JP2006055681A - Composite oxide catalyst - Google Patents
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- JP2006055681A JP2006055681A JP2004236956A JP2004236956A JP2006055681A JP 2006055681 A JP2006055681 A JP 2006055681A JP 2004236956 A JP2004236956 A JP 2004236956A JP 2004236956 A JP2004236956 A JP 2004236956A JP 2006055681 A JP2006055681 A JP 2006055681A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 13
- 150000002825 nitriles Chemical class 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000001294 propane Substances 0.000 claims description 43
- 238000002360 preparation method Methods 0.000 claims description 35
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 29
- 230000003197 catalytic effect Effects 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 239000001282 iso-butane Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000013076 target substance Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 45
- 239000010955 niobium Substances 0.000 description 39
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 32
- 239000007789 gas Substances 0.000 description 30
- 238000005259 measurement Methods 0.000 description 29
- 238000004453 electron probe microanalysis Methods 0.000 description 28
- 239000012071 phase Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 229910052758 niobium Inorganic materials 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000001133 acceleration Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- -1 inorganic acid salt Chemical class 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 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 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000002821 niobium Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005211 surface analysis Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 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 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 description 1
- JGHNXMHWDGTLQX-UHFFFAOYSA-N O.O.O.[Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound O.O.O.[Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JGHNXMHWDGTLQX-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 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
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 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
- 239000011148 porous material Substances 0.000 description 1
- LXXCECZPOWZKLC-UHFFFAOYSA-N praseodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LXXCECZPOWZKLC-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- LACHWJIJRQDEJY-UHFFFAOYSA-N scandium(3+) trinitrate tetrahydrate Chemical compound O.O.O.O.[N+](=O)([O-])[O-].[Sc+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] LACHWJIJRQDEJY-UHFFFAOYSA-N 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は、プロパンまたはイソブタンの気相接触酸化または気相接触アンモ酸化反応に用いる複合酸化物触媒、および該複合酸化物触媒を用いる不飽和酸または不飽和ニトリルの製造方法に関する。 The present invention relates to a composite oxide catalyst used for gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane, and a method for producing an unsaturated acid or an unsaturated nitrile using the composite oxide catalyst.
従来、プロピレンまたはイソブチレンを気相接触酸化または気相接触アンモ酸化して対応する不飽和カルボン酸または不飽和ニトリルを製造する方法が良く知られているが、近年、プロピレンまたはイソブチレンに替わってプロパンまたはイソブタンを気相接触酸化または気相接触アンモ酸化によって対応する不飽和カルボン酸または不飽和ニトリルを製造する方法が着目されており、種々の酸化物触媒が提案されている。例えば、Ｍｏ−Ｖ−Ｎｂ−（Ｓｂ／Ｔｅ）を含む酸化物触媒が、特許文献１、２などに開示されている。 Conventionally, a process for producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by vapor-phase catalytic oxidation or vapor-phase catalytic ammoxidation of propylene or isobutylene is well known, but in recent years propane or isobutylene is replaced by propane or isobutylene. A method for producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by gas phase catalytic oxidation or gas phase catalytic ammoxidation of isobutane has attracted attention, and various oxide catalysts have been proposed. For example, Patent Documents 1 and 2 disclose oxide catalysts containing Mo-V-Nb- (Sb / Te).
また、Ｍｏ、Ｖを含有する触媒に対して、希土類元素等を添加し、更なる触媒性能の向上を達成した例が、特許文献１、３〜６に開示されている。
すなわち、プロパンまたはイソブタンを気相接触酸化または気相接触アンモ酸化し、対応する不飽和カルボン酸または不飽和ニトリルを製造するにあたり、Ｍｏ−Ｖを含有する酸化物触媒に希土類元素等を添加した触媒が有効であり、従来から多くの研究がなされてきた。
Further, Patent Documents 1 and 3 to 6 disclose examples in which a rare earth element or the like is added to a catalyst containing Mo and V to further improve the catalyst performance.
That is, a catalyst in which a rare earth element or the like is added to an oxide catalyst containing Mo-V for producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by subjecting propane or isobutane to gas phase catalytic oxidation or gas phase catalytic ammoxidation. Is effective, and many studies have been made.
特許文献１、３、５、６に開示された希土類元素等の成分を添加したＭｏ−Ｖ含有酸化物触媒を、プロパンまたはイソブタンの気相接触酸化または気相接触アンモ酸化反応に用いるとき、未だ目的物の収率は不十分であった。特に、流動床反応に好適な担持触媒は、目的物の収率が低下しがちである。その反応性能が不十分である原因は、特許文献６に開示されているように、希土類元素等の添加成分がスラリー調合工程において他の金属成分と好ましくない相互作用を起こすことが知られている。 When the Mo-V-containing oxide catalyst added with components such as rare earth elements disclosed in Patent Documents 1, 3, 5, and 6 is used for gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane, it is still The yield of the target product was insufficient. In particular, the supported catalyst suitable for the fluidized bed reaction tends to decrease the yield of the target product. The reason why the reaction performance is insufficient is known that, as disclosed in Patent Document 6, an additive component such as a rare earth element causes an undesirable interaction with other metal components in the slurry preparation step. .
例えば、特許文献１、３、５、６では、比較的平均粒径の大きい、水不溶性の固体を使用すれば、スラリー調合工程での好ましくない相互作用が低減し、目的物の収率が向上する旨を教示している。しかしながら、上記の公報においては、添加元素の触媒成分への均一な分散性に関する記載が一切ないばかりか、使用している固体原料は水不溶性であるため、工業的な触媒製造時に、配管中での詰まりを生ずる恐れがあった。また、過剰に希土類元素等を添加すれば、添加成分から成る酸化物粒子が触媒表面に露出し、目的物の分解反応を促進させ、収率を低下させる。
特許文献４では、焼成後に得られた触媒に、溶液として所望の元素を添加する含浸法について開示されている。この場合、触媒粒子表面および細孔表面にのみ添加成分が分布するため、粒子内部での均一性が良好でないばかりか、含浸操作後に再度焼成が必要となり、操作が煩雑と考えられるばかりか、含浸溶液中に、他の金属成分が溶出し、反応性能が低下する恐れがあること等の問題点があった。
For example, in Patent Documents 1, 3, 5, and 6, if a water-insoluble solid having a relatively large average particle size is used, undesirable interactions in the slurry preparation process are reduced, and the yield of the target product is improved. Teaching to do so. However, in the above publication, there is no description about the uniform dispersibility of the additive element in the catalyst component, and since the solid raw material used is water-insoluble, There was a risk of clogging. Moreover, if rare earth elements or the like are added excessively, oxide particles composed of the added components are exposed on the catalyst surface, promoting the decomposition reaction of the target product and reducing the yield.
Patent Document 4 discloses an impregnation method in which a desired element is added as a solution to a catalyst obtained after calcination. In this case, since the additive component is distributed only on the catalyst particle surface and the pore surface, not only the uniformity inside the particle is not good, but it is necessary to calcinate again after the impregnation operation, and the operation is considered to be complicated. There were problems such as other metal components eluting into the solution and the reaction performance being likely to deteriorate.
一方、工業的触媒においては、初期の反応性能だけでなく、反応を長時間実施した場合にも反応性能を維持することが重要である。劣化した触媒を抜き出し、新しい触媒を補充できればよいが、操作に手間がかかる上、連続運転の妨げになるほか、経済的にも不利である。また、劣化した触媒を抜き出して、再生して補充する方法も考えられるが、再生に時間がかかったり、複雑な再生装置が必要であったり、充分に再生できない等の問題点がある。このため、収率低下の少ない触媒が求められている。例えば、特許文献２においては、Ｍｏ−Ｖ−Ｎｂ−Ｔｅ触媒を１３００時間、プロパンの気相接触アンモ酸化反応させ、アクリロニトリル収率をほぼ維持する触媒例が開示されている。しかしながら、上記の公報における反応評価は１３００時間程度の比較的短い期間のものであり、工業的に必要とされる性能を十分には満足していない。また、希土類元素等を添加したＭｏ−Ｖ含有触媒に関しては、長時間の反応を実施することに関して、何ら記載されていない。 On the other hand, in an industrial catalyst, it is important to maintain not only the initial reaction performance but also the reaction performance when the reaction is carried out for a long time. It is sufficient if the deteriorated catalyst can be extracted and replenished with a new catalyst. However, it is troublesome in operation, hinders continuous operation, and is economically disadvantageous. A method of extracting and replenishing a deteriorated catalyst is also conceivable, but there are problems such as that it takes time to regenerate, a complicated regenerator is required, and sufficient regeneration cannot be performed. For this reason, a catalyst with little yield reduction is calculated | required. For example, Patent Document 2 discloses a catalyst example in which a Mo—V—Nb—Te catalyst is subjected to a gas phase catalytic ammoxidation reaction of propane for 1300 hours to substantially maintain an acrylonitrile yield. However, the reaction evaluation in the above publication is of a relatively short period of about 1300 hours and does not sufficiently satisfy the industrially required performance. In addition, regarding the Mo-V-containing catalyst to which rare earth elements or the like are added, there is no description regarding performing a long-time reaction.
本発明は、少なくともＭｏ、Ｖおよび成分Ｘ（成分Ｘはアルカリ土類金属元素および希土類元素から選ばれる少なくとも１種以上の元素）を含む不飽和酸または不飽和ニトリルの製造に用いる複合酸化物触媒において、成分Ｘが触媒粒子内で均一に分布した、目的物の選択率が高い、新規な複合酸化物触媒を提供することを目的とする。本発明は、更には、上記の複合酸化物触媒を用いて、プロパンまたはイソブタンを気相接触酸化または気相接触アンモ酸化反応させ、対応する不飽和酸または不飽和ニトリルを製造する方法を提供することを目的とする。 The present invention relates to a composite oxide catalyst used for producing an unsaturated acid or unsaturated nitrile containing at least Mo, V and component X (component X is at least one element selected from alkaline earth metal elements and rare earth elements). An object of the present invention is to provide a novel composite oxide catalyst in which the component X is uniformly distributed in the catalyst particles and the selectivity of the target product is high. The present invention further provides a process for producing a corresponding unsaturated acid or unsaturated nitrile by subjecting propane or isobutane to gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction using the above complex oxide catalyst. For the purpose.
