17.22 kg of water, 3.52 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.56 kg of ammonium metavanadate [NH 4 VO 3 ], antimony trioxide [Sb 2 0.75 kg of O 3 ] and 0.07 kg of cerium nitrate [Ce (NO 3 ) 3 ⁇ 6H 2 O] were added, and the mixture was heated at 90 ° C.
- aqueous mixture A-1 0.41 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 3.07 kg of the niobium raw material liquid. The liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1. The obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and 6.95 kg of silica sol containing 30.4% by mass as SiO 2 was added. Next, 0.88 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added and stirred and mixed at 50 ° C. for 1 hour. Next, aqueous liquid B-1 was added.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 2.1% by mass and an average particle size of 55 ⁇ m.
- (Baking) Firing was performed in the same manner as in Example 1 to obtain an oxide catalyst. At this time, the reduction rate of the catalyst precursor was 10.16%.
- Example 10 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Sb 0.26 B 0.1 Ce 0.006 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) 17.7 kg of water, 3.62 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.57 kg of ammonium metavanadate [NH 4 VO 3 ], antimony trioxide [Sb 2 O 3] was 0.77 kg, 0.054 kg of cerium nitrate [Ce (NO 3) 3 ⁇ 6H 2 O ], was added 0.13kg of boric acid [H 3 BO 3], with stirring 90 ° C.
- aqueous liquid mixture A-1 2.5 It heated for the time and was set as the aqueous liquid mixture A-1. 0.43 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 3.16 kg of the niobium raw material liquid. The liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1. The obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and 6.95 kg of silica sol containing 30.4% by mass as SiO 2 was added. Subsequently, 0.90 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added, and the mixture was stirred and mixed at 50 ° C. for 1 hour. Next, aqueous liquid B-1 was added.
- Example 11 Composition formula was prepared a catalyst represented by Mo 1 V 0.22 Nb 0.092 Sb 0.25 W 0.04 Mn 0.003 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) In 15.5 kg of water, 3.56 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.52 kg of ammonium metavanadate [NH 4 VO 3 ], antimony trioxide [Sb 2 0.73 kg of O 3 ] was added, and the mixture was heated at 90 ° C. for 2.5 hours with stirring to obtain an aqueous mixture A-1.
- aqueous liquid B-1 0.42 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 3.11 kg of the niobium raw material liquid. The liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1. The obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and 6.95 kg of silica sol containing 30.4% by mass as SiO 2 was added. Next, 0.89 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added and stirred and mixed at 50 ° C. for 1 hour. Next, aqueous liquid B-1 was added.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 1.9% by mass and an average particle size of 54 ⁇ m.
- (Baking) Firing was performed in the same manner as in Example 1 to obtain an oxide catalyst. At this time, the reduction rate of the catalyst precursor was 10.25%.
- (Evaluation of catalyst yield) When the ammoxidation reaction of the oxide catalyst was evaluated in the same manner as in Example 1, the propane conversion was 88.6% and the acrylonitrile yield was 52.9%.
- Example 12 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Sb 0.26 Al 0.009 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) 18.03 kg of water, 3.68 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.58 kg of ammonium metavanadate [NH 4 VO 3 ], antimony trioxide [Sb 2 0.73 kg of O 3 ] was added, and the mixture was heated at 90 ° C. for 2.5 hours with stirring to obtain an aqueous mixture A-1.
- aqueous liquid B-1 was added to 3.22 kg of the niobium raw material liquid.
- 0.43 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 3.22 kg of the niobium raw material liquid.
- the liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1.
- the obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and 6.95 kg of silica sol containing 30.4% by mass as SiO 2 was added.
- 0.92 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added and stirred and mixed at 50 ° C. for 1 hour.
- aqueous liquid B-1 was added.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 1.8% by mass and an average particle size of 53 ⁇ m.
- (Baking) Firing was performed in the same manner as in Example 1 to obtain an oxide catalyst. At this time, the reduction rate of the catalyst precursor was 9.89%.
- (Catalyst performance evaluation) When the ammoxidation reaction of the oxide catalyst was evaluated in the same manner as in Example 1, the propane conversion was 87.7% and the acrylonitrile yield was 51.9%.
- Example 13 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Sb 0.26 Ce 0.005 Ta 0.01 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) 17.2 kg of water, 3.64 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.58 kg of ammonium metavanadate [NH 4 VO 3 ], antimony trioxide [Sb 2 O 3] was 0.78 kg, cerium nitrate [Ce (NO 3) 3 ⁇ 6H 2 O ] was 0.045 kg, tantalate 0.052kg added, the aqueous mixture was heated with stirring at 90 ° C.
- liquid A-1 0.43 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 3.18 kg of the niobium raw material liquid. The liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1. The obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and 6.95 kg of silica sol containing 30.4% by mass as SiO 2 was added. Next, 0.91 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added and stirred and mixed at 50 ° C. for 1 hour. Next, aqueous liquid B-1 was added.
- the reduction rate of the catalyst precursor at this time was 9.95%. (Catalyst performance evaluation) When the ammoxidation reaction of the oxide catalyst was evaluated in the same manner as in Example 1, the propane conversion was 87.9% and the acrylonitrile yield was 52.1%.
- Example 14 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Sb 0.26 O n / 47 wt% -SiO 2 as follows. (Preparation of raw material mixture) In 17.1 kg of water, 3.49 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.55 kg of ammonium metavanadate [NH 4 VO 3 ], antimony trioxide [Sb 2 0.75 kg of O 3 ] was added, and the mixture was heated at 90 ° C. for 2.5 hours with stirring to obtain an aqueous mixture A-1.
- aqueous liquid B-1 0.43 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 3.05 kg of the niobium raw material liquid. The liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1. The obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and then 7.42 kg of silica sol containing 30.4% by mass as SiO 2 was added. Next, 0.87 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added and stirred and mixed at 50 ° C. for 1 hour. Next, aqueous liquid B-1 was added.
