JP4187839B2 - Method for producing oxide catalyst and method for producing unsaturated nitrile using the catalyst - Google Patents
Method for producing oxide catalyst and method for producing unsaturated nitrile using the catalyst Download PDFInfo
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- JP4187839B2 JP4187839B2 JP26795898A JP26795898A JP4187839B2 JP 4187839 B2 JP4187839 B2 JP 4187839B2 JP 26795898 A JP26795898 A JP 26795898A JP 26795898 A JP26795898 A JP 26795898A JP 4187839 B2 JP4187839 B2 JP 4187839B2
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- Prior art keywords
- oxide
- catalyst
- producing
- propane
- oxide catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 80
- 150000002825 nitriles Chemical class 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 82
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 59
- 239000001294 propane Substances 0.000 claims description 41
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 24
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001282 iso-butane Substances 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 238000002360 preparation method Methods 0.000 description 23
- 229910052787 antimony Inorganic materials 0.000 description 18
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 18
- 229910052720 vanadium Inorganic materials 0.000 description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 229910001873 dinitrogen Inorganic materials 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 239000010955 niobium Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 11
- 239000011733 molybdenum Substances 0.000 description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000010453 quartz Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- XUGISPSHIFXEHZ-GPJXBBLFSA-N [(3r,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C1C=C2C[C@H](OC(C)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 XUGISPSHIFXEHZ-GPJXBBLFSA-N 0.000 description 5
- 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 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- -1 vanadium alkoxide Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000000967 suction filtration Methods 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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 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
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- VXLCNUFORWAGOA-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Sb+]=O Chemical compound [N+](=O)([O-])[O-].[Sb+]=O VXLCNUFORWAGOA-UHFFFAOYSA-N 0.000 description 1
- TXTQARDVRPFFHL-UHFFFAOYSA-N [Sb].[H][H] Chemical compound [Sb].[H][H] TXTQARDVRPFFHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- SZXAQBAUDGBVLT-UHFFFAOYSA-H antimony(3+);2,3-dihydroxybutanedioate Chemical compound [Sb+3].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SZXAQBAUDGBVLT-UHFFFAOYSA-H 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- CNRRZWMERIANGJ-UHFFFAOYSA-N chloro hypochlorite;molybdenum Chemical compound [Mo].ClOCl CNRRZWMERIANGJ-UHFFFAOYSA-N 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 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
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 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
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
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
Description
【０００１】
【発明の属する技術分野】