本発明者らは上記目的を達成するために鋭意検討した結果、本発明に到達した。すなわち、本発明は、下記のとおりである。
（１）少なくともＭｏ、Ｖおよび成分Ｘ（成分Ｘはアルカリ土類金属元素および希土類元素から選ばれる少なくとも１種以上の元素）を含む複合酸化物触媒であって、シリカを含む担体に担持され、成分Ｘが触媒粒子内で均一に分布していることを特徴とする複合酸化物触媒。
（２）該複合酸化物触媒において、該複合酸化物触媒粒子の断面を組成分析した時の成分ＸとＳｉの信号強度比の分散値Ｄｘが、０＜Ｄｘ＜０．５の範囲にあることを特徴とする上記（１）の複合酸化物触媒。
（３）該複合酸化物触媒が成分Ｙ（成分ＹはＴｅ、Ｓｂから選ばれる少なくとも１種以上の元素）を含むことを特徴とする上記（１）、（２）の複合酸化物触媒。
（４）該複合酸化物触媒がＮｂを含むことを特徴とする上記（１）〜（３）の複合酸化物触媒。
（５）成分ＸがＳｃ、Ｙ（イットリウム）、Ｌａ、Ｃｅ、Ｐｒ、Ｙｂから選ばれる少なくとも１種以上の元素であることを特徴とする上記（１）〜（４）の複合酸化物触媒。
（６）該複合酸化物触媒が、ＳｉＯ２換算で２０〜６０重量％のシリカに担持されていることを特徴とする上記（１）〜（５）の複合酸化物触媒。
（７）該複合酸化物触媒がプロパンまたはイソブタンの気相接触酸化反応または気相接触アンモ酸化反応に用いられることを特徴とする上記（１）〜（６）の複合酸化物触媒。
（８）上記（１）〜（７）の複合酸化物触媒を用いることを特徴とする不飽和酸または不飽和ニトリルの製造方法。
（９）少なくともＭｏ化合物、Ｖ化合物およびＸ化合物を含む混合液にシリカを混合し、得られた原料調合液を噴霧乾燥して乾燥粉体を得て、この乾燥粉体を焼成することを特徴とする上記（１）〜（７）に記載の複合酸化物触媒の製造方法。
The inventors of the present invention have reached the present invention as a result of intensive studies to achieve the above object. That is, the present invention is as follows.
(1) A composite oxide catalyst containing at least Mo, V and component X (component X is at least one element selected from alkaline earth metal elements and rare earth elements), supported on a support containing silica, A composite oxide catalyst, wherein the component X is uniformly distributed in the catalyst particles.
(2) In the composite oxide catalyst, the dispersion value D x of the signal intensity ratio between the component X and Si when the cross section of the composite oxide catalyst particle is compositionally analyzed is in the range of 0 <D x <0.5. The composite oxide catalyst according to (1) above, wherein
(3) The composite oxide catalyst according to (1) or (2) above, wherein the composite oxide catalyst contains component Y (component Y is at least one element selected from Te and Sb).
(4) The composite oxide catalyst according to (1) to (3) above, wherein the composite oxide catalyst contains Nb.
(5) The composite oxide catalyst according to (1) to (4) above, wherein the component X is at least one element selected from Sc, Y (yttrium), La, Ce, Pr, and Yb.
(6) The composite oxide catalyst according to (1) to (5) above, wherein the composite oxide catalyst is supported on 20 to 60% by weight of silica in terms of SiO 2 .
(7) The composite oxide catalyst according to the above (1) to (6), wherein the composite oxide catalyst is used for a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction of propane or isobutane.
(8) A method for producing an unsaturated acid or an unsaturated nitrile, comprising using the composite oxide catalyst according to the above (1) to (7).
(9) Silica is mixed with a mixed solution containing at least a Mo compound, a V compound and an X compound, the obtained raw material preparation solution is spray-dried to obtain a dry powder, and the dry powder is fired. The method for producing a composite oxide catalyst according to the above (1) to (7).
本発明によれば、成分Ｘを担体粒子内に均一に分布させた、新規な複合酸化物触媒を提供できる。更には、本発明により得られる複合酸化物触媒を用いることにより、プロパンまたはイソブタンから対応する不飽和酸または不飽和ニトリルを高い収率で製造することができる。 According to the present invention, it is possible to provide a novel composite oxide catalyst in which component X is uniformly distributed in the carrier particles. Furthermore, by using the composite oxide catalyst obtained by the present invention, the corresponding unsaturated acid or unsaturated nitrile can be produced in high yield from propane or isobutane.
以下、本発明を詳細に説明する。本発明の複合酸化物触媒は、少なくともＭｏ、Ｖおよび成分Ｘ（成分Ｘはアルカリ土類金属元素および希土類元素から選ばれる少なくとも１種以上の元素）を含む複合酸化物触媒であって、シリカを含む担体に担持され、成分Ｘが触媒粒子内で均一に分布していることを特徴とする複合酸化物触媒であり、好ましい複合酸化物触媒の具体例としては下記の一般組成式（１）で示されるものを例示することができる。
Ｍｏ１ＶａＮｂｂＹｃＸｄＯｎ （１）
（式中、ａ、ｂ、ｃ、ｄ、ｎはＭｏ１原子当たりの原子比を表し、ａは０．０１≦ａ≦１、ｂは０．０１≦ｂ≦１、ｃは０．０１≦ｃ≦１、ｄは０＜ｄ＜１、そしてｎは構成金属の原子価によって決まる数である。）
Hereinafter, the present invention will be described in detail. The composite oxide catalyst of the present invention is a composite oxide catalyst containing at least Mo, V and component X (component X is at least one element selected from alkaline earth metal elements and rare earth elements), The composite oxide catalyst is characterized in that the component X is supported on the carrier, and the component X is uniformly distributed in the catalyst particles. A specific example of a preferable composite oxide catalyst is represented by the following general composition formula (1): What is shown can be exemplified.
Mo 1 V a Nb b Y c X d O n (1)
(Wherein, a, b, c, d and n represent atomic ratios per Mo atom, a is 0.01 ≦ a ≦ 1, b is 0.01 ≦ b ≦ 1, and c is 0.01 ≦ c. ≦ 1, d is 0 <d <1, and n is a number determined by the valence of the constituent metals.
また、Ｍｏ１原子当たりの原子比ａ〜ｃは、それぞれ、０．１〜０．４、０．０１〜０．２、０．１〜０．５が好ましい。
成分ＸのＭｏ１原子当たりの原子比であるｄは、０．００１≦ｄ＜１が好ましく、０．００１≦ｄ＜０．１が更に好ましく、０．００２≦ｄ＜０．０１が特に好ましい。成分Ｘの元素としては、Ｓｒ、Ｂａ、Ｓｃ、Ｙ（イットリウム）、Ｌａ、Ｃｅ、Ｐｒ、Ｙｂが好ましく、Ｃｅが特に好ましい。
成分ＹのＭｏ１原子当たりの原子比であるｃは、０．０１〜０．６が好ましく、０．１〜０．４が更に好ましい。成分Ｙの元素としては、Ｔｅ、Ｓｂが好適に用いられるが、工業的にはＳｂを用いることが好ましい。
The atomic ratios a to c per Mo atom are preferably 0.1 to 0.4, 0.01 to 0.2, and 0.1 to 0.5, respectively.
D which is an atomic ratio per Mo atom of the component X is preferably 0.001 ≦ d <1, more preferably 0.001 ≦ d <0.1, and particularly preferably 0.002 ≦ d <0.01. As the element of component X, Sr, Ba, Sc, Y (yttrium), La, Ce, Pr, and Yb are preferable, and Ce is particularly preferable.
C, which is an atomic ratio per Mo atom of the component Y, is preferably 0.01 to 0.6, and more preferably 0.1 to 0.4. Te and Sb are preferably used as the element of component Y, but Sb is preferably used industrially.
本発明の製造方法により得られる複合酸化物触媒は、シリカを主成分とする担体によって担持された担持触媒であることが好ましい。複合酸化物触媒がシリカを主成分とする担体によって担持された触媒の場合、高い機械的強度を有するので、流動床反応器を用いた気相接触酸化反応または気相接触アンモ酸化反応に好適である。シリカを主成分とする担体中のシリカの含有量は、触媒構成元素の酸化物と担体から成る担持酸化物触媒の全重量に対して、ＳｉＯ２換算で２０〜６０重量％であることが好ましく、より好ましくは２５〜５５重量％である。 The composite oxide catalyst obtained by the production method of the present invention is preferably a supported catalyst supported by a support mainly composed of silica. In the case where the composite oxide catalyst is a catalyst supported by a support containing silica as a main component, it has high mechanical strength and is suitable for gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction using a fluidized bed reactor. is there. The content of silica in the support mainly composed of silica is preferably 20 to 60% by weight in terms of SiO 2 with respect to the total weight of the supported oxide catalyst comprising the oxide of the catalyst constituent element and the support. More preferably, it is 25 to 55% by weight.