- Example 15 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Sb 0.26 Ti 0.008 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) In 18.0 kg of water, 3.68 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.58 kg of ammonium metavanadate [NH 4 VO 3 ], antimony trioxide [Sb 2 0.73 kg of O 3 ] was added, and the mixture was heated at 90 ° C. for 2.5 hours with stirring to obtain an aqueous mixture A-1.
- aqueous liquid B-1 was added to 3.22 kg of the niobium raw material liquid.
- 0.43 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 3.22 kg of the niobium raw material liquid.
- the liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1.
- the obtained aqueous mixed liquid A-1 was cooled to 70 ° C., and 6.95 kg of silica sol containing 30.4% by mass as SiO 2 was added.
- 0.92 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added and stirred and mixed at 50 ° C. for 1 hour.
- aqueous liquid B-1 was added.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 2.1% by mass and an average particle size of 51 ⁇ m.
- (Baking) Firing was performed in the same manner as in Example 1 to obtain an oxide catalyst. At this time, the reduction rate of the catalyst precursor was 9.99%.
- (Catalyst performance evaluation) When the ammoxidation reaction of the oxide catalyst was evaluated in the same manner as in Example 1, the propane conversion was 87.9% and the acrylonitrile yield was 51.8%.
- Example 16 Composition formula was prepared a catalyst represented by Mo 1 V 0.24 Nb 0.092 Te 0.26 O n / 44 wt% -SiO 2 as follows. (Preparation of raw material mixture) 18.3 kg of water, 3.74 kg of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O], 0.59 kg of ammonium metavanadate [NH 4 VO 3 ], telluric acid [H 6 TeO 6 1.06 kg was added and heated at 90 ° C. for 2.5 hours with stirring to obtain an aqueous mixed solution A-1. 0.44 kg of hydrogen peroxide containing 30% by mass as H 2 O 2 was added to 3.05 kg of the niobium raw material liquid.
- aqueous liquid B-1 The liquid temperature was maintained at about 20 ° C., and the mixture was stirred and mixed to obtain aqueous liquid B-1.
- the obtained aqueous mixed liquid A-1 was cooled to 70 ° C., 6.95 kg of silica sol containing 30.4% by mass as SiO 2 was added, and the mixture was stirred and mixed at 50 ° C. for 1 hour.
- aqueous liquid B-1 was added. Furthermore, a liquid in which 1.41 kg of fumed silica was dispersed in 19.7 kg of water was added to obtain a raw material mixture.
- the “preparation of raw material mixture” step was repeated 10 times to prepare a total of about 80 kg of the raw material mixture.
- Preparation of dry powder Spray drying was performed in the same manner as in Example 1 to obtain a dry powder.
- Classification operation Classification was performed in the same manner as in Example 1.
- the dry powder particles after classification had a particle content of 25 ⁇ m or less of 2.2% by mass and an average particle size of 50 ⁇ m.
- Boking was performed in the same manner as in Example 1 to obtain an oxide catalyst. At this time, the reduction rate of the catalyst precursor was 9.7%.
- the oxide catalyst obtained by the production method of the present embodiment has a particle content of 25 ⁇ m or less and an average particle size of catalyst precursor particles adjusted to a specific range, and propane gas phase contact ammonia Excellent propane conversion and acrylonitrile yield were shown in the oxidation reaction.
- the oxide catalysts of Comparative Examples 1 to 4 the content of the catalyst precursor particles of 25 ⁇ m or less and the average particle diameter were not adjusted to the specific ranges of the present embodiment, and the propane conversion rate and acrylonitrile were not adjusted. The yield was inferior.