本発明は、プロパンまたはイソブタンの気相接触アンモ酸化反応に用いる、モリブデン、バナジウムおよびアンチモンを含有する触媒の製造方法、およびその触媒を用いた不飽和ニトリルの製造方法に関する。
【０００２】
【従来の技術】
最近、プロピレンまたはイソブチレンに代えてプロパンまたはイソブタンを用い、気相接触アンモ酸化反応によって、不飽和ニトリルを製造する技術が着目されており、多数の触媒が提案されている。
例えば、Ｍｏ−Ｖ−Ｔｅ−Ｎｂを含む複合酸化物が特開平２−２５７号公報、特開平５−１４８２１２号公報、特開平５−２０８１３６号公報、特開平６−２２７８１９号公報、特開平６−２８５３７２号公報、特開平７−１４４１３２号公報、特開平７−２３２０７１号公報、特開平８−５７３１９号公報、特開平８−１４１４０１号公報等に開示されている。これらの触媒においては収率が高く、不飽和ニトリルの空時収量も大きいが、触媒成分であるテルルが飛散して、触媒劣化の原因となるという問題がある。
【０００３】
特開平５−２９３３７４号公報には、バナジウム、アンチモンを主成分としモリブデンを微量添加した酸化物触媒が記載されている。この触媒においては、反応温度が高いうえに不飽和ニトリルの収率が低いという問題がある。
Ｎｅｗ Ｄｅｖｅｌｏｐｍｅｎｔｓ ｉｎ Ｓｅｌｅｃｔｉｖｅ Ｏｘｉｄａｔｉｏｎ ｐｐ．５１５〜５２５（１９９０）において、Ｍｏ／Ｖ／Ｓｂ＝１／０．１４／０．７１のモル比を持つ複合酸化物をアルミナに担持して調製した触媒についてプロパンのアンモ酸化反応の成績が報告されているが、選択性および活性が低いという問題がある。
【０００４】
米国特許第４，７６０，１５９号明細書にはＢｉ−Ｖ−Ｍｏ−Ｓｂからなる酸化物触媒が記載されている。これらの触媒の主成分はビスマスやバナジウム、アンチモンであるが、反応温度が高い上に不飽和ニトリルの収率が低いという問題がある。
特開平９−１５７２４１号公報、特開平１０−２８８６２号公報等にＭｏ−Ｖ−Ｓｂ−Ｎｂからなる酸化物触媒が記載され、Ｍｏ／Ｖ／Ｓｂ／Ｎｂ＝１／０．３／０．１５〜０．２／０．０５のモル比をもつ酸化物触媒が開示されている。これらの触媒において不飽和ニトリルの収率は比較的高いが、空時収量が０．１１〜０．２２（μｍｏｌ／（（ｇ・ｓ／ｍｌ）・ｇ））と小さく、反応器あたりの生産性が低くなるという問題がある。一方、空時収量を大きくするために反応温度を高くすると、不飽和ニトリルの選択率が下がり、その結果収率が下がるという問題が生じる。
【０００５】
また、Ａｐｐｌｉｅｄ Ｃａｔａｌｙｓｉｓ Ａ Ｇｅｎｅｒａｌ １５７，１４３−１７２（１９９７）に記載されているように、アンモニアはプロパンのアンモ酸化反応の目的生成物であるアクリロニトリルに転化されるだけではなく、副生物のアセトニトリルと青酸、そして酸化分解物としての窒素に転換される。Ｍｏ−Ｖ−Ｓｂ−Ｎｂからなる酸化物触媒はアンモニアから窒素への分解率が大きいことが難点であり、これを抑制してアンモニアの利用効率を高めることが望まれている。プロパンまたはイソブタンのアンモ酸化反応に用いるＭｏ−Ｖ−Ｓｂを含む酸化物触媒において、不飽和ニトリルの収率、空時収量が高く、しかもアンモニアから窒素への分解率の低い触媒は得られていない。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、プロパンまたはイソブタンの気相接触アンモ酸化反応によって不飽和ニトリルを製造する際に用いる、飛散性の少ない成分であるアンチモンを含有する酸化物触媒であって、且つ不飽和ニトリルの収率、空時収量が高く、しかもアンモニアから窒素への酸化分解率が低い触媒を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは、プロパンまたはイソブタンをアンモニア存在下に気相接触酸化させて不飽和ニトリルを製造する際に用いる、モリブデン、バナジウムおよびアンチモンを含有する酸化物触媒を鋭意検討した結果、これら３成分を含有する酸化物を、アンモニア水溶液に接触させた後に酸素不存在下で焼成して得られた酸化物触媒を用いることによって、不飽和ニトリルの収率、空時収量が高く、しかもアンモニアから窒素への酸化分解率が抑制されて、アンモニアの利用効率が改良されることを見いだし、本発明をなすに至った。
【０００８】
即ち、本発明は、
（１） プロパンまたはイソブタンを気相接触アンモ酸化させて不飽和ニトリルを製造する際に用いる酸化物触媒の製造方法において、下記式（Ｉ）で示される成分組成を有する酸化物をアンモニア水溶液に接触させ、アンモニア水溶液を分離除去し、酸素不存在下で焼成することを特徴とする酸化物触媒の製造方法、
Ｍｏ１ＶａＳｂｂＺｃＯｎ （Ｉ）
（式（Ｉ）において、ＺはＮｂ、Ｗ、Ｃｒ、Ｔｉ、Ｔａ、Ｚｒ、Ｈｆ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ｚｎ、Ｂ、Ｇａ、Ｉｎ、Ｇｅ、Ｓｎ、Ｐ、Ｐｂ、Ｂｉ、Ｙ、希土類元素およびアルカリ土類金属から選ばれる少なくとも１種類以上の元素であり、ａ、ｂ、ｃおよびｎはＭｏ１原子あたりの原子比を表し、０．１≦ａ≦１、０．０１≦ｂ≦０．６、０≦ｃ≦１、そしてｎは構成金属の酸化状態によって決まる原子比である。）
（２） 焼成温度が４００℃〜７００℃であることを特徴とする（１）に記載の酸化物触媒の製造方法、
（３） 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アンモ酸化反応させ対応する不飽和ニトリルを製造するにあたり、（１）又は（２）記載の酸化物触媒の製造方法で得られた触媒を用いることを特徴とする不飽和ニトリルの製造方法、に関するものである。
【０００９】
以下、本発明を詳細に説明する。本発明の特徴は、プロパンまたはイソブタンを気相接触アンモ酸化させて不飽和ニトリルを製造するために用いる酸化物触媒の製造方法において、式（Ｉ）で示される成分組成を有する酸化物をアンモニア水溶液に接触させ、ついでアンモニア水溶液を分離除去して得られた酸化物触媒を不飽和ニトリル製造用酸化物触媒として用いるところにある。
Ｍｏ１ＶａＳｂｂＺｃＯｎ（Ｉ）
（式（Ｉ）において、ＸはＮｂ、Ｗ、Ｃｒ、Ｔｉ、Ｔａ、Ｚｒ、Ｈｆ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ｚｎ、Ｂ、Ｇａ、Ｉｎ、Ｇｅ、Ｓｎ、Ｐ、Ｐｂ、Ｂｉ、Ｙ、希土類元素およびアルカリ土類金属から選ばれる少なくとも１種類以上の元素であり、好ましくはＮｂ、Ｗ、Ｓｎ、Ｔｉ、特に好ましくはＮｂ、Ｔｉである。ａ、ｂ、ｃおよびｎはＭｏ１原子あたりの原子比を表し、０．１≦ａ≦１、好ましくは０．１≦ａ≦０．５、特に好ましくは０．２≦ａ≦０．４、ｂは０．０１≦ｂ≦０．６、好ましくは０．１≦ｂ≦０．３、特に好ましくは０．１≦ｂ≦０．２５、ｃは０≦ｃ≦１、好ましくは０．０１≦ｃ≦０．５、特に好ましくは０．０１≦ｃ≦０．２であり、ｎは構成金属の酸化状態によって決まる原子比である。）
【００１０】
アンモニアの濃度は０．１重量％〜５０重量％が好ましく、特に好ましくは１重量％〜１０重量％である。式（Ｉ）で示される成分組成を有する酸化物をアンモニア水溶液へ接触させる方法は、回分操作方式と流通操作方式があげられる。回分操作方式の場合は、槽型反応器を用い該酸化物をアンモニア水溶液中に懸濁させる。アンモニア水溶液の重量に対する該酸化物の重量は、好ましくは１〜２０重量％である。接触させる時間は特に制限はないが、好ましくは２時間以上、さらに好ましくは６時間以上である。アンモニア水溶液の温度は０〜１００℃で好適に用いることができるが、０〜５０℃がより好ましい。接触を効率よく行うため、該懸濁液を撹拌機を用いて撹拌してもよいし、気泡を吹き込んで撹拌してもよい。流通操作方式としては、該酸化物を充填した固定床にアンモニア水溶液を流通させる等の方法を用いることができる。
【００１１】