本発明の複合酸化物触媒において、特に重要な点の一つは、成分Ｘが触媒粒子内で均一に分布していることである。ここで、均一とは、触媒粒子中で成分Ｘの分布に偏りがないことを言う。好ましくは、成分Ｘを含有する酸化物粒子の８０％以上（重量比率）が１μｍ以下の粒径を有する微粒子として、触媒粒子内に存在することを言う。なお好適に均一を定義すれば、均一とは、該触媒粒子の断面を組成分析した時に成分Ｘ（成分Ｘはアルカリ土類金属元素および希土類元素から選ばれる少なくとも１種以上の元素）とＳｉとの信号強度比の分散値（標準偏差を平均値で除した値）が０〜０．５の範囲にあることを言う。また、該分散値はＤｘと表すことにする。 In the composite oxide catalyst of the present invention, one particularly important point is that the component X is uniformly distributed in the catalyst particles. Here, “uniform” means that the distribution of the component X is not biased in the catalyst particles. Preferably, 80% or more (weight ratio) of the oxide particles containing component X are present in the catalyst particles as fine particles having a particle size of 1 μm or less. In addition, if uniformly defined, preferably, uniform means component X (component X is at least one element selected from alkaline earth metal elements and rare earth elements) and Si when composition of the cross section of the catalyst particles is analyzed. The signal intensity ratio variance (the value obtained by dividing the standard deviation by the average value) is in the range of 0 to 0.5. The variance value is represented as Dx.
上記の組成分析には、一般的な組成分析方法、例えば、ＳＥＭ−ＥＤＸ、ＸＰＳ、ＳＩＭＳ、ＥＰＭＡ等を用いることができる。好ましくはＥＰＭＡを用いることができる。
ここで、ＥＰＭＡとは、Ｅｌｅｃｔｒｏｎ Ｐｒｏｂｅ Ｘ−ｒａｙ Ｍｉｃｒｏａｎａｌｙｚｅｒ (但し、このＸ−ｒａｙを省略して呼ばれることもある。)の通称であり、この分析装置は、加速された電子線を物質に照射することによって得られる特性Ｘ線を観測することにより、電子線を当てた微小領域（スポット）の組成分析を行うことができる装置である。このＥＰＭＡによって、一般に、触媒粒子や担体粒子等の固体粒子の断面について、特定元素の濃度分布や組成変化の情報が得られる。
For the above composition analysis, a general composition analysis method such as SEM-EDX, XPS, SIMS, EPMA or the like can be used. Preferably, EPMA can be used.
Here, EPMA is a common name of Electron Probe X-ray Microanalyzer (sometimes called by omitting this X-ray), and this analyzer irradiates a substance with an accelerated electron beam. By observing characteristic X-rays obtained in this way, the apparatus can perform composition analysis of a minute region (spot) irradiated with an electron beam. This EPMA generally provides information on the concentration distribution and composition change of a specific element with respect to the cross section of solid particles such as catalyst particles and carrier particles.
なお、本発明において、上記ＥＰＭＡによる成分ＸとＳｉの強度比の分散値（ＤＸ）は、測定しようとする粒子の断面について、通常の触媒分野で行われる粒子断面のＥＰＭＡによる面分析の手法に従って、次のようにして測定・算出されたものである。すなわち、まず、その触媒粒子断面の任意の位置（ｘ，ｙ）に対するＳｉのＸ線ピーク強度（カウント数IＳｉ）の分布の測定を、触媒粒子断面の全領域をカバーするように行う。ついで、同様に、成分Ｘについても触媒粒子断面の全領域をカバーするようにＸ線ピーク強度（カウント数ＩＸ）の分布を測定する。得られたＳｉおよび成分Ｘに関する一連のデータ（ｘ，ｙ，IＳｉ、ＩＸ）を基に、同一の位置（ｘ、ｙ）での成分ＸおよびＳｉのピーク強度比ＩＲ（IＲ＝IＸ／ＩＳｉ）を求め、ＩＲの単純平均（IＲ）ａｖおよび標準偏差Ｓを求める。その標準偏差Ｓを単純平均（IＲ）ａｖで除した値を前記の分散値（ＤＸ）とする。この時、単純平均及び標準偏差は通常の方法で求めればよい。 In the present invention, the dispersion value (D X ) of the intensity ratio between the component X and Si by the above-mentioned EPMA is the method of surface analysis by EPMA of the particle cross section performed in the normal catalyst field for the cross section of the particle to be measured. According to the above, it was measured and calculated as follows. That is, first, the distribution of the X-ray peak intensity (count number I Si ) of Si at an arbitrary position (x, y) in the catalyst particle cross section is measured so as to cover the entire area of the catalyst particle cross section. Next, similarly, the distribution of the X-ray peak intensity (count number I X ) is also measured for the component X so as to cover the entire region of the catalyst particle cross section. Based on the series of data (x, y, I Si , I X ) on the obtained Si and component X, the peak intensity ratio I R (I R = I) of the component X and Si at the same position (x, y) I X / I Si ), and a simple average (I R ) av and standard deviation S of I R are obtained. A value obtained by dividing the standard deviation S by a simple average (I R ) av is defined as the variance value (D X ). At this time, the simple average and standard deviation may be obtained by ordinary methods.
なお、この測定における粒子断面のエッジ効果によるデータの不確定さを避けるべく、触媒粒子断面における断面積の１０％の領域であって、粒子外周部分に相当する領域を除外し、触媒粒子断面における中心から９０％の領域のデータを有効領域として算出することが好ましい。もちろん、始めから、粒子外周部の１０％分の領域を除した触媒粒子断面の内部のみについて、ＥＰＭＡによる上記の面分析を行い、そのデータから、上記のように分散値ＤＸを求めてもよい。 In order to avoid the uncertainty of the data due to the edge effect of the particle cross section in this measurement, the area corresponding to 10% of the cross sectional area in the cross section of the catalyst particle and excluding the area corresponding to the outer peripheral portion of the particle is excluded. It is preferable to calculate data in an area 90% from the center as an effective area. Of course, from the beginning, the only internal catalyst particle cross sections obtained by dividing 10% of the area of the particle outer peripheral portion, perform the above surface analysis by EPMA, from that data, be calculated variance value D X as above Good.
上記触媒粒子断面の面分析は、上記したように通常の触媒分野で行われている手法に準じて行えばよいのであるが、通常、次のようにして好適に行うことができる。
すなわち、まず、測定しようとする粒子を適当なマトリックス樹脂中に包埋させ、これを研磨し、埋設した触媒粒子の断面が見えるまで全体を削る。次いで、断面の見えた触媒粒子について次のようにしてＥＰＭＡ測定を行う。
(1)ＥＰＭＡ測定における観測視野内に上記触媒粒子の断面がくるように試料の位置を設定する。
(2)該触媒粒子断面に電子線を照射し、電子線を当てた部分から出てくるシリコンまたは成分Ｘの特性Ｘ線の強度をカウントし、分析する領域を電子線で走査することによって面分析を行う。
The surface analysis of the cross section of the catalyst particles may be performed in accordance with the method used in the normal catalyst field as described above, but can be suitably performed as follows.
That is, first, the particles to be measured are embedded in an appropriate matrix resin, polished, and the whole is shaved until a section of the embedded catalyst particles can be seen. Next, EPMA measurement is performed on the catalyst particles whose cross section is visible as follows.
(1) The position of the sample is set so that the cross section of the catalyst particle comes within the observation field of view in EPMA measurement.
(2) Irradiate the cross section of the catalyst particles with an electron beam, count the intensity of the characteristic X-rays of silicon or component X coming out from the portion irradiated with the electron beam, and scan the area to be analyzed with the electron beam Perform analysis.
本発明の複合酸化物触媒は、一般的な方法で調製することができ、例えば次の３つの工程を経て製造することができる。
（Ｉ）原料を調合する工程
（II）工程（Ｉ）で得られた原料調合液を乾燥し、触媒前駆体を得る工程
（III）工程（II）で得られた触媒前駆体を焼成する工程
The composite oxide catalyst of the present invention can be prepared by a general method, and can be produced, for example, through the following three steps.
(I) Step of preparing raw materials (II) Step of drying the raw material preparation liquid obtained in step (I) to obtain a catalyst precursor (III) Step of firing the catalyst precursor obtained in step (II)
本発明における調合とは、水性溶媒に、触媒構成元素の原料を溶解または分散させることである。
原料とは、工程（Ｉ）で用いるものである。本発明の複合酸化物触媒を調製するにあたり、金属の原料は特に限定されないが、例えば、下記の化合物を用いることができる。
The preparation in the present invention is to dissolve or disperse the raw material of the catalyst constituent element in the aqueous solvent.
The raw material is used in step (I). In preparing the composite oxide catalyst of the present invention, the metal raw material is not particularly limited. For example, the following compounds can be used.
ＭｏとＶの原料は、それぞれ、ヘプタモリブデン酸アンモニウム［（ＮＨ４）６Ｍｏ７Ｏ２４・４Ｈ２Ｏ］とメタバナジン酸アンモニウム［ＮＨ４ＶＯ３］を好適に用いることができる。
Ｎｂの原料としては、ニオブ酸、ニオブの無機酸塩およびニオブの有機酸塩を用いることができる。特にニオブ酸が良い。ニオブ酸はＮｂ２Ｏ５・ｎＨ２Ｏで表され、ニオブ水酸化物または酸化ニオブ水和物とも称される。更にジカルボン酸／ニオブのモル比が１〜４のＮｂ原料液として用いることが好ましい。ジカルボン酸はシュウ酸が好ましい。
Ｓｂの原料としては三酸化二アンチモン〔Ｓｂ２Ｏ３〕が好ましい。
Ｔｅの原料としてはテルル酸〔Ｈ６ＴｅＯ６〕が好ましい。
As the raw materials for Mo and V, ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 · 4H 2 O] and ammonium metavanadate [NH 4 VO 3 ] can be preferably used, respectively.