- the oxide catalyst obtained after this baking was classified, and it was inferior to the propane conversion and the acrylonitrile yield.
- the manufacturing method of the oxide catalyst used for the gaseous-phase catalytic oxidation of propane or isobutane or a gaseous-phase catalytic ammoxidation reaction Comprising: The method of manufacturing stably the catalyst which shows a favorable yield is provided. can do.
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Abstract
Description
特許文献1には、プロパン又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に用いる触媒であって、特定の還元率及び比表面積を有するものが記載されている。この特定の還元率及び比表面積を有する触媒は、適度な活性を示し、反応成績(目的生成物の選択率と収率)が良く、また、経時的な収率低下が少ないことが記載されている。
一方、気相接触酸化又は気相接触アンモ酸化反応に用いる反応方式として、反応熱の除熱が容易で触媒層の温度がほぼ均一に保持できること、触媒を反応器から運転中に抜き出したり、触媒を追加したりすることが容易であること等の理由から、流動床反応が好まれている。流動床反応において用いる触媒としては、反応中の飛散によってロスする触媒を削減するため、或いは、流動性の改善のために粒子径を一定の範囲に調整した触媒が開示されている。
特許文献3には、金属酸化物触媒から遊離したモリブデン化合物が反応装置表面に針状結晶として析出する気相酸化反応において、粒径が20μm以下である触媒粒子が占める割合が2重量%以下である触媒を用いて反応させることにより、小さい粒子が針状結晶の間に絡まって固まることが少なくなり、反応器内の除熱コイルの伝熱係数の低下、配管の閉塞、触媒消費量の増加、反応装置の内表面が触媒粒子に覆われること等を防止できることが開示されている。
また、特許文献4及び5には、噴霧乾燥により得られた乾燥粒子を分級操作にかけ、所望の粒子径範囲外の乾燥粒子を分離し、分離した乾燥粒子を粉砕して噴霧乾燥前のスラリーに混合し再利用する方法が開示されている。
そこで、触媒性能が低い原因を本発明者が検討した結果、上述したような、粒径を調整して製造した触媒は、所望の還元率を満たしていないことが分かった。また、さらなる検討により、Moに加えてV及びNbを含有する酸化物触媒の場合には、小粒径の触媒が製造工程で存在することが、触媒性能、特に触媒又は後述する触媒前駆体の還元率の調整に影響することを突き止めた。特許文献1には、Mo、V及びNbを含有する触媒を所期の還元率で得たことが記載されているが、これは焼成工程等を比較的小さいスケールにして触媒を調製しているため、還元率の調整ムラが生じ難かったためと推定される。
即ち、特許文献1に記載されているように、酸化物の還元率が触媒性能に影響し得ることは知られているものの、特に、焼成工程をスケールアップし、長期間の連続式焼成で大量製造する場合に、望ましい還元率を実現する触媒の製造方法は知られていなかった。
[1]
プロパンも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に用いる酸化物触媒の製造方法であって、
(i)Mo、V、Nbを含み、Mo1原子に対するV、Nbの原子比をそれぞれa、bとしたときに、0.1≦a≦1、0.01≦b≦1、を満たす触媒原料混合液を調製する工程、
(ii)前記触媒原料混合液を乾燥する工程、及び
(iii)粒子径25μm以下の粒子含有率が20質量%以下であり、かつ、平均粒子径が35~70μmの粒子を不活性ガス雰囲気下で焼成する工程、
を含む、酸化物触媒の製造方法。
[2]
前記工程(iii)は、粒子径25μm以下の粒子含有率が8質量%以下であり、かつ、平均粒子径が45~65μmの粒子を不活性ガス雰囲気下で焼成する工程である、上記[1]記載の酸化物触媒の製造方法。
[3]
前記工程(ii)は、前記触媒原料混合液を噴霧乾燥する工程である、上記[1]又は[2]記載の酸化物触媒の製造方法。
[4]
前記工程(ii)で乾燥して得られる粒子の分級操作をさらに含む、上記[1]~[3]のいずれか記載の酸化物触媒の製造方法。
[5]
前記分級操作における粒子の回収率が75質量%以上である、上記[4]記載の酸化物触媒の製造方法。
[6]
前記酸化物触媒は、触媒構成元素の酸化物とシリカの全重量に対し、SiO2換算で10~80質量%のシリカに担持されている、上記[1]~[5]のいずれか記載の酸化物触媒の製造方法。
[7]
前記工程(iii)は、前段焼成した触媒前駆体粒子を本焼成する工程を含む、上記[1]~[6]のいずれか記載の酸化物触媒の製造方法。
[8]
前記本焼成における温度範囲が550~800℃である、上記[7]記載の酸化物触媒の製造方法。
[9]
前記前段焼成の温度範囲が250~400℃であり、前記本焼成の温度範囲が580~750℃である、上記[7]記載の酸化物触媒の製造方法。
[10]
焼成方法が連続式である、上記[7]~[9]のいずれか記載の酸化物触媒の製造方法。
[11]
焼成器を回転しながら焼成する、上記[7]~[10]のいずれか記載の酸化物触媒の製造方法。
[12]
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]~[11]のいずれか記載の製造方法により得られた酸化物触媒にプロパン又はイソブタンを接触させ、気相接触酸化又は気相接触アンモ酸化反応に供する工程を含む製造方法。
工程(i)は、Mo、V、Nbを含み、Mo1原子に対するV、Nbの原子比をそれぞれa、bとしたときに、0.1≦a≦1、0.01≦b≦1、を満たす触媒原料混合液を調製する工程である。
ヘプタモリブデン酸アンモニウム、メタバナジン酸アンモニウム、三酸化二アンチモン粉末を水に添加し、80℃以上に加熱して混合液(A)を調製する。このとき、例えば触媒がTeやBやCeを含む場合、テルル酸、ホウ酸、硝酸セリウムを同時に添加することができる。
次に、ニオブ酸とシュウ酸を水中で加熱撹拌して混合液(B)を調製する。混合液(B)は以下に示す方法で得られる。即ち、水にニオブ酸とシュウ酸を加え、撹拌することによって水溶液又は水性懸濁液を得る。懸濁する場合は、少量のアンモニア水を添加するか、又は、加熱することによってニオブ化合物の溶解を促進することができる。次いで、この水溶液又は水性懸濁液を冷却し、濾別することによってニオブ含有液を得る。冷却は簡便には氷冷によって、濾別は簡便にはデカンテーション又は濾過によって実施できる。得られたニオブ含有液にシュウ酸を適宜加え、好適なシュウ酸/ニオブ比に調製することもできる。シュウ酸/ニオブのモル比は、好ましくは2~5であり、より好ましくは2~4である。さらに、得られたニオブ混合液に過酸化水素を添加し、混合液(B)を調製してもよい。このとき、過酸化水素/ニオブのモル比は、好ましくは0.5~20であり、より好ましくは1~10である。
工程(ii)は、前記触媒原料混合液を乾燥する工程である。