該酸化物をアンモニア水溶液に接触させたのち、アンモニア水溶液を分離除去して本発明の酸化物触媒を得る。分離は遠心分離、濾紙やメンブレンフィルターを用いた濾別、デカンテーション等で行うことができる。該酸化物触媒は、アンモニア水溶液を分離除去したのち水洗し、乾燥させることが好ましい。このようにして得られた酸化物触媒は、焼成されることが好ましい。焼成は回転炉、トンネル炉、管状炉、流動焼成炉等を用い、実質的に酸素を含まない窒素等の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、４００〜７００℃、好ましくは５００〜６５０℃で実施することが好ましい。焼成時間は０．５〜５時間、好ましくは１〜３時間である。本発明において酸素不存在下とは、不活性ガス中の酸素濃度が、ガスクロマトグラフィーまたは微量酸素分析計で測定して１０００ｐｐｍ以下、好ましくは１００ｐｐｍ以下であることを言う。
【００１２】
上記アンモニア水溶液への接触処理は繰り返し行うことができ、繰り返し操作により不飽和ニトリルの収率、及び空時収量をさらに大きくすることができる。式（Ｉ）で示される成分組成を有する酸化物を製造するための成分金属の原料は、下記の化合物を用いることができる。バナジウム原料としてはメタバナジン酸アンモニウム、酸化バナジウム（Ｖ）、バナジウムのオキシ塩化物、バナジウムのアルコキシド等を用いることができ、好ましくはメタバナジン酸アンモニウム、酸化バナジウム（Ｖ）である。
【００１３】
モリブデン原料はヘプタモリブデン酸アンモニウム、モリブデン酸化物、モリブデンのオキシ塩化物、モリブデンの塩化物、モリブデンのアルコキシド等を用いることができ、好ましくはヘプタモリブデン酸アンモニウムである。
アンチモン原料は酸化アンチモン（ＩＩＩ）、酸化アンチモン（Ｖ）アンチモン（ＩＩＩ）、塩化アンチモン（ＩＩＩ）、塩化酸化アンチモン（ＩＩＩ）、硝酸酸化アンチモン（ＩＩＩ）、アンチモンのアルコキシド、アンチモンの酒石酸塩等の有機酸塩等、３価のアンチモンを含む化合物等を用いることができ、好ましくは酸化アンチモン（ＩＩＩ）である。
【００１４】
Ｎｂ、Ｗ、Ｃｒ、Ｔｉ、Ｔａ、Ｚｒ、Ｈｆ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ｚｎ、Ｂ、Ｇａ、Ｉｎ、Ｇｅ、Ｓｎ、Ｐ、Ｐｂ、Ｂｉ、Ｙ、希土類元素およびアルカリ土類金属の原料はシュウ酸塩、水酸化物、酸化物、硝酸塩、酢酸塩、アンモニウム塩、炭酸塩、アルコキシド等を用いることができる。ニオブ、チタンを用いる場合は、シュウ酸塩の水溶液を好適に用いることができる。ニオブのシュウ酸塩については例えば、ニオブ酸をシュウ酸水溶液に溶解することで製造できる。不溶なニオブ酸がある場合には、濾過等で不溶分を除去しておくことが好ましい。シュウ酸／ニオブのモル比は、好ましくは１〜１０であり、さらに好ましくは２〜６である。
【００１５】
本発明の触媒は、担体であるシリカも含めた全重量に対して２０〜６０重量％、好ましくは２０〜４０重量％のシリカに担持させて用いることができる。シリカの原料はシリカゾルを好適に用いることができる。アンモニウムイオンで安定化したゾルを用いることが好ましい。
本発明において、式（Ｉ）で示される成分組成を有する酸化物は、下記の原料調合、乾燥および焼成の３つの工程を経て製造することができる。
＜原料調合工程＞
メタバナジン酸アンモニウムと酸化アンチモン（ＩＩＩ）を含んだ混合液を空気雰囲気下にて加熱しつつ反応させる。加熱したときの該混合液の温度は７０℃〜１１０℃が好ましい。バナジウムとアンチモンを含有する混合液の加熱は蒸散する水分を補給しつつ行ってもよいし、または冷却管を反応容器に取り付けて還流条件で行ってもよい。加熱時間は３時間以上、特に好ましくは４〜５０時間である。バナジウム源として、メタバナジン酸アンモニウムを用いるかわりに酸化バナジウム（Ｖ）の過酸化水素水溶液を用いてもよい。なおここでいうバナジウムとアンチモンの２成分を含有する混合液は、水溶液であってもよいし、また微細な粒子が懸濁したスラリーでもよい。このようにして得たバナジウムとアンチモンを含有する混合液にヘプタモリブデン酸アンモニウムや、その水溶液を添加することによりモリブデン、バナジウム、アンチモンの３成分を含む混合液を得ることができる。
【００１６】
また、モリブデン、バナジウム、アンチモンの３成分を含む混合液の調製法はほかに、ヘプタモリブデン酸アンモニウムと酸化アンチモン（ＩＩＩ）を含む混合液を加熱しつつ反応させて、のちにバナジウムを含有する化合物または水溶液を添加して混合液を得る方法もある。
次に、ここで得られたモリブデン、バナジウム、アンチモンの３成分を含む混合液を酸化処理する。酸化処理の方法として、モリブデン、バナジウム、アンチモンの３成分を含む混合液を空気中５０〜３００℃以上の温度で１時間以上、好ましくは７０〜１１０℃の温度で４時間以上加熱する方法や、過酸化水素水を用いる方法等がある。過酸化水素水を用いる場合、好ましくはアンチモン量に対してモル比で０．０１〜２、特に好ましくは０．１〜１相当の過酸化水素を含む過酸化水素水を用いる。
【００１７】
さらにＸ成分を用いる場合には、Ｘ成分をモリブデン、バナジウム、アンチモンの３成分を含む混合液を酸化処理した後に該混合液に添加しても良いし、酸化処理する前に該混合液に添加しても良い。Ｘ成分としてニオブを用いる場合、ニオブ酸とシュウ酸を水に溶解した水溶液を用いることが好ましい。
Ｗ、Ｃｒ、Ｔｉ、Ｔａ、Ｚｒ、Ｈｆ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ｚｎ、Ｂ、Ｇａ、Ｉｎ、Ｇｅ、Ｓｎ、Ｐ、Ｐｂ、Ｂｉ、Ｙ、希土類元素およびアルカリ土類金属を用いる場合には、これらの金属の硝酸塩、シュウ酸塩、酢酸塩、水酸化物、酸化物、アンモニウム塩、炭酸塩等や、それらの水溶液やスラリーを、酸化処理した後もしくは酸化処理前のモリブデン、バナジウム、アンチモンの３成分を含む混合液に添加する。
【００１８】
シリカ担持触媒を製造する場合には、上記調合順序のいずれかのステップにおいてシリカゾルを添加して触媒原料液を得ることができる。
＜乾燥工程＞
原料調合工程で得られた触媒原料液を噴霧乾燥法または蒸発乾固法によって乾燥させ、乾燥粉体を得ることができる。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。このとき熱風の乾燥機入口温度は１５０〜３００℃が好ましい。噴霧乾燥は簡便には１００℃〜３００℃に加熱された鉄板上へ触媒原料液を噴霧することによって行うこともできる。
＜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式（１）で示される酸化物を得ることができる。焼成は回転炉、トンネル炉、管状炉、流動焼成炉等を用い、実質的に酸素を含まない窒素等の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、５００〜７００℃、好ましくは５５０〜６５０℃で実施することができる。焼成時間は０．５〜５時間、好ましくは１〜３時間である。不活性ガス中の酸素濃度は、ガスクロマトグラフィーまたは微量酸素分析計で測定して１０００ｐｐｍ以下、好ましくは、１００ｐｐｍ以下である。焼成は反復することができる。この焼成の前に空気雰囲気下または空気流通下で２００℃〜４２０℃、好ましくは２５０℃〜３５０℃で１０分〜５時間前焼成することができる。また、得られた酸化物を粉砕してさらに焼成することができる。
【００１９】
このようにして得られた式（１）で示される酸化物を前述したように、アンモニア水溶液に接触させ、ついでアンモニア水溶液を分離除去し、酸素不存在下で焼成して、本発明の酸化物触媒が得られる。得られた本発明の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アンモ酸化させて、不飽和ニトリルを製造することができる。プロパンまたはイソブタンおよび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。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。