As a raw material of Nb, niobic acid, an inorganic acid salt of niobium, and an organic acid salt of niobium can be used. Niobic acid is particularly good. Niobic acid is represented by Nb 2 O 5 .nH 2 O and is also referred to as niobium hydroxide or niobium oxide hydrate. Furthermore, it is preferable to use as a Nb raw material liquid having a dicarboxylic acid / niobium molar ratio of 1 to 4. The dicarboxylic acid is preferably oxalic acid.
As a raw material of Sb, diantimony trioxide [Sb 2 O 3 ] is preferable.
As a raw material of Te, telluric acid [H 6 TeO 6 ] is preferable.
成分Ｘの原料としては、これらの元素を含む物質であれば特に制限はないが、これらの元素を含む化合物やこれらの元素の金属を適当な試薬で可溶化したものを使用することができる。これらの元素を含む化合物としては、通常、硝酸塩、カルボン酸塩、カルボン酸アンモニウム塩、ペルオキソカルボン酸塩、ペルオキソカルボン酸アンモニウム塩、ハロゲン化アンモニウム塩、ハロゲン化物、アセチルアセトナート、アルコキシド等を使用することができる、好ましくは硝酸塩、カルボン酸塩等の水溶性原料が使用される。
シリカの原料にはシリカゾルを用いることができるが、シリカ原料の一部または全量に、粉体シリカを用いることもできる。該粉体シリカは、高熱法で製造されたものが好ましい。さらに、該粉体シリカは水に分散させて使用することが尚好ましい。
以下に、工程（Ｉ）〜（III）からなる本発明の好ましい触媒調製例を説明する。
The raw material of component X is not particularly limited as long as it is a substance containing these elements, but compounds containing these elements or metals obtained by solubilizing these elements with a suitable reagent can be used. As compounds containing these elements, nitrates, carboxylates, ammonium carboxylates, peroxocarboxylates, ammonium peroxocarboxylates, ammonium halides, halides, acetylacetonates, alkoxides, etc. are usually used. Preferably, water-soluble raw materials such as nitrates and carboxylates are used.
Silica sol can be used as the silica raw material, but powdered silica can also be used for a part or all of the silica raw material. The powder silica is preferably produced by a high heat method. Further, it is more preferable to use the powdered silica dispersed in water.
Below, the preferable catalyst preparation example of this invention which consists of process (I)-(III) is demonstrated.
（工程Ｉ：原料を調合する工程）
Ｍｏ化合物、Ｖ化合物、Ｘ成分、必要によりその他原料となる成分を水に添加し、加熱して混合液（Ａ）を調製する。この時、容器内は窒素雰囲気でもよい。Ｎｂを含ませる場合には、Ｎｂ化合物とジカルボン酸を水中で加熱撹拌して混合液（Ｂ０）を調製する。更に、混合液（Ｂ０）に、過酸化水素を添加し、混合液（Ｂ）を調製してもよい。この時、Ｈ２Ｏ２／Ｎｂ（モル比）は０．５〜２０、特に、１〜１０が好ましい。混合液（Ｂ０）又は（Ｂ）には更にシュウ酸を加えることもできる。
目的とする組成に合わせて、混合液（Ａ）、混合液（Ｂ０）又は（Ｂ）を好適に混合して、原料調合液を得る。
本発明のアンモ酸化用触媒がシリカ担持触媒の場合、シリカゾルを含むように原料調合液が調製される。シリカゾルは適宜添加することができる。
(Process I: Process of preparing raw materials)
Mo compound, V compound, X component, and other ingredients as necessary are added to water and heated to prepare a mixed solution (A). At this time, the inside of the container may be a nitrogen atmosphere. When Nb is included, the Nb compound and dicarboxylic acid are heated and stirred in water to prepare a mixed solution (B 0 ). Further, the mixture (B 0), adding hydrogen peroxide, a mixed solution (B) may be prepared. At this time, H 2 O 2 / Nb (molar ratio) is 0.5 to 20, especially 1 to 10 are preferred. Oxalic acid can also be added to the mixed solution (B 0 ) or (B).
According to the target composition, the mixed solution (A), the mixed solution (B 0 ) or (B) is suitably mixed to obtain a raw material preparation solution.
When the catalyst for ammoxidation of the present invention is a silica-supported catalyst, the raw material preparation liquid is prepared so as to contain silica sol. Silica sol can be added as appropriate.
（工程II：乾燥工程）
工程（Ｉ）で得られた原料調合液を噴霧乾燥法によって乾燥させ、乾燥粉体を得る。噴霧乾燥法における噴霧化は遠心方式、二流体ノズル方式または高圧ノズル方式を採用することができる。乾燥熱源は、スチーム、電気ヒーターなどによって加熱された空気を用いることができる。熱風の乾燥機入口温度は１５０〜３００℃が好ましい。
(Process II: Drying process)
The raw material preparation liquid obtained in the step (I) is dried by a spray drying method to obtain a dry powder. The atomization in the spray drying method can employ a centrifugal method, a two-fluid nozzle method, or a high-pressure nozzle method. As the drying heat source, air heated by steam, an electric heater or the like can be used. The dryer inlet temperature of hot air is preferably 150 to 300 ° C.
（工程III：焼成工程）
乾燥工程で得られた乾燥粉体を焼成することによって酸化物触媒を得る。焼成は窒素ガス、アルゴンガス、ヘリウムガスなどの実質的に酸素を含まない不活性ガス雰囲気下、好ましくは、不活性ガスを流通させながら、５００〜８００℃、好ましくは６００〜７００℃で実施する。焼成時間は０．５〜２０時間、好ましくは１〜８時間である。
焼成は、回転炉、トンネル炉、管状炉、流動焼成炉等を用いて行うことができる。焼成は反復することができる。
焼成工程の前に、乾燥粉体を大気雰囲気下または空気流通下で２００〜４００℃、１〜５時間で前焼成することも好ましい。
(Process III: Firing process)
An oxide catalyst is obtained by firing the dry powder obtained in the drying step. Firing is performed in an inert gas atmosphere substantially free of oxygen such as nitrogen gas, argon gas, helium gas, preferably at 500 to 800 ° C., preferably 600 to 700 ° C. while circulating the inert gas. . The firing time is 0.5 to 20 hours, preferably 1 to 8 hours.
Firing can be performed using a rotary furnace, tunnel furnace, tubular furnace, fluidized firing furnace, or the like. Firing can be repeated.
Prior to the firing step, it is also preferable to pre-fire the dry powder at 200 to 400 ° C. for 1 to 5 hours in an air atmosphere or air circulation.
このようにして製造された酸化物触媒の存在下、プロパンまたはイソブタンを気相接触酸化または気相接触アンモ酸化反応させて、対応する不飽和酸または不飽和ニトリルを製造する。
プロパンまたはイソブタンとアンモニアの供給原料は必ずしも高純度である必要はなく、工業グレードのガスを使用できる。
Propane or isobutane is subjected to gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction in the presence of the oxide catalyst thus prepared to produce the corresponding unsaturated acid or unsaturated nitrile.
The feedstock for propane or isobutane and ammonia does not necessarily have to be high purity, and industrial grade gases can be used.
供給酸素源として空気、酸素を富化した空気または純酸素を用いることができる。更に、希釈ガスとしてヘリウム、アルゴン、炭酸ガス、水蒸気、窒素などを供給してもよい。
プロパンまたはイソブタンの気相接触酸化は以下の条件で行うことが出来る。
反応に供給する酸素のプロパンまたはイソブタンに対するモル比は０．１〜６、好ましくは０．５〜４である。
Air, oxygen-enriched air, or pure oxygen can be used as the supply oxygen source. Further, helium, argon, carbon dioxide gas, water vapor, nitrogen or the like may be supplied as a dilution gas.
The gas phase catalytic oxidation of propane or isobutane can be carried out under the following conditions.
The molar ratio of oxygen supplied to the reaction to propane or isobutane is 0.1 to 6, preferably 0.5 to 4.
反応温度は３００〜５００℃、好ましくは３５０〜４５０℃である。
反応圧力は５×１０４〜５×１０５Ｐａ、好ましくは１×１０５〜３×１０５Ｐａである。
接触時間は０．１〜１０（ｓｅｃ・ｇ／ｃｃ）、好ましくは０．５〜５（ｓｅｃ・ｇ／ｃｃ）である。本発明において、接触時間は次式で決定される。
接触時間（ｓｅｃ・ｇ／ｃｃ）＝（Ｗ／Ｆ）×２７３／（２７３＋Ｔ）
ここで、Ｗ、Ｆ及びＴは次のように定義される。
Ｗ＝充填触媒量（ｇ）
Ｆ＝標準状態(０℃、1.013×105Ｐａ)での原料混合ガス流量(Ｎcc／sec)
Ｔ＝反応温度（℃）
The reaction temperature is 300 to 500 ° C, preferably 350 to 450 ° C.
The reaction pressure is 5 × 10 4 to 5 × 10 5 Pa, preferably 1 × 10 5 to 3 × 10 5 Pa.
The contact time is 0.1 to 10 (sec · g / cc), preferably 0.5 to 5 (sec · g / cc). In the present invention, the contact time is determined by the following equation.
Contact time (sec · g / cc) = (W / F) × 273 / (273 + T)
Here, W, F, and T are defined as follows.
W = filled catalyst amount (g)
F = Raw material mixed gas flow rate (Ncc / sec) under standard conditions (0 ° C, 1.013 x 10 5 Pa)
T = reaction temperature (° C.)