乾燥粉体は通常、アンモニウム根、有機酸、無機酸を含んでおり、不活性ガスを流通させながら焼成する場合、これらが蒸発、分解等をする際に触媒構成元素が還元される。アンモニウム根は蒸発してアンモニアガスとなり、触媒前駆体粒子を気相から還元する。触媒前駆体の還元率は、特に後述する前段焼成における焼成時間や焼成温度により変化する。焼成時間が長い場合、あるいは焼成温度が高い場合は還元が進み易く、還元率が高くなる。比較的小粒径の前駆体を多く含む場合、典型的には平均粒子径が35μm未満、あるいは粒子径25μm以下の粒子含有率が20質量%を超えると、不活性ガスに同伴されたり焼成管の回転と共に舞い上がったりして焼成管中を逆戻りする小粒子が多く、焼成管内に滞留する時間が所望の時間より長い粒子が存在し、還元率を好ましい範囲にすることが困難になる。また、小粒子はアンモニアガスと接触する表面が多く還元されやすいことも考えられる。逆に、平均粒子径が70μmを超えると、粒子が大きいため、アンモニアガスと接触する表面が少なく還元されにくくなり、結果として、還元率を好ましい範囲に調整することが困難になると考えられる。
(25μm以下の粒子含有率)=(篩を通った粒子の質量)÷{(篩を通った粒子の質量)+(篩上に残った粒子の質量)}×100
本実施の形態の製造方法は、上記工程(i)及び工程(ii)に加えて、さらに(iii)粒子径25μm以下の粒子含有率が20質量%以下であり、かつ、平均粒子径が35~70μmの粒子を不活性ガス雰囲気下で焼成する工程を含む。
還元率(%)=((n0-n)/n0)×100・・・(1)
(式中:nは触媒前駆体における酸素以外の構成元素の原子価を満足する酸素原子の数であり、n0は触媒前駆体の酸素以外の構成元素がそれぞれの最高酸化数を有する時に必要な酸素原子の数である。)
により表される。触媒前駆体の還元率は、好ましくは8~12%、より好ましくは9~11%、さらに好ましくは9.5~10.5%である。
ビーカーに試料約200mgを精秤する。さらに、濃度が既知のKMnO4水溶液を過剰量添加する。さらに、精製水150mL、1:1硫酸(即ち、濃硫酸と精製水を容量比1/1で混合して得られる硫酸水溶液)2mLを添加した後、ビーカーに時計皿で蓋をし、70℃±2℃の湯浴中で1Hr攪拌し、試料を酸化させる。この時、KMnO4は過剰に存在させており、液中には未反応のKMnO4が存在するため、液色は紫色であることを確認する。酸化終了後、ろ紙にてろ過を行い、ろ液全量を回収する。濃度が既知のシュウ酸ナトリウム水溶液を、ろ液中に存在するKMnO4に対し過剰量添加し、液温が70℃となるように加熱攪拌する。液が無色透明になることを確認し、1:1硫酸2mLを添加する。液温を70℃±2℃に保ちながら攪拌を続け、濃度が既知のKMnO4水溶液で滴定する。液色がKMnO4によりかすかな淡桃色が約30秒続くところを終点とする。全KMnO4量、全Na2C2O4量から、試料の酸化に消費されたKMnO4量を求める。この値から、(n0-n)を算出し、これに基づき還元率を求める。
試料の構成元素が揮発、逃散しない条件で、触媒前駆体又は触媒が焼成された焼成温度よりも高い温度まで加熱し、酸素による完全酸化を行い、増加した重量(結合した酸素の量)を求め、これから(n0-n)の値を求め、これに基づき還元率を求める。
本実施の形態の好ましい酸化物触媒の例は、以下の組成式(2)で表される。
Mo1VaNbbXcYdOn・・・(2)
(式中、成分XはTe及びSbから選ばれる少なくとも1種以上の元素を示し、YはMn、W、B、Ti、Al、Ta、アルカリ金属、アルカリ土類金属から選ばれる1以上の元素を示し、a、b、c、d及びnは、それぞれ、バナジウム(V)、ニオブ(Nb)、元素X、元素Y及び酸素(O)のモリブデン(Mo)1原子に対する原子比を示し、0.1≦a≦1、0.01≦b≦1、0.01≦c≦1、0≦d≦1を満たし、nは酸素以外の構成元素の原子価によって決まる酸素原子の数である。)
本実施の形態の製造方法により得られた酸化物触媒を用いて、プロパン又はイソブタンを分子状酸素と気相で反応(気相接触酸化反応)させて、対応する不飽和カルボン酸(アクリル酸又はメタクリル酸)を製造することができる。また、この触媒を用いて、プロパン又はイソブタンをアンモニア及び分子状酸素と気相で反応(気相接触アンモ酸化反応)させて、対応する不飽和ニトリル(アクリロニトリル又はメタクリロニトリル)を製造することができる。
接触時間(sec・g/cc)=(W/F)×273/(273+T)×P
ここで、
W=触媒の重量(g)、
F=標準状態(0℃、1atm)での原料混合ガス流量(Ncc/sec)、
T=反応温度(℃)、そして
P=反応圧力(atm)である。
プロパン転化率(Pn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
アクリロニトリル収率(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原料液を調製した。水500kgにNb2O5として80.2質量%を含有するニオブ酸76.33kgとシュウ酸二水和物〔H2C2O4・2H2O〕29.02g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0.532(mol-Nb/kg-液)であった。
この液を95℃で1時間加熱撹拌することによって、ニオブ化合物が溶解した水溶液を得た。この水溶液を静置、氷冷後、固体を吸引濾過によって濾別し、均一なニオブ化合物水溶液を得た。同じような操作を数回繰り返して、得られたニオブ化合物水溶液を一つにし、ニオブ原料液とした。このニオブ原料液のシュウ酸/ニオブのモル比は下記の分析により2.60であった。
るつぼに、このニオブ原料液10gを精秤し、95℃で一夜乾燥後、600℃で1時間熱処理し、Nb2O50.7868gを得た。この結果から、ニオブ濃度は0.5920(mol-Nb/kg-液)であった。
300mLのガラスビーカーにこのニオブ原料液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。得られた溶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、1.54(mol-シュウ酸/kg)であった。
2KMnO4+3H2SO4+5H2C2O4→K2SO4+2MnSO4+10CO2+8H2O
得られたニオブ原料液を、以下の酸化物触媒の製造においてニオブ原料液として用いた。
組成式がMo1V0.24Nb0.092Sb0.26On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水18.07kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.69kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.58kg、三酸化二アンチモン〔Sb2O3〕を0.79kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.23kgに、H2O2として30質量%を含有する過酸化水素水0.43kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後に、SiO2として30.4質量%を含有するシリカゾル6.95kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.92kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。さらに、フュームドシリカ1.41kgを19.7kgの水に分散させた液を添加して原料混合液を得た。
なお、後述する「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。
(乾燥粉体の調製)
得られた原料混合液を、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℃、出口温度は120℃であった。
(分級操作)
得られた乾燥粉体を分級機にかけ、所望のファイン含有率・粒子径となるように調整した。分級機は、日清エンジニアリング(株)製ターボクラシファイアTC-25Mを用いた。分級機への粉体供給量は40kg/hr、風量7m3/min、ローター回転数は1250rpmであった。分級後、得られた乾燥粉体粒子の25μm以下の粒子含有率は1.8質量%であり、平均粒子径は55μmであった。平均粒子径は、BECKMAN COULTER製LS230により測定した。
(焼成)