【００２０】
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０．１〜１．５、好ましくは０．２〜１．２である。反応に供給される分子状酸素のプロパンまたはイソブタンに対するモル比は、０．２〜６、好ましくは０．４〜４である。
反応圧力は０．１〜１０ａｔｍ、好ましくは１〜３ａｔｍである。
反応温度は３５０℃〜６００℃、好ましくは３８０℃〜４７０℃である。
接触時間は０．１〜３０（ｇ・ｓ／ｍｌ）、好ましくは０．５〜１０（ｇ・ｓ／ｍｌ）である。
反応は、固定床、流動床、移動床など従来の方式を採用できる。反応は単流方式でもリサイクル方式でもよい。
【００２１】
【発明の実施の形態】
以下に本発明をプロパンのアンモ酸化反応の実施例で説明する。各例において、プロパン転化率、アクリロニトリル選択率、アクリロニトリル収率およびアクリロニトリルの空時収量は、それぞれ次の定義に従う。
・プロパン転化率（％）＝（反応したプロパンのモル数（μｍｏｌ））／（供給したプロパンのモル数（μｍｏｌ））×１００
・アクリロニトリル選択率（％）＝（生成したアクリロニトリルのモル数（μｍｏｌ））／（反応したプロパンのモル数（μｍｏｌ））×１００
・アクリロニトリル収率（％）＝（生成したアクリロニトリルのモル数（μｍｏｌ））／（供給したプロパンのモル数（μｍｏｌ））×１００
・アクリロニトリルの空時収量（μｍｏｌ／（（ｇ・ｓ／ｍｌ）・ｇ））＝（生成したアクリロニトリルのモル数（μｍｏｌ））／（（接触時間（ｇ・ｓ／ｍｌ））・（触媒重量（ｇ）））
・アンモニア分解率（％）＝２×（生成した窒素のモル数）／（供給したアンモニアのモル数）×１００
【００２２】
【実施例１】
＜酸化物調製＞
組成式がＭｏ1Ｖ0.29Ｓｂ0.14Ｎｂ0.06Ｏnで示される酸化物を次のように調製した。水８０ｇにメタバナジン酸アンモニウム［ＮＨ4ＶＯ3］１．９２ｇと酸化アンチモン（ＩＩＩ）［Ｓｂ2Ｏ3］１．１６ｇを添加し、油浴を用いて１００℃で８時間撹拌しつつ大気下で還流した。得られた２成分含有混合液にヘプタモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を１０．０ｇ添加し３成分含有混合液を得たのち、大気下水浴で８５℃に保ちつつ４時間撹拌し、室温まで冷却して触媒調合液を得た。
【００２３】
一方、水２５ｇにＮｂ2Ｏ5換算で７６重量％を含有するニオブ酸０．６０ｇ、シュウ酸二水和物［Ｈ2Ｃ2Ｏ4・２Ｈ2Ｏ］０．９６ｇを加え７０℃にて加熱溶解したのち、３０℃にて放冷し、ニオブ酸含有水溶液を得た。
触媒調合液にニオブ酸含有水溶液を添加したのち、空気雰囲気下３０℃で３０分撹拌して触媒原料液を得た。得られた触媒原料液を１４０℃に加熱したテフロンコーティング鉄板上に噴霧し乾燥粉体を得た。得られた粉体から１２．０ｇを、３００℃の恒温槽にて空気を流通させながら１時間加熱処理したのち、内径２０ｍｍの石英管に充填し、３５０Ｎｍｌ・ｍｉｎ-1の窒素ガス流通下、６００℃で２時間焼成して酸化物を得た。用いた窒素ガスの酸素濃度は微量酸素分析計（３０６ＷＡ型 テレダインアナリティカルインスツールメント社製）を用いて測定した結果、１ｐｐｍであった。
【００２４】
＜触媒調製＞
酸化物調製で得た酸化物のうち３．０ｇを、５重量％のアンモニア水溶液５０．０ｇに添加し懸濁させ、２５℃で６時間撹拌して懸濁液を得た。得られた懸濁液を吸引濾過することによってアンモニア水溶液を分離除去して酸化物を濾別したのち、さらに純水５０ｍｌを４回注ぐことによって酸化物を洗浄した。ついで２００℃の恒温槽で空気流通下にて乾燥させ、得られた粉体の全量を内径２０ｍｍの石英管に充填し、３５０Ｎｍｌ・ｍｉｎ-1の窒素ガス流通下、５５０℃で２時間焼成して酸化物触媒を得た。なお、用いた窒素ガスは、酸化物調製において、６００℃焼成の際に用いたものと同じである。
＜プロパンのアンモ酸化反応試験＞
得られた酸化物触媒０．３ｇを内径４ｍｍの固定床型反応管に充填し、反応温度Ｔ＝４３０℃、プロパン：アンモニア：酸素：ヘリウム＝１：１．２：２．９：１１．９のモル比の混合ガスを流量Ｆ＝６Ｎｍｌ・ｍｉｎ-1で流した。このとき圧力Ｐは１ａｔｍであった。接触時間は、酸化物重量をＷ（ｇ）として１．１７（＝Ｗ／Ｆ×６０×２７３／（２７３＋Ｔ）×Ｐ）（ｇ・ｓ／ｍｌ）である。反応ガスの分析はオンラインガスクロマトグラフィーで行った。得られた結果をプロパン転化率、アクリロニトリル選択率、アクリロニトリルの空時収量およびアンモニア分解率を指標として表１に示す。
【００２５】
【実施例２】
＜触媒調製＞
実施例１の酸化物調製で得た酸化物のうち４．５ｇを、５重量％のアンモニア水溶液８０ｇに添加し懸濁させ、２５℃で１５時間撹拌して懸濁液を得た。得られた懸濁液を吸引濾過することによってアンモニア水溶液を分離除去して酸化物を濾別したのち、さらに純水５０ｍｌを４回注ぐことによって酸化物を洗浄した。ついで２００℃の恒温槽で空気流通下にて乾燥させ、得られた粉体の全量をさらに内径２０ｍｍの石英管に充填し、５００Ｎｍｌ・ｍｉｎ-1の窒素ガス流通下、５５０℃で２時間焼成して酸化物触媒を得た。用いた窒素ガスは、実施例１の触媒調製と同じである。
＜プロパンのアンモ酸化反応試験＞
得られた酸化物触媒について、混合ガス流量Ｆ＝６．４Ｎｍｌ・ｍｉｎ-1とし、接触時間を１．１０（ｇ・ｓ／ｍｌ）とした以外は、実施例１と同じ条件下にてプロパンのアンモ酸化反応試験を行った。得られた結果を表１に示す。
【００２６】
【比較例１】
実施例１の酸化物調製で得た酸化物をそのまま用いた。
＜プロパンのアンモ酸化反応試験＞
プロパンのアンモ酸化反応試験を、実施例１と同じ条件下にて行った。得られた結果を表１に示す。
【００２７】
【実施例３】
＜酸化物調製＞
メタバナジン酸アンモニウム［ＮＨ4ＶＯ3］を２．０５ｇ、酸化アンチモン（ＩＩＩ）［Ｓｂ2Ｏ3］を１．１６ｇ、Ｎｂ2 Ｏ5 換算で７６重量％を含有するニオブ酸０．５０ｇを用いた以外は実施例１を反復して、組成式がＭｏ1Ｖ0.31Ｓｂ0.14Ｎｂ0.06Ｏnで示される酸化物を調製した。
＜触媒調製＞
上記酸化物調製で得られた酸化物のうち３．０ｇを、１０重量％のアンモニア水溶液５０ｇに添加し懸濁させ、２５℃で６時間撹拌して懸濁液を得た。得られた懸濁液を吸引濾過することによって酸化物を濾別したのち、さらに純水５０ｍｌを４回注ぐことによって酸化物を洗浄した。ついで２００℃の恒温槽で空気流通下にて乾燥させ、得られた粉体の全量を内径２０ｍｍの石英管に充填し、５００Ｎｍｌ・ｍｉｎ-1の窒素ガス流通下、５５０℃で２時間焼成して酸化物触媒を得た。窒素ガスは、実施例１の触媒調製と同じである。
＜プロパンのアンモ酸化反応試験＞
得られた酸化物触媒についてプロパンのアンモ酸化反応試験を、実施例１と同じ条件下にて行った。得られた結果を表１に示す。
【００２８】
【実施例４】
＜触媒調製＞
実施例３で得られた酸化物のうち１．５ｇを、２重量％のアンモニア水溶液５０ｇに添加し懸濁させ、２５℃で６時間撹拌して懸濁液を得た。得られた懸濁液を吸引濾過することによって酸化物を濾別したのち、さらに純水５０ｍｌを４回注ぐことによって酸化物を洗浄した。ついで２００℃の恒温槽で空気流通下にて乾燥させ、得られた粉体の全量をさらに内径２０ｍｍの石英管に充填し、５００Ｎｍｌ・ｍｉｎ-1の窒素ガス流通下、５５０℃で２時間焼成して酸化物触媒を得た。窒素ガスは、実施例１の触媒調製と同じである。
＜プロパンのアンモ酸化反応試験＞
得られた酸化物触媒についてプロパンのアンモ酸化反応試験を、実施例１と同じ条件下にて行った。得られた結果を表１に示す。