プロパンまたはイソブタンの気相接触アンモ酸化は以下の条件で行うことが出来る。
反応に供給する酸素のプロパンまたはイソブタンに対するモル比は０．１〜６、好ましくは０．５〜４である。
反応に供給するアンモニアのプロパンまたはイソブタンに対するモル比は０．３〜１．５、好ましくは０．７〜１．２である。
反応温度は３５０〜５００℃、好ましくは３８０〜４７０℃である。
反応圧力は５×１０４〜５×１０５Ｐａ、好ましくは１×１０５〜３×１０５Ｐａである。
接触時間は０．１〜１０（ｓｅｃ・ｇ／ｃｃ）、好ましくは０．５〜５（ｓｅｃ・ｇ／ｃｃ）である。
反応方式は、固定床、流動床、移動床など従来の方式を採用できるが、反応熱の除去が容易な流動床反応器が好ましい。
また、本発明の反応は、単流式であってもリサイクル式であってもよい。
The gas phase catalytic ammoxidation of propane or isobutane can be carried out under the following conditions.
The molar ratio of oxygen supplied to the reaction to propane or isobutane is 0.1 to 6, preferably 0.5 to 4.
The molar ratio of ammonia to propane or isobutane supplied to the reaction is 0.3 to 1.5, preferably 0.7 to 1.2.
The reaction temperature is 350 to 500 ° C, preferably 380 to 470 ° C.
The reaction pressure is 5 × 10 4 to 5 × 10 5 Pa, preferably 1 × 10 5 to 3 × 10 5 Pa.
The contact time is 0.1 to 10 (sec · g / cc), preferably 0.5 to 5 (sec · g / cc).
As the reaction method, a conventional method such as a fixed bed, a fluidized bed, or a moving bed can be adopted, but a fluidized bed reactor in which reaction heat can be easily removed is preferable.
The reaction of the present invention may be a single flow type or a recycle type.
＜実施例＞
以下に本発明の複合酸化物触媒について、触媒の調製実施例およびプロパンの気相接触アンモ酸化反応によるアクリロニトリルの製造実施例を用いて説明するが、本発明はその要旨を越えない限りこれら実施例に限定されるものではない。
<Example>
Hereinafter, the composite oxide catalyst of the present invention will be described with reference to preparation examples of the catalyst and examples of production of acrylonitrile by the gas-phase catalytic ammoxidation reaction of propane. It is not limited to.
プロパンのアンモ酸化反応の成績は反応ガスを分析した結果を基に、次式で定義されるプロパン転化率およびアクリロニトリル選択率を指標として評価した。 The results of the propane ammoxidation reaction were evaluated based on the results of analysis of the reaction gas, using the propane conversion and acrylonitrile selectivity defined by the following equations as indicators.
（ニオブ混合液の調製）
特開平１１−２５３８０１号公報に倣って、以下の方法でニオブ混合液を調製した。
水２５５２ｇにＮｂ２Ｏ５として８０重量％を含有するニオブ酸３５２ｇとシュウ酸二水和物〔Ｈ２Ｃ２Ｏ４・２Ｈ２Ｏ〕１３４４ｇを混合した。仕込みのシュウ酸／ニオブのモル比は５．０３、仕込みのニオブ濃度は０．５０（ｍｏｌ−Ｎｂ／Ｋｇ−液）である。この液を９５℃で１時間加熱撹拌することによって、ニオブが溶解した混合液を得た。この混合液を静置、氷冷後、固体を吸引濾過によって濾別し、均一なニオブ混合液を得た。このニオブ混合液のシュウ酸／ニオブのモル比は下記の分析により２．５２であった。
るつぼにこのニオブ混合液１０ｇを精秤し、９５℃で一夜乾燥後、６００℃で１時間熱処理し、Ｎｂ２Ｏ５０．８２２８ｇを得た。この結果から、ニオブ濃度は０．６１８（ｍｏｌ−Ｎｂ／Ｋｇ−液）であった。
３００ｍｌのガラスビーカーにこのニオブ混合液３ｇを精秤し、約８０℃の熱水２００ｍｌを加え、続いて１：１硫酸１０ｍｌを加えた。得られた混合液をホットスターラー上で液温７０℃に保ちながら、攪拌下、１／４規定ＫＭｎＯ４を用いて滴定した。ＫＭｎＯ４によるかすかな淡桃色が約３０秒以上続く点を終点とした。シュウ酸の濃度は、滴定量から次式に従って計算した結果、１．５５８（ｍｏｌ−シュウ酸／Ｋｇ）であった。
2ＫＭｎＯ４＋3Ｈ２ＳＯ４＋5Ｈ２Ｃ２Ｏ４→Ｋ２ＳＯ４＋2ＭｎＳＯ４＋10ＣＯ２＋8Ｈ２Ｏ
得られたニオブ混合液は、下記の触媒調製のニオブ混合液（Ｂ０）として用いた。
(Preparation of niobium mixture)
According to Japanese Patent Laid-Open No. 11-253801, a niobium mixed solution was prepared by the following method.
To 552 g of water, 352 g of niobic acid containing 80% by weight as Nb 2 O 5 and 1344 g of oxalic acid dihydrate [H 2 C 2 O 4 .2H 2 O] were mixed. The molar ratio of the charged oxalic acid / niobium is 5.03, and the charged niobium concentration is 0.50 (mol-Nb / Kg-solution). This solution was heated and stirred at 95 ° C. for 1 hour to obtain a mixed solution in which niobium was dissolved. The mixture was allowed to stand and ice-cooled, and then the solid was separated by suction filtration to obtain a uniform niobium mixture. The molar ratio of oxalic acid / niobium in this niobium mixed solution was 2.52 according to the following analysis.
10 g of this niobium mixed solution was precisely weighed in a crucible, dried overnight at 95 ° C., and then heat-treated at 600 ° C. for 1 hour to obtain 0.8228 g of Nb 2 O 5 . From this result, the niobium concentration was 0.618 (mol-Nb / Kg-solution).
3 g of this niobium mixture 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 mixed liquid 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 1.558 (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 mixed solution was used as a niobium mixed solution (B 0 ) for catalyst preparation described below.
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｃｅ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
水４５８４ｇにヘプタモリブデン酸アンモニウム〔（ＮＨ４）６Ｍｏ７Ｏ２４・４Ｈ２Ｏ〕を９１５．０ｇ、メタバナジン酸アンモニウム〔ＮＨ４ＶＯ３〕を１２７．３ｇ、三酸化二アンチモン〔Ｓｂ２Ｏ３〕を１８８．８ｇ、および硝酸セリウム６水和物［Ｃｅ（ＮＯ３）３・６Ｈ２Ｏ］を１１．２５ｇ加え、攪拌しながら９０℃で２時間３０分に加熱して混合液Ａ−１を得た。
ニオブ混合液（Ｂ０）７５４．６ｇに、Ｈ２Ｏ２として３０ｗｔ％を含有する過酸化水素水を１０５．８ｇ添加し、室温で１０分間攪拌混合して、混合液Ｂ−１を調製した。
得られた混合液Ａ−１を７０℃に冷却した後にＳｉＯ２として３０．２ｗｔ％を含有するシリカゾル２９８０ｇを添加し、更に、Ｈ２Ｏ２として３０ｗｔ％含有する過酸化水素水２２０．４ｇを添加し、５０℃で１時間撹拌を続けた。次に混合液Ｂ−１を添加して原料調合液を得た。
得られた原料調合液を、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℃、そして出口温度は１２０℃であった。
得られた乾燥粉体４８０ｇを直径３インチのＳＵＳ製焼成管に充填し、５．０ＮＬ／ｍｉｎの窒素ガス流通下、管を回転させながら、６４０℃で２時間焼成して触媒を得た。
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Ce 0.005 O n /45.0wt%-SiO 2 as follows.
Water 4584g ammonium heptamolybdate [(NH 4) 6 Mo 7 O 24 · 4H 2 O ] was 915.0g, 127.3g of ammonium metavanadate [NH 4 VO 3], antimony trioxide [Sb 2 O 3 ] And 11.25 g of cerium nitrate hexahydrate [Ce (NO 3 ) 3 · 6H 2 O] were added, and the mixture was heated at 90 ° C. for 2 hours and 30 minutes with stirring to obtain a mixed solution A-1. Got.
105.8 g of hydrogen peroxide containing 30 wt% as H 2 O 2 was added to 754.6 g of the niobium mixed solution (B 0 ), and the mixture was stirred and mixed at room temperature for 10 minutes to prepare a mixed solution B-1. .
After cooling the obtained mixed liquid A-1 to 70 ° C., 2980 g of silica sol containing 30.2 wt% as SiO 2 was added, and further, 220.4 g of hydrogen peroxide containing 30 wt% as H 2 O 2 was added. The mixture was added and stirring was continued at 50 ° C. for 1 hour. Next, the mixed solution B-1 was added to obtain a raw material preparation solution.
The obtained raw material mixture was supplied to a centrifugal spray dryer and dried to obtain a microspherical dry powder. The dryer inlet temperature was 210 ° C and the outlet temperature was 120 ° C.
480 g of the obtained dry powder was filled in a SUS calcining tube having a diameter of 3 inches, and calcined at 640 ° C. for 2 hours while rotating the tube under a nitrogen gas flow of 5.0 NL / min to obtain a catalyst.
（組成分析）
得られた酸化物触媒に対して、島津製作所製ＥＰＭＡ１６００を用いてＥＰＭＡ測定を行った。測定条件は、加速電圧０−３０ｋＶ、Ｓｔｅｐ幅１．０μｍ、スポット径１．０μｍであった。Ｓｉ測定時の分光結晶にはＬＩＦ（フッ化リチウム）（２００面を使用）、Ｃｅ測定時にはＰＥＴ（ポリエチレンテレフタラート）（００２面を使用）を用いた。検出器には、Ｋｒイグザトロン検出器（比例計数管）を使用した。得られた結果を表１に示す。
(Composition analysis)
EPMA measurement was performed on the obtained oxide catalyst using EPMA 1600 manufactured by Shimadzu Corporation. The measurement conditions were an acceleration voltage of 0-30 kV, a step width of 1.0 μm, and a spot diameter of 1.0 μm. LIF (lithium fluoride) (using the 200 plane) was used as the spectral crystal during the Si measurement, and PET (polyethylene terephthalate) (using the 002 plane) was used during the Ce measurement. A Kr igzatron detector (proportional counter) was used as a detector. The obtained results are shown in Table 1.