内径200mm、長さ1500mmのSUS製焼成管に、高さ35mmの7枚の堰板を、加熱炉部分の長さを8等分するように設置した。この焼成管を5rpmで回転させながら、分級操作により得られた乾燥粉体を550g/hrの速度で流通し、8.2Nリットル/minの窒素ガス流通下、360℃まで約6時間かけて昇温し、360℃で2時間保持する温度プロファイルとなるように加熱炉の温度を設定し、前段連続式焼成を実施した。このときの触媒前駆体の還元率は、10.23%であった。別の内径200mm、長さ1800mmのSUS製焼成管で、高さ35mmの7枚の堰板を加熱炉部分の長さを8等分するように設置したものに、触媒前駆体を400g/hrの速度で流通し、焼成管を5rpmで回転させながら、8.0Nリットル/minの窒素ガス流通下、650℃まで2℃/minで昇温し、650℃で2時間焼成し、1℃/minで降温する温度プロファイルとなるように加熱炉の温度を設定し、本焼成を連続式で実施した。本焼成中、焼成管の粉導入側部分(加熱炉に覆われていない部分)に、打撃部先端がSUS製の質量3kgのハンマーを設置したハンマリング装置で、回転軸に垂直な方向で焼成管上部40mmの高さから15秒に1回打撃を加えた。本焼成中、焼成管内部への固着は少なく、触媒相温度の低下は起こらず、排出量も安定していた。振動加速度を振動計(旭化成テクノシステム(株)製MD-220)により測定したところ、51m/s2であった。
(触媒の性能評価)
内径25mmのバイコールガラス流動床型反応管に、酸化物触媒45gを充填し、反応温度440℃、反応圧力常圧下にプロパン:アンモニア:酸素:ヘリウム=1:1:3.0:13のモル比の混合ガスを接触時間3.0(sec・g/cc)で通過させた。触媒の性能を評価した結果、プロパン転化率89%、アクリロニトリル収率52.5%であった。
分級機へのローター回転数を1400rpmとした以外は実施例1と同様の方法により、酸化物触媒を得た。分級後の乾燥粉体粒子の25μm以下の粒子含有率は4.1質量%であり、平均粒子径は52μmであった。また、触媒前駆体の還元率は9.98%であった。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率88.2%、アクリロニトリル収率51.8%であった。
分級機へのローター回転数を1500rpmとした以外は実施例1と同様の方法により、酸化物触媒を得た。分級後の乾燥粉体粒子の25μm以下の粒子含有率は6.0質量%であり、平均粒子径は51μmであった。また、触媒前駆体の還元率は10.10%であった。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率87.9%、アクリロニトリル収率51.0%であった。
組成式がMo1V0.24Nb0.092Sb0.26On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水4.52kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を0.93kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.15kg、三酸化二アンチモン〔Sb2O3〕を0.20kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液0.81kgに、H2O2として30質量%を含有する過酸化水素水0.11kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後に、SiO2として30.4質量%を含有するシリカゾル1.74kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.23kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。さらに、フュームドシリカ0.35kgを4.93kgの水に分散させた液を添加して原料混合液を得た。
(乾燥粉体の調製)
得られた原料混合液を、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℃、出口温度は120℃であった。
(分級操作)
得られた乾燥粉体200gを目開き25μm、直径20cmの篩を用いて2分間バイブレーターをあてて篩にかけ、分級操作をおこなった。分級後、得られた乾燥粉体粒子の25μm以下の粒子含有率は0.2質量%であり、平均粒子径は56μmであった。平均粒子径は、BECKMAN COULTER製LS230により測定した。
(焼成)
分級操作により得られた乾燥粉体粒子100gを直径50mmのガラス製焼成管に充填し、0.25Nリットル/minの窒素ガス流通下、焼成管を回転させながら、360℃まで約6時間かけて昇温し、360℃で2時間保持した。このときの還元率は9.93%であった。その後、650℃まで2時間で昇温し、650℃で2時間焼成して触媒を得た。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率88.8%、アクリロニトリル収率52.8%であった。
打撃部先端がSUS製の質量2kgのハンマーを設置したハンマリング装置で、回転軸に垂直な方向で焼成管上部35mmの高さから15秒に1回打撃を加えた以外は、実施例1と同様の方法で酸化物触媒を得た。振動加速度を振動計(旭化成テクノシステム(株)製MD-220)により測定したところ、14m/s2であった。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率88.3%、アクリロニトリル収率52.1%であった。
打撃部先端がSUS製の質量13kgのハンマーを設置したハンマリング装置で、回転軸に垂直な方向で焼成管上部50mmの高さから15秒に1回打撃を加えた以外は、実施例1と同様の方法で酸化物触媒を得た。振動加速度を振動計(旭化成テクノシステム(株)製MD-220)により測定したところ、210m/s2であった。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率88.4%、アクリロニトリル収率52.4%であった。
実施例1と同様の方法で乾燥粉体を得た後、分級操作を行わずに実施例1と同様の方法で前段連続式焼成を実施した。
前段焼成により得られた触媒前駆体粒子200gを目開き25μm、直径20cmの篩を用いて2分間バイブレーターをあてて篩にかけ、分級操作をおこなった。分級後、得られた触媒前駆体粒子の25μm以下の粒子含有率は0.4質量%であり、平均粒子径は54μmであった。平均粒子径は、BECKMAN COULTER製LS230により測定した。このとき触媒前駆体の還元率は10.18%であった。
分級操作により得られた触媒前駆体粒子90gを直径50mmのガラス製焼成管に充填し、0.30Nリットル/minの窒素ガス流通下、焼成管を回転させながら、650℃まで2時間で昇温し、650℃で2時間焼成して触媒を得た。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率88.5%、アクリロニトリル収率51.9%であった。
噴霧乾燥後、分級操作を行わなかったこと以外は、実施例1と同様の方法により酸化物触媒を得た。乾燥粉体粒子の25μm以下の粒子含有率は25質量%であり、平均粒子径は34μmであった。このときの触媒前駆体の還元率は10.21%であった。また、25μm以下の粒子の還元率は10.54%であり、25μm以上の粒子の還元率は10.10%であった。酸化物触媒のアンモ酸化反応における性能を実施例1同様に評価したところ、プロパン転化率86%、アクリロニトリル収率47.5%であった。
分級機の回転数を3000rpmとした以外は、実施例1と同様の方法により酸化物触媒を得た。分級後の乾燥粉体粒子の25μm以下の粒子含有率は22質量%であり、平均粒子径は46μmであった。このときの触媒前駆体の還元率は10.15%であった。また、25μm以上の粒子の還元率は10.11%であり、25μm以下の粒子の還元率は10.30%であった。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率86.8%、アクリロニトリル収率49.5%であった。