【００２９】
【比較例２】
実施例３の酸化物調製で得られた酸化物をそのまま用いた。
＜プロパンのアンモ酸化反応試験＞
得られた酸化物についてプロパンのアンモ酸化反応試験を、実施例１と同じ条件下にて行った。得られた結果を表１に示す。
【００３０】
【実施例５】
実施例１で得られた酸化物触媒のうち１．５ｇを、５重量％のアンモニア水溶液２５ｇに添加し懸濁させ、２５℃で６時間撹拌して懸濁液を得た。得られた懸濁液を吸引濾過することによって酸化物触媒を濾別したのち、さらに純水５０ｍｌを４回注ぐことによって酸化物触媒を洗浄した。ついで２００℃の恒温槽で空気流通下にて乾燥させ、得られた粉体の全量を内径２０ｍｍの石英管に充填し、５００Ｎｍｌ・ｍｉｎ-1の窒素ガス流通下、５５０℃で２時間焼成して酸化物触媒を得た。窒素ガスは実施例１の触媒調製と同じである。
＜プロパンのアンモ酸化反応試験＞
得られた酸化物触媒について、用いた触媒重量を０．１ｇとし、混合ガス流量Ｆ＝１２．０Ｎｍｌ・ｍｉｎ-1とし、接触時間を、０．５８（ｇ・ｓ／ｍｌ）とした以外は、実施例１と同じ条件下にてプロパンのアンモ酸化反応試験を行った。得られた結果を表１に示す。
【００３１】
【比較例３】
実施例３で得られた酸化物のうち１．５ｇを、蒸留水２５ｇに添加し懸濁させ、２５℃で６時間撹拌して懸濁液を得た。得られた懸濁液を吸引濾過することによって酸化物を濾別したのち、さらに純水５０ｍｌを４回注ぐことによって酸化物を洗浄した。ついで２００℃の恒温槽で空気流通下にて乾燥させ、得られた粉体の全量を内径２０ｍｍの石英管に充填し、５００Ｎｍｌ・ｍｉｎ-1の窒素ガス流通下、５５０℃で２時間焼成して触媒を得た。窒素ガスは、実施例１の触媒調製と同じである。
＜プロパンのアンモ酸化反応試験＞
得られた酸化物についてプロパンのアンモ酸化反応試験を、実施例１と同じ条件下にて行った。得られた結果を表１に示す。
【００３２】
【表１】
【発明の効果】
本発明の方法によって得られた酸化物触媒を用いれば、飛散性の少ない成分であるアンチモンを含む触媒により、比較的低い温度にて、プロパンまたはイソブタンから高い収率、空時収量で不飽和ニトリルを製造することができる。また、アンモニアから窒素への分解を抑制して、効率よく不飽和ニトリルを製造することができ、アンモニアの利用効率が改良できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a catalyst containing molybdenum, vanadium and antimony used in a gas phase catalytic ammoxidation reaction of propane or isobutane, and a method for producing an unsaturated nitrile using the catalyst.
[0002]
[Prior art]
Recently, a technique for producing an unsaturated nitrile by a gas phase catalytic ammoxidation reaction using propane or isobutane instead of propylene or isobutylene has attracted attention, and many catalysts have been proposed.
For example, composite oxides containing Mo-V-Te-Nb are disclosed in JP-A-2-257, JP-A-5-148212, JP-A-5-208136, JP-A-6-227819, and JP-A-6. JP-A-7-285372, JP-A-7-144132, JP-A-7-232011, JP-A-8-57319, JP-A-8-141401, and the like. These catalysts have a high yield and a large space-time yield of unsaturated nitriles, but there is a problem that tellurium, which is a catalyst component, scatters and causes catalyst deterioration.
[0003]
Japanese Patent Application Laid-Open No. 5-293374 discloses an oxide catalyst containing vanadium and antimony as main components and a small amount of molybdenum added. This catalyst has problems that the reaction temperature is high and the yield of unsaturated nitrile is low.
New Developments in Selective Oxidation pp. 515-525 (1990) reports the results of ammoxidation of propane for a catalyst prepared by supporting a composite oxide with a molar ratio of Mo / V / Sb = 1 / 0.14 / 0.71 on alumina. However, there is a problem of low selectivity and activity.
[0004]
U.S. Pat. No. 4,760,159 describes an oxide catalyst comprising Bi-V-Mo-Sb. The main components of these catalysts are bismuth, vanadium and antimony, but there are problems that the reaction temperature is high and the yield of unsaturated nitrile is low.
JP-A-9-157241, JP-A-10-28862, etc. describe oxide catalysts composed of Mo-V-Sb-Nb, and Mo / V / Sb / Nb = 1 / 0.3 / 0.15. Oxide catalysts having a molar ratio of ˜0.2 / 0.05 are disclosed. In these catalysts, the yield of unsaturated nitrile is relatively high, but the space-time yield is as small as 0.11 to 0.22 (μmol / ((g · s / ml) · g)), and the production per reactor is There is a problem that the property becomes low. On the other hand, when the reaction temperature is increased in order to increase the space time yield, there arises a problem that the selectivity of the unsaturated nitrile decreases and as a result, the yield decreases.