（プロパンのアンモ酸化反応）
内径２５ｍｍのバイコールガラス流動床型反応管に調製して得られた触媒を３５ｇ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＝１：１：３：１８のモル比の混合ガスを接触時間２．８（ｓｅｃ・ｇ／ｃｃ）で供給した。反応開始後、５時間後に得られた結果を表１に、１２００時間後および２４００時間後に得られた結果を表２に示す。
(Propane ammoxidation reaction)
Filled with 35 g of the catalyst prepared in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and at a reaction temperature of 440 ° C. and a reaction pressure of normal pressure, a molar ratio of propane: ammonia: oxygen: helium = 1: 1: 3: 18 The mixed gas with a specific ratio was supplied at a contact time of 2.8 (sec · g / cc). The results obtained 5 hours after the start of the reaction are shown in Table 1, and the results obtained after 1200 hours and 2400 hours are shown in Table 2.
［比較例１］
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｃｅ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
水４６０２ｇにヘプタモリブデン酸アンモニウム〔（ＮＨ４）６Ｍｏ７Ｏ２４・４Ｈ２Ｏ〕を９１８．５ｇ、メタバナジン酸アンモニウム〔ＮＨ４ＶＯ３〕を１２７．８ｇ、三酸化二アンチモン〔Ｓｂ２Ｏ３〕を１８９．６ｇ、および水酸化セリウム［Ｃｅ（ＯＨ）４］を４．４６ｇ加え、攪拌しながら９０℃で２時間３０分に加熱して混合液Ａ−２を得た。
ニオブ混合液（Ｂ０）７５７．５ｇに、Ｈ２Ｏ２として３０ｗｔ％を含有する過酸化水素水を１０６．２ｇ添加し、室温で１０分間攪拌混合して、混合液Ｂ−２を調製した。
得られた混合液Ａ−２を７０℃に冷却した後にＳｉＯ２として３０．２ｗｔ％を含有するシリカゾル２９８０ｇを添加し、次に混合液Ｂ−２を添加して原料調合液を得た。
得られた原料調合液を、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℃、そして出口温度は１２０℃であった。
得られた乾燥粉体４８０ｇを直径３インチのＳＵＳ製焼成管に充填し、５．０ＮＬ／ｍｉｎの窒素ガス流通下、管を回転させながら、６４０℃で２時間焼成して触媒を得た。
[Comparative Example 1]
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Ce 0.005 O n /45.0wt%-SiO 2 as follows.
918.5 g of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 · 4H 2 O], 127.8 g of ammonium metavanadate [NH 4 VO 3 ], 4antimony trioxide [Sb 2 O 3] 189.6 g and 4.46 g of cerium hydroxide [Ce (OH) 4 ] were added, and the mixture was heated at 90 ° C. for 2 hours 30 minutes with stirring to obtain a mixed solution A-2.
107.5 g of hydrogen peroxide containing 30 wt% as H 2 O 2 was added to 757.5 g of the niobium mixed solution (B 0 ), and the mixture was stirred and mixed at room temperature for 10 minutes to prepare a mixed solution B-2. .
After the obtained mixed liquid A-2 was cooled to 70 ° C., 2980 g of silica sol containing 30.2 wt% as SiO 2 was added, and then mixed liquid B-2 was added to obtain a raw material preparation liquid.
The obtained raw material mixture was supplied to a centrifugal spray dryer and dried to obtain a microspherical dry powder. The dryer inlet temperature was 210 ° C and the outlet temperature was 120 ° C.
480 g of the obtained dry powder was filled in a SUS calcining tube having a diameter of 3 inches, and calcined at 640 ° C. for 2 hours while rotating the tube under a nitrogen gas flow of 5.0 NL / min to obtain a catalyst.
（組成分析）
得られた酸化物触媒に対して実施例１と同様の方法でＥＰＭＡ測定を行った。得られた結果を表１に示す。
(Composition analysis)
The obtained oxide catalyst was subjected to EPMA measurement in the same manner as in Example 1. The obtained results are shown in Table 1.
（プロパンのアンモ酸化反応）
内径２５ｍｍのバイコールガラス流動床型反応管に調製して得られた触媒を３５ｇ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＝１：１：３：１８のモル比の混合ガスを接触時間２．８（ｓｅｃ・ｇ／ｃｃ）で供給した。反応開始後、５時間後に得られた結果を表１に、１２００時間後および２４００時間後に得られた結果を表２に示す。
(Propane ammoxidation reaction)
Filled with 35 g of the catalyst prepared in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and at a reaction temperature of 440 ° C. and a reaction pressure of normal pressure, a molar ratio of propane: ammonia: oxygen: helium = 1: 1: 3: 18 The mixed gas with a specific ratio was supplied at a contact time of 2.8 (sec · g / cc). The results obtained 5 hours after the start of the reaction are shown in Table 1, and the results obtained after 1200 hours and 2400 hours are shown in Table 2.
［比較例２］
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｃｅ０．０５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
セリウム原料として水酸化セリウム［Ｃｅ（ＯＨ）４］４４．６ｇを添加した以外の調製操作は実施例１と同様に行った。
（組成分析）
得られた酸化物触媒に対して実施例１と同様の方法でＥＰＭＡ測定を行った。得られた結果を表１に示す。
（プロパンのアンモ酸化反応）
得られた酸化物触媒に対して、プロパンのアンモ酸化反応を実施例１と同様に行った。得られた結果を表１に示す。
[Comparative Example 2]
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Ce 0.05 O n /45.0wt%-SiO 2 as follows.
The preparation operation was performed in the same manner as in Example 1 except that 44.6 g of cerium hydroxide [Ce (OH) 4 ] was added as a cerium raw material.
(Composition analysis)
The obtained oxide catalyst was subjected to EPMA measurement in the same manner as in Example 1. The obtained results are shown in Table 1.
(Propane ammoxidation reaction)
The ammoxidation reaction of propane was performed on the obtained oxide catalyst in the same manner as in Example 1. The obtained results are shown in Table 1.
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｃｅ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
水４５８４ｇにヘプタモリブデン酸アンモニウム〔（ＮＨ４）６Ｍｏ７Ｏ２４・４Ｈ２Ｏ〕を９１５．０ｇ、メタバナジン酸アンモニウム〔ＮＨ４ＶＯ３〕を１２７．３ｇ、三酸化二アンチモン〔Ｓｂ２Ｏ３〕を１８８．８ｇ、および硝酸セリウム６水和物［Ｃｅ（ＮＯ３）３・６Ｈ２Ｏ］を１１．２５ｇ加え、攪拌しながら９０℃で２時間３０分に加熱して混合液Ａ−４を得た。
ニオブ混合液（Ｂ０）７５４．６ｇに、Ｈ２Ｏ２として３０ｗｔ％を含有する過酸化水素水を１０５．８ｇ添加し、室温で１０分間攪拌混合して、混合液Ｂ−４を調製した。
得られた混合液Ａ−４を７０℃に冷却した後にＳｉＯ２として３０．２ｗｔ％を含有するシリカゾル１４９０ｇを添加し、更に、Ｈ２Ｏ２として３０ｗｔ％含有する過酸化水素水２２０．４ｇを添加し、５０℃で１時間撹拌を続けた。次に混合液Ｂ−４、粉体シリカ４５０ｇを水６３００ｇに分散させた分散液を順次添加して原料調合液を得た。
得られた原料調合液を、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℃、そして出口温度は１２０℃であった。
得られた乾燥粉体４８０ｇを直径３インチのＳＵＳ製焼成管に充填し、５．０ＮＬ／ｍｉｎの窒素ガス流通下、管を回転させながら、６４０℃で２時間焼成して触媒を得た。
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Ce 0.005 O n /45.0wt%-SiO 2 as follows.
Water 4584g ammonium heptamolybdate [(NH 4) 6 Mo 7 O 24 · 4H 2 O ] was 915.0g, 127.3g of ammonium metavanadate [NH 4 VO 3], antimony trioxide [Sb 2 O 3 ] And 11.25 g of cerium nitrate hexahydrate [Ce (NO 3 ) 3 · 6H 2 O] were added, and the mixture was heated at 90 ° C. for 2 hours and 30 minutes with stirring to obtain a mixed solution A-4 Got.
105.8 g of hydrogen peroxide containing 30 wt% as H 2 O 2 was added to 754.6 g of the niobium mixed solution (B 0 ), and the mixture was stirred and mixed at room temperature for 10 minutes to prepare a mixed solution B-4. .
After cooling the obtained mixed liquid A-4 to 70 ° C., 1490 g of silica sol containing 30.2 wt% as SiO 2 was added, and further, 220.4 g of hydrogen peroxide containing 30 wt% as H 2 O 2 was added. The mixture was added and stirring was continued at 50 ° C. for 1 hour. Next, a mixed liquid B-4 and a dispersion obtained by dispersing 450 g of powdered silica in 6300 g of water were sequentially added to obtain a raw material preparation liquid.
The obtained raw material mixture was supplied to a centrifugal spray dryer and dried to obtain a microspherical dry powder. The dryer inlet temperature was 210 ° C and the outlet temperature was 120 ° C.
480 g of the obtained dry powder was filled in a SUS calcining tube having a diameter of 3 inches, and calcined at 640 ° C. for 2 hours while rotating the tube under a nitrogen gas flow of 5.0 NL / min to obtain a catalyst.
（組成分析）
得られた酸化物触媒に対して実施例１と同様の方法でＥＰＭＡ測定を行った。得られた結果を表１に示す。
(Composition analysis)
The obtained oxide catalyst was subjected to EPMA measurement in the same manner as in Example 1. The obtained results are shown in Table 1.