分級機の回転数を2500rpmとした以外は、実施例1と同様の方法により酸化物触媒を得た。分級後の乾燥粉体粒子の25μm以下の粒子含有率は18質量%であり、平均粒子径は34μmであった。このときの触媒前駆体の還元率は10.0%であった。また、25μm以上の粒子の還元率は9.93%であり、25μm以下の粒子の還元率は10.32%であった。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率85.0%、アクリロニトリル収率48.8%であった。
目開き53μmの篩により分級操作を行ったこと以外は、実施例1と同様の方法により酸化物触媒を得た。分級後の乾燥粉体粒子の25μm以下の粒子含有率は0質量%であり、平均粒子径は71μmであった。このときの触媒前駆体の還元率は10.08%であった。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率87.1%、アクリロニトリル収率49.4%であった。
触媒前駆体粒子の分級を行わず、本焼成後に触媒の分級を実施例1と同条件で行ったこと以外は、実施例1と同様の方法により酸化物触媒を得た。分級後の触媒の25μm以下の粒子の含有率は2質量%であり、平均粒子径は53μmであった。このときの触媒前駆体の還元率は10.19%であった。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率87.6%、アクリロニトリル収率49.9%であった。
焼成工程を空気流通下で行った以外は実施例1と同様の方法により酸化物触媒を得た。このときの触媒前駆体の還元率は4.2%であった。酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価したところ、プロパン転化率38.7%、アクリロニトリル収率6.5%であった。
組成式がMo1V0.24Nb0.092Sb0.26W0.025On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水17.6kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.59kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.57kg、三酸化二アンチモン〔Sb2O3〕を0.77kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.14kgに、H2O2として30質量%を含有する過酸化水素水0.42kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後にSiO2として30.4質量%を含有するシリカゾル6.95kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.89kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。続いて、WO3として50.2質量%を含有するメタタングステン酸アンモニウム0.23kgを加え、さらに、フュームドシリカ1.41kgを19.71kgの水に分散させた液を添加して原料混合液を得た。「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。
(乾燥粉体の調製)
実施例1と同様に噴霧乾燥を行い、乾燥粉体を得た。
(分級操作)
実施例1と同様に分級を行った。分級後の乾燥粉体粒子の25μm以下の粒子含有率は1.7質量%であり、平均粒子径は52μmであった。
(焼成)
実施例1と同様に焼成を行い、酸化物触媒を得た。このとき触媒前駆体の還元率は10.19%であった。
(触媒の性能評価)
酸化物触媒のアンモ酸化反応における性能を実施例1と同様に評価をしたところ、プロパン転化率88.8%、アクリロニトリル収率53.0%であった。
組成式がMo1V0.24Nb0.092Sb0.26W0.04Ce0.008On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水17.22kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.52kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.56kg、三酸化二アンチモン〔Sb2O3〕を0.75kg、硝酸セリウム〔Ce(NO3)3・6H2O〕を0.07kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.07kgに、H2O2として30質量%を含有する過酸化水素水0.41kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後にSiO2として30.4質量%を含有するシリカゾル6.95kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.88kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。続いて、WO3として50.2質量%を含有するメタタングステン酸アンモニウム0.37kgを加え、さらに、フュームドシリカ1.41kgを19.71kgの水に分散させた液を添加して原料混合液を得た。「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。
(乾燥粉体の調製)
実施例1と同様に噴霧乾燥を行い、乾燥粉体を得た。
(分級操作)
実施例1と同様に分級を行なった。分級後の乾燥粉体粒子の25μm以下の粒子含有率は2.1質量%であり、平均粒子径は55μmであった。
(焼成)
実施例1と同様に焼成を行い、酸化物触媒を得た。このとき触媒前駆体の還元率は10.16%であった。
(触媒の性能評価)
実施例1と同様に酸化物触媒のアンモ酸化反応評価をしたところ、プロパン転化率88.9%、アクリロニトリル収率52.8%であった。
組成式がMo1V0.24Nb0.092Sb0.26B0.1Ce0.006On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水17.7kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.62kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.57kg、三酸化二アンチモン〔Sb2O3〕を0.77kg、硝酸セリウム〔Ce(NO3)3・6H2O〕を0.054kg、ホウ酸〔H3BO3〕を0.13kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.16kgに、H2O2として30質量%を含有する過酸化水素水0.42kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後にSiO2として30.4質量%を含有するシリカゾル6.95kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.90kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。さらに、フュームドシリカ1.41kgを19.7kgの水に分散させた液を添加して原料混合液を得た。なお、「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。
(乾燥粉体の調製)
実施例1と同様に噴霧乾燥を行い、乾燥粉体を得た。
(分級操作)
実施例1と同様に分級を行なった。分級後の乾燥粉体粒子の25μm以下の粒子含有率は1.6質量%であり、平均粒子径は53μmであった。
(焼成)
実施例1と同様に焼成を行い、酸化物触媒を得た。このとき触媒前駆体の還元率は9.5%であった。
(触媒の性能評価)
実施例1と同様に酸化物触媒のアンモ酸化反応評価をしたところ、プロパン転化率88.5%、アクリロニトリル収率52.6%であった。