[0005]
In addition, as described in Applied Catalysis A General 157, 143-172 (1997), ammonia is not only converted into acrylonitrile, which is a target product of the ammoxidation reaction of propane, but also by-products of acetonitrile and hydrocyanic acid. And converted to nitrogen as an oxidative degradation product. The oxide catalyst composed of Mo-V-Sb-Nb has a difficulty in that the decomposition rate from ammonia to nitrogen is large, and it is desired to suppress this and increase the utilization efficiency of ammonia. In the oxide catalyst containing Mo-V-Sb used for the ammoxidation reaction of propane or isobutane, a catalyst having a high unsaturated nitrile yield and a high space-time yield and a low decomposition rate from ammonia to nitrogen has not been obtained. .
[0006]
[Problems to be solved by the invention]
An object of the present invention is an oxide catalyst containing antimony, which is a component having a low scattering property, used for producing an unsaturated nitrile by a gas phase catalytic ammoxidation reaction of propane or isobutane. An object of the present invention is to provide a catalyst having a high yield and space time yield and a low oxidative decomposition rate from ammonia to nitrogen.
[0007]
[Means for Solving the Problems]
As a result of intensive investigations on an oxide catalyst containing molybdenum, vanadium and antimony used in the production of an unsaturated nitrile by gas-phase catalytic oxidation of propane or isobutane in the presence of ammonia, the present inventors have studied these three components. By using an oxide catalyst obtained by contacting an oxide containing N2 with an aqueous ammonia solution and calcining in the absence of oxygen , the yield of unsaturated nitrile and the space-time yield are high, and ammonia to nitrogen oxidative decomposition rate is suppressed to, it found that utilization efficiency of the ammonia is improved, leading to the completion of the present invention.
[0008]
That is, the present invention
(1) In a method for producing an oxide catalyst used for producing an unsaturated nitrile by gas phase catalytic ammoxidation of propane or isobutane, an oxide having a component composition represented by the following formula (I) is contacted with an aqueous ammonia solution Separating and removing the aqueous ammonia solution , and calcining in the absence of oxygen , a method for producing an oxide catalyst,
Mo 1 V a Sb b Z c O n (I)
(In the formula (I), Z is Nb, W, Cr, Ti, Ta, Zr, Hf, Mn, Re, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, B, Ga. , In, Ge, Sn, P, Pb, Bi, Y, at least one element selected from rare earth elements and alkaline earth metals, and a, b, c and n represent the atomic ratio per Mo atom. 0.1 ≦ a ≦ 1, 0.01 ≦ b ≦ 0.6, 0 ≦ c ≦ 1, and n is an atomic ratio determined by the oxidation state of the constituent metals.
(2) The method for producing an oxide catalyst according to (1) , wherein the firing temperature is 400 ° C to 700 ° C,
(3) In producing a corresponding unsaturated nitrile by subjecting propane or isobutane to gas phase catalytic ammoxidation reaction in the presence of an oxide catalyst, the oxide catalyst was obtained by the method for producing an oxide catalyst described in (1) or (2) . The present invention relates to a method for producing an unsaturated nitrile characterized by using a catalyst.
[0009]
Hereinafter, the present invention will be described in detail. The present invention is characterized in that an oxide having a component composition represented by formula (I) is converted into an aqueous ammonia solution in a method for producing an oxide catalyst used for producing an unsaturated nitrile by gas phase catalytic ammoxidation of propane or isobutane. Then, the oxide catalyst obtained by separating and removing the aqueous ammonia solution is used as an oxide catalyst for producing an unsaturated nitrile.
Mo 1 V a Sb b Z c O n (I)
(In the formula (I), X is Nb, W, Cr, Ti, Ta, Zr, Hf, Mn, Re, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, B, Ga. , In, Ge, Sn, P, Pb, Bi, Y, at least one element selected from rare earth elements and alkaline earth metals, preferably Nb, W, Sn, Ti, particularly preferably Nb, Ti A, b, c and n represent the atomic ratio per Mo atom, 0.1 ≦ a ≦ 1, preferably 0.1 ≦ a ≦ 0.5, particularly preferably 0.2 ≦ a ≦ 0. .4, b is 0.01 ≦ b ≦ 0.6, preferably 0.1 ≦ b ≦ 0.3, particularly preferably 0.1 ≦ b ≦ 0.25, c is 0 ≦ c ≦ 1, preferably 0.01 ≦ c ≦ 0.5, particularly preferably 0.01 ≦ c ≦ 0.2, and n depends on the oxidation state of the constituent metals. Is an atomic ratio determined Te.)
[0010]
The concentration of ammonia is preferably 0.1 wt% to 50 wt%, particularly preferably 1 wt% to 10 wt%. Examples of the method of bringing the oxide having the component composition represented by the formula (I) into contact with the aqueous ammonia solution include a batch operation method and a distribution operation method. In the case of the batch operation method, the oxide is suspended in an aqueous ammonia solution using a tank reactor. The weight of the oxide with respect to the weight of the aqueous ammonia solution is preferably 1 to 20% by weight. The contacting time is not particularly limited, but is preferably 2 hours or more, more preferably 6 hours or more. Although the temperature of ammonia aqueous solution can be used suitably at 0-100 degreeC , 0-50 degreeC is more preferable. In order to perform contact efficiently, the suspension may be stirred using a stirrer, or may be stirred by blowing bubbles. As the flow operation method, a method such as flowing an aqueous ammonia solution through a fixed bed filled with the oxide can be used.
[0011]
After the oxide is contacted with an aqueous ammonia solution, to obtain an oxide catalyst of the present invention an aqueous ammonia solution was separated and removed. Separation can be performed by centrifugation, filtration using a filter paper or membrane filter, decantation, or the like. The oxide catalyst is preferably washed with water and dried after separating and removing the aqueous ammonia solution . The oxide catalyst thus obtained is preferably calcined. Firing is carried out using a rotary furnace, tunnel furnace, tubular furnace, fluidized firing furnace or the like, under an inert gas atmosphere such as nitrogen that does not substantially contain oxygen, preferably 400 to 700 ° C. while circulating an inert gas, It is preferable to carry out at 500 to 650 ° C. The firing time is 0.5 to 5 hours, preferably 1 to 3 hours. In the present invention, “in the absence of oxygen” means that the oxygen concentration in the inert gas is 1000 ppm or less, preferably 100 ppm or less as measured by gas chromatography or a trace oxygen analyzer.
[0012]
The contact treatment with the aqueous ammonia solution can be repeated, and the yield of unsaturated nitrile and the space time yield can be further increased by repeated operations. The following compounds can be used as raw materials for the component metal for producing the oxide having the component composition represented by the formula (I). As the vanadium raw material, ammonium metavanadate, vanadium oxide (V), vanadium oxychloride, vanadium alkoxide, or the like can be used, and preferably ammonium metavanadate or vanadium oxide (V).