（プロパンのアンモ酸化反応）
内径２５ｍｍのバイコールガラス流動床型反応管に調製して得られた触媒を３５ｇ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＝１：１：３：１８のモル比の混合ガスを接触時間２．８（ｓｅｃ・ｇ／ｃｃ）で供給した。得られた結果を表１に示す。
(Propane ammoxidation reaction)
Filled with 35 g of the catalyst prepared in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm, and at a reaction temperature of 440 ° C. and a reaction pressure of normal pressure, a molar ratio of propane: ammonia: oxygen: helium = 1: 1: 3: 18 The mixed gas with a specific ratio was supplied at a contact time of 2.8 (sec · g / cc). The obtained results are shown in Table 1.
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｓｃ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
硝酸セリウムに代えて硝酸スカンジウム４水和物［Ｓｃ（ＮＯ３）３・４Ｈ２Ｏ］７．８５ｇを添加した以外の調製操作は実施例２と同様に行った。
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Sc 0.005 O n /45.0wt%-SiO 2 as follows.
The preparation operation was performed in the same manner as in Example 2 except that 7.85 g of scandium nitrate tetrahydrate [Sc (NO 3 ) 3 .4H 2 O] was added instead of cerium nitrate.
（組成分析）
得られた酸化物触媒に対して、島津製作所製ＥＰＭＡ１６００を用いてＥＰＭＡ測定を行った。測定条件は、加速電圧０−３０ｋＶ、Ｓｔｅｐ幅１．０μｍ、スポット径１．０μｍであった。ＳｉおよびＳｃ測定時の分光結晶にはＬＩＦ（フッ化リチウム）（２００面を使用）を用いた。検出器には、Ｋｒイグザトロン検出器（比例計数管）を使用した。得られた結果を表１に示す。
(Composition analysis)
EPMA measurement was performed on the obtained oxide catalyst using EPMA 1600 manufactured by Shimadzu Corporation. The measurement conditions were an acceleration voltage of 0-30 kV, a step width of 1.0 μm, and a spot diameter of 1.0 μm. LIF (lithium fluoride) (using the 200 plane) was used as the spectroscopic crystal when measuring Si and Sc. A Kr igzatron detector (proportional counter) was used as a detector. The obtained results are shown in Table 1.
（プロパンのアンモ酸化反応）
得られた酸化物触媒に対して、プロパンのアンモ酸化反応を実施例１と同様に行った。得られた結果を表１に示す。
(Propane ammoxidation reaction)
The ammoxidation reaction of propane was performed on the obtained oxide catalyst in the same manner as in Example 1. The obtained results are shown in Table 1.
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｙ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
硝酸セリウム６水和物に代えて、硝酸イットリウム６水和物［Ｙ（ＮＯ３）３・６Ｈ２Ｏ］９．９２ｇを添加した以外の調製操作は実施例２と同様に行った。
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Y 0.005 O n /45.0wt%-SiO 2 as follows.
A preparation operation was performed in the same manner as in Example 2 except that 9.92 g of yttrium nitrate hexahydrate [Y (NO 3 ) 3 .6H 2 O] was added instead of cerium nitrate hexahydrate.
（組成分析）
得られた酸化物触媒に対して、島津製作所製ＥＰＭＡ１６００を用いてＥＰＭＡ測定を行った。測定条件は、加速電圧０−３０ｋＶ、Ｓｔｅｐ幅１．０μｍ、スポット径１．０μｍであった。Ｓｉ測定時の分光結晶にはＬＩＦ（フッ化リチウム）（２００面を使用）、Ｙ測定時にはＰＥＴ（ポリエチレンテレフタラート）（００２面を使用）を用いた。検出器には、Ｋｒイグザトロン検出器（比例計数管）を使用した。得られた結果を表１に示す。
(Composition analysis)
EPMA measurement was performed on the obtained oxide catalyst using EPMA 1600 manufactured by Shimadzu Corporation. The measurement conditions were an acceleration voltage of 0-30 kV, a step width of 1.0 μm, and a spot diameter of 1.0 μm. LIF (lithium fluoride) (using the 200 plane) was used as the spectroscopic crystal during the Si measurement, and PET (polyethylene terephthalate) (using the 002 plane) was used during the Y measurement. A Kr igzatron detector (proportional counter) was used as a detector. The obtained results are shown in Table 1.
（プロパンのアンモ酸化反応）
得られた酸化物触媒に対して、プロパンのアンモ酸化反応を実施例１と同様に行った。
反応開始後、５時間後に得られた結果を表１に、１２００時間後および２４００時間後に得られた結果を表２に示す。
(Propane ammoxidation reaction)
The ammoxidation reaction of propane was performed on the obtained oxide catalyst in the same manner as in Example 1.
The results obtained 5 hours after the start of the reaction are shown in Table 1, and the results obtained after 1200 hours and 2400 hours are shown in Table 2.
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｌａ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
硝酸セリウム６水和物に代えて、硝酸ランタン６水和物［Ｌａ（ＮＯ３）３・６Ｈ２Ｏ］１１．２１ｇを添加した以外の調製操作は実施例２と同様に行った。
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 La 0.005 O n /45.0wt%-SiO 2 as follows.
The preparation operation was performed in the same manner as in Example 2 except that 11.21 g of lanthanum nitrate hexahydrate [La (NO 3 ) 3 .6H 2 O] was added instead of cerium nitrate hexahydrate.
（組成分析）
得られた酸化物触媒に対して、島津製作所製ＥＰＭＡ１６００を用いてＥＰＭＡ測定を行った。測定条件は、加速電圧０−３０ｋＶ、Ｓｔｅｐ幅１．０μｍ、スポット径１．０μｍであった。ＳｉおよびＬａ測定時の分光結晶にはＬＩＦ（フッ化リチウム）（２００面を使用）を用いた。検出器には、Ｋｒイグザトロン検出器（比例計数管）を使用した。得られた結果を表１に示す。
(Composition analysis)
EPMA measurement was performed on the obtained oxide catalyst using EPMA 1600 manufactured by Shimadzu Corporation. The measurement conditions were an acceleration voltage of 0-30 kV, a step width of 1.0 μm, and a spot diameter of 1.0 μm. LIF (lithium fluoride) (using the 200 plane) was used as the spectroscopic crystal when measuring Si and La. A Kr igzatron detector (proportional counter) was used as a detector. The obtained results are shown in Table 1.
（プロパンのアンモ酸化反応）
得られた酸化物触媒に対して、プロパンのアンモ酸化反応を実施例１と同様に行った。得られた結果を表１に示す。
(Propane ammoxidation reaction)
The ammoxidation reaction of propane was performed on the obtained oxide catalyst in the same manner as in Example 1. The obtained results are shown in Table 1.
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｐｒ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
硝酸セリウム６水和物に代えて、硝酸プラセオジム６水和物［Ｐｒ（ＮＯ３）３・６Ｈ２Ｏ］１１．２７ｇを添加した以外の調製操作は実施例２と同様に行った。
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Pr 0.005 O n /45.0wt%-SiO 2 as follows.
The preparation operation was performed in the same manner as in Example 2 except that 11.27 g of praseodymium nitrate hexahydrate [Pr (NO 3 ) 3 .6H 2 O] was added instead of cerium nitrate hexahydrate.
（組成分析）
得られた酸化物触媒に対して、島津製作所製ＥＰＭＡ１６００を用いてＥＰＭＡ測定を行った。測定条件は、加速電圧０−３０ｋＶ、Ｓｔｅｐ幅１．０μｍ、スポット径１．０μｍであった。ＳｉおよびＰｒ測定時の分光結晶にはＬＩＦ（フッ化リチウム）（２００面を使用）を用いた。検出器には、Ｋｒイグザトロン検出器（比例計数管）を使用した。得られた結果を表１に示す。
(Composition analysis)
EPMA measurement was performed on the obtained oxide catalyst using EPMA 1600 manufactured by Shimadzu Corporation. The measurement conditions were an acceleration voltage of 0-30 kV, a step width of 1.0 μm, and a spot diameter of 1.0 μm. LIF (lithium fluoride) (using the 200 plane) was used as the spectral crystal during the measurement of Si and Pr. A Kr igzatron detector (proportional counter) was used as a detector. The obtained results are shown in Table 1.
（プロパンのアンモ酸化反応）
得られた酸化物触媒に対して、プロパンのアンモ酸化反応を実施例１と同様に行った。得られた結果を表１に示す。
(Propane ammoxidation reaction)
The ammoxidation reaction of propane was performed on the obtained oxide catalyst in the same manner as in Example 1. The obtained results are shown in Table 1.
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｙｂ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
硝酸セリウム６水和物に代えて、硝酸イッテルビウム３水和物［Ｙｂ（ＮＯ３）３・３Ｈ２Ｏ］１０．７０ｇを添加した以外の調製操作は実施例２と同様に行った。
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Yb 0.005 O n /45.0wt%-SiO 2 as follows.
The preparation operation was performed in the same manner as in Example 2 except that 10.70 g of ytterbium nitrate trihydrate [Yb (NO 3 ) 3 .3H 2 O] was added instead of cerium nitrate hexahydrate.
（組成分析）
得られた酸化物触媒に対して、島津製作所製ＥＰＭＡ１６００を用いてＥＰＭＡ測定を行った。測定条件は、加速電圧０−３０ｋＶ、Ｓｔｅｐ幅１．０μｍ、スポット径１．０μｍであった。ＳｉおよびＹｂ測定時の分光結晶にはＬＩＦ（フッ化リチウム）（２００面を使用）を用いた。検出器には、Ｋｒイグザトロン検出器（比例計数管）を使用した。得られた結果を表１に示す。
(Composition analysis)
EPMA measurement was performed on the obtained oxide catalyst using EPMA 1600 manufactured by Shimadzu Corporation. The measurement conditions were an acceleration voltage of 0-30 kV, a step width of 1.0 μm, and a spot diameter of 1.0 μm. LIF (lithium fluoride) (using the 200 plane) was used as the spectral crystal during the measurement of Si and Yb. A Kr igzatron detector (proportional counter) was used as a detector. The obtained results are shown in Table 1.