組成式がMo1V0.22Nb0.092Sb0.25W0.04Mn0.003On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水15.5kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.56kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.52kg、三酸化二アンチモン〔Sb2O3〕を0.76kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.11kgに、H2O2として30質量%を含有する過酸化水素水0.42kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後にSiO2として30.4質量%を含有するシリカゾル6.95kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.89kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。続いて、硝酸マンガン〔Mn(NO3)2・6H2O〕0.017kg、WO3として50%を含有するメタタングステン酸アンモニウム0.37kgを加え、さらに、フュームドシリカ1.41kgを19.7kgの水に分散させた液を添加して原料混合液を得た。「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。
(乾燥粉体の調製)
実施例1と同様に噴霧乾燥を行い、乾燥粉体を得た。
(分級操作)
実施例1と同様に分級を行い、分級後の乾燥粉体粒子の25μm以下の粒子含有率は1.9質量%であり、平均粒子径は54μmであった。
(焼成)
実施例1と同様に焼成を行い、酸化物触媒を得た。このとき触媒前駆体の還元率は10.25%であった。
(触媒の収率評価)
実施例1と同様に酸化物触媒のアンモ酸化反応評価をしたところ、プロパン転化率88.6%、アクリロニトリル収率52.9%であった。
組成式がMo1V0.24Nb0.092Sb0.26Al0.009On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水18.03kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.68kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.58kg、三酸化二アンチモン〔Sb2O3〕を0.79kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.22kgに、H2O2として30質量%を含有する過酸化水素水0.43kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後にSiO2として30.4質量%を含有するシリカゾル6.95kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.92kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。続いて、酸化アルミニウム〔Al2O3〕0.0095kgを水0.29kgに分散させたものを添加し、さらに、フュームドシリカ1.41kgを19,71kgの水に分散させた液を添加して原料混合液を得た。「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。(乾燥粉体の調製)
実施例1と同様に噴霧乾燥を行い、乾燥粉体を得た。
(分級操作)
実施例1と同様に分級を行った。分級後の乾燥粉体粒子の25μm以下の粒子含有率は1.8質量%であり、平均粒子径は53μmであった。
(焼成)
実施例1と同様に焼成を行い、酸化物触媒を得た。このときの触媒前駆体の還元率は9.89%であった。
(触媒の性能評価)
実施例1同様に酸化物触媒のアンモ酸化反応評価をしたところ、プロパン転化率87.7%、アクリロニトリル収率51.9%であった。
組成式がMo1V0.24Nb0.092Sb0.26Ce0.005Ta0.01On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水17.2kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.64kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.58kg、三酸化二アンチモン〔Sb2O3〕を0.78kg、硝酸セリウム〔Ce(NO3)3・6H2O〕を0.045kg、タンタル酸0.052kgを加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.18kgに、H2O2として30質量%を含有する過酸化水素水0.43kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後にSiO2として30.4質量%を含有するシリカゾル6.95kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.91kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。さらに、フュームドシリカ1.41kgを19.71kgの水に分散させた液を添加して原料混合液を得た。「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。
(乾燥粉体の調製)
実施例1と同様に噴霧乾燥を行い、乾燥粉体を得た。
(分級操作)
実施例1と同様に分級を行った。分級後の乾燥粉体粒子の25μm以下の粒子含有率は2.0質量%であり、平均粒子径は52μmであった。
(焼成)
実施例1と同様に焼成を行い、酸化物触媒を得た。このときの触媒前駆体の還元率は9.95%であった。
(触媒の性能評価)
実施例1と同様に酸化物触媒のアンモ酸化反応評価をしたところ、プロパン転化率87.9%、アクリロニトリル収率52.1%であった。
組成式がMo1V0.24Nb0.092Sb0.26On/47質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水17.1kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.49kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.55kg、三酸化二アンチモン〔Sb2O3〕を0.75kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.05kgに、H2O2として30質量%を含有する過酸化水素水0.41kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後にSiO2として30.4質量%を含有するシリカゾル7.42kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.87kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。さらに、フュームドシリカ1.50kgを21.1kgの水に分散させた液を添加して原料混合液を得た。なお、「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。
(乾燥粉体の調製)
実施例1と同様に噴霧乾燥を行い、乾燥粉体を得た。
(分級操作)
実施例1と同様に分級を行った。分級後の乾燥粉体粒子の25μm以下の粒子含有率は1.5質量%であり、平均粒子径は56μmであった。
(焼成)
実施例1と同様に焼成を行い、酸化物触媒を得た。このとき触媒前駆体の還元率は10.32%であった。
(触媒の性能評価)
実施例1と同様に酸化物触媒のアンモ酸化反応評価をしたところ、プロパン転化率89.0%、アクリロニトリル収率52.9%であった。