[0013]
As the molybdenum raw material, ammonium heptamolybdate, molybdenum oxide, molybdenum oxychloride, molybdenum chloride, molybdenum alkoxide, and the like can be used, and preferably ammonium heptamolybdate.
Antimony raw materials are organic such as antimony oxide (III), antimony oxide (V), antimony (III), antimony chloride (III), antimony chloride (III), antimony oxide nitrate (III), alkoxide of antimony, antimony tartrate, etc. A compound containing trivalent antimony such as an acid salt can be used, and antimony (III) oxide is preferable.
[0014]
Nb, W, Cr, Ti, Ta, Zr, Hf, Mn, Re, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, B, Ga, In, Ge, Sn, P, As raw materials for Pb, Bi, Y, rare earth elements and alkaline earth metals, oxalate, hydroxide, oxide, nitrate, acetate, ammonium salt, carbonate, alkoxide and the like can be used. When niobium or titanium is used, an oxalate aqueous solution can be preferably used. Niobium oxalate can be produced, for example, by dissolving niobic acid in an aqueous oxalic acid solution. When there is insoluble niobic acid, it is preferable to remove the insoluble matter by filtration or the like. The molar ratio of oxalic acid / niobium is preferably 1-10, more preferably 2-6.
[0015]
The catalyst of the present invention can be used by being supported on 20 to 60% by weight, preferably 20 to 40% by weight of silica based on the total weight including silica as a support. Silica sol can be suitably used as the silica raw material. It is preferable to use a sol stabilized with ammonium ions.
In this invention, the oxide which has a component composition shown by Formula (I) can be manufactured through three processes of the following raw material preparation, drying, and baking.
<Raw material preparation process>
A mixed solution containing ammonium metavanadate and antimony (III) oxide is reacted with heating in an air atmosphere. As for the temperature of this liquid mixture when heated, 70 to 110 degreeC is preferable. Heating of the mixed solution containing vanadium and antimony may be performed while replenishing transpirational moisture, or may be performed under reflux conditions with a cooling tube attached to the reaction vessel. The heating time is 3 hours or more, particularly preferably 4 to 50 hours. Instead of using ammonium metavanadate as the vanadium source, an aqueous hydrogen peroxide solution of vanadium (V) oxide may be used. The mixed solution containing the two components of vanadium and antimony here may be an aqueous solution or a slurry in which fine particles are suspended. By adding ammonium heptamolybdate or an aqueous solution thereof to the mixed solution containing vanadium and antimony thus obtained, a mixed solution containing three components of molybdenum, vanadium, and antimony can be obtained.
[0016]
In addition, a method for preparing a mixed solution containing three components of molybdenum, vanadium, and antimony is a compound containing vanadium after reacting with heating a mixed solution containing ammonium heptamolybdate and antimony (III) oxide. Alternatively, there is a method of obtaining a mixed solution by adding an aqueous solution.
Next, the mixed solution containing the three components of molybdenum, vanadium, and antimony obtained here is oxidized. As a method of oxidation treatment, a method of heating a mixed solution containing three components of molybdenum, vanadium, and antimony in air at a temperature of 50 to 300 ° C. or more for 1 hour or more, preferably 70 to 110 ° C. for 4 hours or more, There is a method using hydrogen peroxide solution. When using a hydrogen peroxide solution, a hydrogen peroxide solution containing a hydrogen peroxide equivalent to 0.01 to 2, particularly preferably 0.1 to 1, is preferably used in a molar ratio with respect to the antimony amount.
[0017]
Furthermore, when using the X component, the X component may be added to the mixed solution after oxidizing the mixed solution containing the three components of molybdenum, vanadium, and antimony, or may be added to the mixed solution before the oxidizing treatment. You may do it. When niobium is used as the X component, it is preferable to use an aqueous solution in which niobic acid and oxalic acid are dissolved in water.
W, Cr, Ti, Ta, Zr, Hf, Mn, Re, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, B, Ga, In, Ge, Sn, P, Pb, When Bi, Y, rare earth elements and alkaline earth metals are used, nitrates, oxalates, acetates, hydroxides, oxides, ammonium salts, carbonates and the like of these metals, and their aqueous solutions and slurries Is added to a mixed solution containing three components of molybdenum, vanadium and antimony after the oxidation treatment or before the oxidation treatment.
[0018]
In the case of producing a silica-supported catalyst, the catalyst raw material liquid can be obtained by adding silica sol in any step of the above-mentioned preparation sequence.
<Drying process>
The catalyst raw material liquid obtained in the raw material preparation step can be dried by spray drying or evaporation to dryness 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. At this time, the dryer inlet temperature of hot air is preferably 150 to 300 ° C. Spray drying can also be performed simply by spraying the catalyst raw material liquid onto an iron plate heated to 100 ° C to 300 ° C.
<Baking process>
The oxide shown by Formula (1) can be obtained by baking the dry powder obtained at the drying process. Firing is performed using a rotary furnace, a tunnel furnace, a tubular furnace, a fluidized firing furnace, or the like, under an inert gas atmosphere such as nitrogen that does not substantially contain oxygen, preferably while circulating an inert gas, at 500 to 700 ° C., Preferably it can implement at 550-650 degreeC. The firing time is 0.5 to 5 hours, preferably 1 to 3 hours. The oxygen concentration in the inert gas is 1000 ppm or less, preferably 100 ppm or less as measured by gas chromatography or a trace oxygen analyzer. Firing can be repeated. Prior to this calcination, the calcination can be performed at 200 ° C. to 420 ° C., preferably 250 ° C. to 350 ° C. for 10 minutes to 5 hours in an air atmosphere or under air flow. Further, the obtained oxide can be pulverized and further baked.
[0019]
The oxide represented by the formula (1) thus obtained was brought into contact with an aqueous ammonia solution as described above, and then the aqueous ammonia solution was separated and removed , and calcined in the absence of oxygen to obtain the oxide of the present invention. A catalyst is obtained. Unsaturated nitriles can be produced by gas phase catalytic ammoxidation of propane or isobutane in the presence of the resulting oxide catalyst of the present invention. Propane or isobutane and ammonia feeds do not necessarily have to be high purity, and industrial grade gases can be used. 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.
[0020]
The molar ratio of ammonia to propane or isobutane supplied to the reaction is 0.1 to 1.5, preferably 0.2 to 1.2. The molar ratio of molecular oxygen supplied to the reaction to propane or isobutane is 0.2 to 6, preferably 0.4 to 4.
The reaction pressure is 0.1 to 10 atm, preferably 1 to 3 atm.
The reaction temperature is 350 ° C to 600 ° C, preferably 380 ° C to 470 ° C.
The contact time is 0.1 to 30 (g · s / ml), preferably 0.5 to 10 (g · s / ml).