（プロパンのアンモ酸化反応）
得られた酸化物触媒に対して、プロパンのアンモ酸化反応を実施例１と同様に行った。得られた結果を表１に示す。
(Propane ammoxidation reaction)
The ammoxidation reaction of propane was performed on the obtained oxide catalyst in the same manner as in Example 1. The obtained results are shown in Table 1.
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｓｒ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
硝酸セリウム６水和物に代えて、硝酸ストロンチウム［Ｓｒ（ＮＯ３）２］５．４８ｇを添加した以外の調製操作は実施例２と同様に行った。
（組成分析）
得られた酸化物触媒に対して、島津製作所製ＥＰＭＡ１６００を用いてＥＰＭＡ測定を行った。測定条件は、加速電圧０−３０kV、Ｓｔｅｐ幅１．０μｍ、スポット径１．０μｍであった。ＳｉおよびＳｒ測定時の分光結晶にはＬＩＦ（フッ化リチウム）（２００面を使用）を用いた。検出器には、Ｋｒイグザトロン検出器（比例計数管）を使用した。得られた結果を表１に示す。
（プロパンのアンモ酸化反応）
得られた酸化物触媒に対して、プロパンのアンモ酸化反応を実施例１と同様に行った。得られた結果を表１に示す。
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Sr 0.005 O n /45.0wt%-SiO 2 as follows.
The preparation operation was carried out in the same manner as in Example 2 except that 5.48 g of strontium nitrate [Sr (NO 3 ) 2 ] was added instead of cerium nitrate hexahydrate.
(Composition analysis)
EPMA measurement was performed on the obtained oxide catalyst using EPMA 1600 manufactured by Shimadzu Corporation. The measurement conditions were an acceleration voltage of 0-30 kV, a step width of 1.0 μm, and a spot diameter of 1.0 μm. LIF (lithium fluoride) (using the 200 plane) was used as the spectral crystal during the measurement of Si and Sr. A Kr igzatron detector (proportional counter) was used as a detector. The obtained results are shown in Table 1.
(Propane ammoxidation reaction)
The ammoxidation reaction of propane was performed on the obtained oxide catalyst in the same manner as in Example 1. The obtained results are shown in Table 1.
［実施例９］
（触媒の調製）
仕込み組成式がＭｏ１Ｖ０．２１Ｎｂ０．０９Ｓｂ０．２５Ｂａ０．００５Ｏｎ／４５．０ｗｔ％−ＳｉＯ２で示される酸化物触媒を次のようにして製造した。
硝酸セリウム６水和物に代えて、硝酸バリウム［Ｂａ（ＮＯ３）２］６．７７ｇを添加した以外の調製操作は実施例２と同様に行った。
（組成分析）
得られた酸化物触媒に対して、島津製作所製ＥＰＭＡ１６００を用いてＥＰＭＡ測定を行った。測定条件は、加速電圧０−３０kV、Ｓｔｅｐ幅１．０μｍ、スポット径１．０μｍであった。ＳｉおよびＢａ測定時の分光結晶にはＬＩＦ（フッ化リチウム）（２００面を使用）を用いた。検出器には、Ｋｒイグザトロン検出器（比例計数管）を使用した。得られた結果を表１に示す。
（プロパンのアンモ酸化反応）
得られた酸化物触媒に対して、プロパンのアンモ酸化反応を実施例１と同様に行った。反応開始後、５時間後に得られた結果を表１に、１２００時間後および２４００時間後に得られた結果を表２に示す。
[Example 9]
(Preparation of catalyst)
Mixing composition formula was produced by the oxide catalyst represented by Mo 1 V 0.21 Nb 0.09 Sb 0.25 Ba 0.005 O n /45.0wt%-SiO 2 as follows.
The preparation operation was performed in the same manner as in Example 2 except that 6.77 g of barium nitrate [Ba (NO 3 ) 2 ] was added instead of cerium nitrate hexahydrate.
(Composition analysis)
EPMA measurement was performed on the obtained oxide catalyst using EPMA 1600 manufactured by Shimadzu Corporation. The measurement conditions were an acceleration voltage of 0-30 kV, a step width of 1.0 μm, and a spot diameter of 1.0 μm. LIF (lithium fluoride) (using the 200 plane) was used as the spectroscopic crystal when measuring Si and Ba. A Kr igzatron detector (proportional counter) was used as a detector. The obtained results are shown in Table 1.
(Propane ammoxidation reaction)
The ammoxidation reaction of propane was performed on the obtained oxide catalyst in the same manner as in Example 1. The results obtained 5 hours after the start of the reaction are shown in Table 1, and the results obtained after 1200 hours and 2400 hours are shown in Table 2.
本発明は、プロパンまたはイソブタンを気相接触酸化反応または気相接触アンモ酸化反応させて対応する不飽和酸または不飽和ニトリルを製造する工業的製造プロセスに有用に利用できる。 INDUSTRIAL APPLICABILITY The present invention can be usefully applied to an industrial production process for producing a corresponding unsaturated acid or unsaturated nitrile by subjecting propane or isobutane to a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction.
Claims (9)
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| JP2004236956A JP5263855B2 (en) | 2004-08-17 | 2004-08-17 | Catalyst made of complex oxide |
| PCT/JP2005/014919 WO2006019078A1 (en) | 2004-08-17 | 2005-08-15 | Catalyst composed of complex oxide |
| KR1020077003890A KR100893429B1 (en) | 2004-08-17 | 2005-08-15 | Catalyst composed of complex oxide |
| US11/659,335 US8642501B2 (en) | 2004-08-17 | 2005-08-15 | Composite oxide catalyst |
| EP05780202.7A EP1806178B1 (en) | 2004-08-17 | 2005-08-15 | Catalyst composed of complex oxide |
| CN2005800278209A CN101005892B (en) | 2004-08-17 | 2005-08-15 | Catalyst composed of complex oxide |
| MYPI20053856A MY154500A (en) | 2004-08-17 | 2005-08-17 | Catalyst composed of complex oxide |
| TW094128071A TWI280153B (en) | 2004-08-17 | 2005-08-17 | Composite oxide catalyst |
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| JP2004236956A JP5263855B2 (en) | 2004-08-17 | 2004-08-17 | Catalyst made of complex oxide |
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Cited By (6)
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| JP2007050404A (en) * | 2005-08-15 | 2007-03-01 | China Petrochemical Corp | Fluid-bed catalyst for preparation of ethylene and propylene by catalytic cracking |
| JP2014196318A (en) * | 2007-02-16 | 2014-10-16 | イネオス ユーエスエイ リミテッド ライアビリティ カンパニー | Method for ammoxidation of propane and isobutane using mixed metal oxide catalyst |
| WO2015133510A1 (en) * | 2014-03-06 | 2015-09-11 | 旭化成ケミカルズ株式会社 | Oxide catalyst, production method therefor, and unsaturated-nitrile production method |
| WO2015151726A1 (en) * | 2014-03-31 | 2015-10-08 | 旭化成ケミカルズ株式会社 | Method for producing oxide catalyst and method for producing unsaturated nitrile |
| CN114471596A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and method for preparing catalyst |
| EP4098362A4 (en) * | 2020-01-31 | 2023-07-19 | Asahi Kasei Kabushiki Kaisha | Composition for catalyst production, production method of composition for catalyst production, and production method for producing oxide catalyst |
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| CN106881103A (en) * | 2015-12-15 | 2017-06-23 | 上海华谊新材料有限公司 | The application method of composite oxide catalysts |
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| JP2000202293A (en) * | 1999-01-19 | 2000-07-25 | Asahi Chem Ind Co Ltd | Catalyst and production of unsaturated nitrile using same |
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| JP2007050404A (en) * | 2005-08-15 | 2007-03-01 | China Petrochemical Corp | Fluid-bed catalyst for preparation of ethylene and propylene by catalytic cracking |
| JP2014196318A (en) * | 2007-02-16 | 2014-10-16 | イネオス ユーエスエイ リミテッド ライアビリティ カンパニー | Method for ammoxidation of propane and isobutane using mixed metal oxide catalyst |
| WO2015133510A1 (en) * | 2014-03-06 | 2015-09-11 | 旭化成ケミカルズ株式会社 | Oxide catalyst, production method therefor, and unsaturated-nitrile production method |
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| US10179763B2 (en) | 2014-03-06 | 2019-01-15 | Asahi Kasei Kabushiki Kaisha | Oxide catalyst and method for producing same, and method for producing unsaturated nitrile |
| WO2015151726A1 (en) * | 2014-03-31 | 2015-10-08 | 旭化成ケミカルズ株式会社 | Method for producing oxide catalyst and method for producing unsaturated nitrile |
| JPWO2015151726A1 (en) * | 2014-03-31 | 2017-04-13 | 旭化成株式会社 | Method for producing oxide catalyst and method for producing unsaturated nitrile |
| EP4098362A4 (en) * | 2020-01-31 | 2023-07-19 | Asahi Kasei Kabushiki Kaisha | Composition for catalyst production, production method of composition for catalyst production, and production method for producing oxide catalyst |
| CN114471596A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and method for preparing catalyst |
| CN114471596B (en) * | 2020-10-27 | 2023-09-29 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and method for preparing catalyst |
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| CN101005892B (en) | 2010-06-09 |
| CN101005892A (en) | 2007-07-25 |
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