組成式がMo1V0.24Nb0.092Sb0.26Ti0.008On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水18.0kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.68kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.58kg、三酸化二アンチモン〔Sb2O3〕を0.79kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.22kgに、H2O2として30質量%を含有する過酸化水素水0.43kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後にSiO2として30.4質量%を含有するシリカゾル6.95kgを添加した。次いで、H2O2として30質量%を含有する過酸化水素水0.92kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。続いて、酸化チタン〔TiO2〕0.013kgを水0.14kg中で攪拌・分散させたもの、さらに、フュームドシリカ1.41kgを19.71kgの水に分散させた液を添加して原料混合液を得た。「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。
(乾燥粉体の調製)
実施例1と同様に噴霧乾燥を行い、乾燥粉体を得た。
(分級操作)
実施例1と同様に分級を行った。分級後の乾燥粉体粒子の25μm以下の粒子含有率は2.1質量%であり、平均粒子径は51μmであった。
(焼成)
実施例1と同様に焼成を行い、酸化物触媒を得た。このとき触媒前駆体の還元率は9.99%であった。
(触媒の性能評価)
実施例1と同様に酸化物触媒のアンモ酸化反応評価をしたところ、プロパン転化率87.9%、アクリロニトリル収率51.8%であった
組成式がMo1V0.24Nb0.092Te0.26On/44質量%-SiO2で示される触媒を次のようにして製造した。
(原料混合液の調製)
水18.3kgにヘプタモリブデン酸アンモニウム〔(NH4)6Mo7O24・4H2O〕を3.74kg、メタバナジン酸アンモニウム〔NH4VO3〕を0.59kg、テルル酸〔H6TeO6〕を1.06kg加え、攪拌しながら90℃で2.5時間加熱して水性混合液A-1とした。
上記ニオブ原料液3.05kgに、H2O2として30質量%を含有する過酸化水素水0.44kgを添加した。液温をおよそ20℃に維持し、攪拌混合して、水性液B-1とした。
得られた水性混合液A-1を70℃に冷却した後にSiO2として30.4質量%を含有するシリカゾル6.95kgを添加し、50℃で1時間撹拌混合した。次に水性液B-1を添加した。さらに、フュームドシリカ1.41kgを19.7kgの水に分散させた液を添加して原料混合液を得た。「乾燥粉体の調製」工程及び「焼成」工程を連続式で行うために、「原料混合液の調製」工程を10回繰り返し、原料混合液を合計約80kg調製した。
(乾燥粉体の調製)
実施例1と同様に噴霧乾燥を行い、乾燥粉体を得た。
(分級操作)
実施例1と同様に分級を行った。分級後の乾燥粉体粒子の25μm以下の粒子含有率は2.2質量%であり、平均粒子径は50μmであった。
(焼成)
実施例1と同様に焼成を行い、酸化物触媒を得た。このとき触媒前駆体の還元率は、9.7%であった。
(触媒の性能評価)
実施例1と同様に酸化物触媒のアンモ酸化反応評価をしたところ、プロパン転化率88.0%、アクリロニトリル収率52.4%であった
以下の表1及び2に、各実施例及び比較例における酸化物触媒の組成、物性、性能評価等をまとめた。なお、表中のファイン率とは、粒子径25μm以下の粒子含有率(質量%)のことを示す。
これに対して比較例1~4の酸化物触媒は、触媒前駆体粒子の25μm以下の粒子含有率及び平均粒子径が本実施の形態の特定範囲に調整されておらず、プロパン転化率及びアクリロニトリル収率に劣っていた。
また、比較例5では、本焼成後に得られた酸化物触媒を分級しており、プロパン転化率及びアクリロニトリル収率に劣っていた。
さらに、比較例6では、空気流通下で焼成を行っており、プロパン転化率及びアクリロニトリル収率に劣っていた。
従って、本実施の形態によれば、プロパンも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に用いる酸化物触媒の製造方法であって、良好な収率を示す触媒を、効率良く、安定的に製造する方法を提供することができることが実証された。
Claims (12)
- プロパンも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に用いる酸化物触媒の製造方法であって、
(i)Mo、V、Nbを含み、Mo1原子に対するV、Nbの原子比をそれぞれa、bとしたときに、0.1≦a≦1、0.01≦b≦1、を満たす触媒原料混合液を調製する工程、
(ii)前記触媒原料混合液を乾燥する工程、及び
(iii)粒子径25μm以下の粒子含有率が20質量%以下であり、かつ、平均粒子径が35~70μmの粒子を不活性ガス雰囲気下で焼成する工程、
を含む、酸化物触媒の製造方法。 - 前記工程(iii)は、粒子径25μm以下の粒子含有率が8質量%以下であり、かつ、平均粒子径が45~65μmの粒子を不活性ガス雰囲気下で焼成する工程である、請求項1記載の酸化物触媒の製造方法。
- 前記工程(ii)は、前記触媒原料混合液を噴霧乾燥する工程である、請求項1又は2記載の酸化物触媒の製造方法。
- 前記工程(ii)で乾燥して得られる粒子の分級操作をさらに含む、請求項1~3のいずれか1項記載の酸化物触媒の製造方法。
- 前記分級操作における粒子の回収率が75質量%以上である、請求項4記載の酸化物触媒の製造方法。
- 前記酸化物触媒は、触媒構成元素の酸化物とシリカの全重量に対し、SiO2換算で10~80質量%のシリカに担持されている、請求項1~5のいずれか1項記載の酸化物触媒の製造方法。
- 前記工程(iii)は、前段焼成した触媒前駆体粒子を本焼成する工程を含む、請求項1~6のいずれか1項記載の酸化物触媒の製造方法。
- 前記本焼成における温度範囲が550~800℃である、請求項7記載の酸化物触媒の製造方法。
- 前記前段焼成の温度範囲が250~400℃であり、前記本焼成の温度範囲が580~750℃である、請求項7記載の酸化物触媒の製造方法。
- 焼成方法が連続式である、請求項7~9のいずれか1項記載の酸化物触媒の製造方法。
- 焼成器を回転しながら焼成する、請求項7~10のいずれか1項記載の酸化物触媒の製造方法。
- 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1~11いずれか1項記載の製造方法により得られた酸化物触媒にプロパン又はイソブタンを接触させ、気相接触酸化又は気相接触アンモ酸化反応に供する工程を含む製造方法。
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Publication number | Publication date |
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TWI399240B (zh) | 2013-06-21 |
US20100286432A1 (en) | 2010-11-11 |
KR20100097174A (ko) | 2010-09-02 |
EP2226121A1 (en) | 2010-09-08 |
KR101191572B1 (ko) | 2012-10-15 |
TW200942325A (en) | 2009-10-16 |
CN101909745B (zh) | 2013-04-17 |
EP2226121A4 (en) | 2011-05-11 |
CN101909745A (zh) | 2010-12-08 |
US9731285B2 (en) | 2017-08-15 |
JP5191008B2 (ja) | 2013-04-24 |
EP2226121B1 (en) | 2015-08-26 |
JPWO2009081758A1 (ja) | 2011-05-06 |
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