For the reaction, conventional methods such as a fixed bed, a fluidized bed and a moving bed can be adopted. The reaction may be a single flow method or a recycle method.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described with reference to examples of ammoxidation reaction of propane. In each example, propane conversion, acrylonitrile selectivity, acrylonitrile yield, and space-time yield of acrylonitrile follow the following definitions, respectively.
Propane conversion rate (%) = (mol number of reacted propane (μmol)) / (mol number of fed propane (μmol)) × 100
Acrylonitrile selectivity (%) = (number of moles of acrylonitrile produced (μmol)) / (number of moles of reacted propane (μmol)) × 100
Acrylonitrile yield (%) = (number of moles of acrylonitrile produced (μmol)) / (number of moles of supplied propane (μmol)) × 100
Space time yield of acrylonitrile (μmol / ((g · s / ml) · g)) = (number of moles of acrylonitrile produced (μmol)) / ((contact time (g · s / ml))) (catalyst weight (G)))
Ammonia decomposition rate (%) = 2 × (number of moles of produced nitrogen) / (number of moles of supplied ammonia) × 100
[0022]
[Example 1]
<Oxide preparation>
Composition formula was prepared oxide represented by Mo 1 V 0.29 Sb 0.14 Nb 0.06 O n as follows. 1.92 g of ammonium metavanadate [NH 4 VO 3 ] and 1.16 g of antimony (III) oxide [Sb 2 O 3 ] were added to 80 g of water, and the mixture was stirred in an oil bath at 100 ° C. for 8 hours under the atmosphere. Refluxed. 10.0 g of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 · 4H 2 O] was added to the resulting two- component mixed liquid to obtain a three-component mixed liquid, and then 85 ° C. in an atmospheric water bath. The mixture was stirred for 4 hours and cooled to room temperature to obtain a catalyst preparation.
[0023]
On the other hand, 0.60 g of niobic acid containing 76% by weight in terms of Nb 2 O 5 and 0.96 g of oxalic acid dihydrate [H 2 C 2 O 4 .2H 2 O] were added to 25 g of water at 70 ° C. After heating and dissolving, the mixture was allowed to cool at 30 ° C. to obtain a niobic acid-containing aqueous solution.
After adding a niobic acid-containing aqueous solution to the catalyst preparation liquid, the mixture was stirred at 30 ° C. for 30 minutes in an air atmosphere to obtain a catalyst raw material liquid. The obtained catalyst raw material liquid was sprayed on a Teflon-coated iron plate heated to 140 ° C. to obtain a dry powder. 12.0 g of the obtained powder was heat treated for 1 hour while circulating air in a 300 ° C. constant temperature bath, then filled in a quartz tube with an inner diameter of 20 mm, and under a nitrogen gas flow of 350 Nml · min −1 . The oxide was obtained by baking at 600 ° C. for 2 hours. The oxygen concentration of the nitrogen gas used was 1 ppm as a result of measurement using a trace oxygen analyzer (manufactured by 306WA Teledyne Analytical Instruments).
[0024]
<Catalyst preparation>
3.0 g of the oxide obtained in the oxide preparation was added to and suspended in 50.0 g of a 5 wt% aqueous ammonia solution and stirred at 25 ° C. for 6 hours to obtain a suspension. The resulting suspension was filtered with suction to separate and remove the aqueous ammonia solution, and the oxide was filtered off. The oxide was then washed by pouring 50 ml of pure water four times. Next, it was dried in a constant temperature bath at 200 ° C. under air flow, and the resulting powder was filled in a quartz tube with an inner diameter of 20 mm and baked at 550 ° C. for 2 hours under a nitrogen gas flow of 350 Nml · min −1. Thus, an oxide catalyst was obtained. Note that the nitrogen gas used is the same as that used for the 600 ° C. firing in the oxide preparation.
<Propane Ammoxidation Test>
0.3 g of the obtained oxide catalyst was charged into a fixed bed type reaction tube having an inner diameter of 4 mm, reaction temperature T = 430 ° C., propane: ammonia: oxygen: helium = 1: 1.2: 2.9: 11.9. A mixed gas having a molar ratio of 5 was flowed at a flow rate F = 6 Nml · min −1 . At this time, the pressure P was 1 atm. The contact time is 1.17 (= W / F × 60 × 273 / (273 + T) × P) (g · s / ml) where the oxide weight is W (g). Analysis of the reaction gas was performed by on-line gas chromatography. The obtained results are shown in Table 1 using propane conversion, acrylonitrile selectivity, space time yield of acrylonitrile and ammonia decomposition rate as indices.
[0025]
[Example 2]
<Catalyst preparation>
4.5 g of the oxide obtained in the oxide preparation of Example 1 was added to and suspended in 80 g of a 5 wt% aqueous ammonia solution, and stirred at 25 ° C. for 15 hours to obtain a suspension. The resulting suspension was filtered with suction to separate and remove the aqueous ammonia solution, and the oxide was filtered off. The oxide was then washed by pouring 50 ml of pure water four times. Next, it was dried in a constant temperature bath at 200 ° C. under air flow, and the total amount of the obtained powder was further filled into a quartz tube with an inner diameter of 20 mm, and baked at 550 ° C. for 2 hours under a nitrogen gas flow of 500 Nml · min −1. Thus, an oxide catalyst was obtained. The nitrogen gas used is the same as in the catalyst preparation of Example 1.
<Propane Ammoxidation Test>
For the obtained oxide catalyst, propane was used under the same conditions as in Example 1 except that the mixed gas flow rate F was 6.4 Nml · min −1 and the contact time was 1.10 (g · s / ml). An ammoxidation reaction test was conducted. The obtained results are shown in Table 1.
[0026]
[Comparative Example 1]
The oxide obtained in the oxide preparation of Example 1 was used as it was.
<Propane Ammoxidation Test>
The propane ammoxidation reaction test was performed under the same conditions as in Example 1. The obtained results are shown in Table 1.
[0027]
[Example 3]
<Oxide preparation>
2.05 g of ammonium metavanadate [NH 4 VO 3 ], 1.16 g of antimony (III) oxide [Sb 2 O 3 ], and 0.50 g of niobic acid containing 76% by weight in terms of Nb 2 O 5 were used. except for this example 1 was repeated to prepare an oxide composition formula represented by Mo 1 V 0.31 Sb 0.14 Nb 0.06 O n.
<Catalyst preparation>
3.0 g of the oxide obtained by the above oxide preparation was added to 50 g of a 10 wt% aqueous ammonia solution to suspend it, and stirred at 25 ° C. for 6 hours to obtain a suspension. The obtained suspension was subjected to suction filtration to separate oxides, and then the oxides were washed by pouring 50 ml of pure water four times. Next, it was dried in a constant temperature bath at 200 ° C. under air flow, and the resulting powder was filled in a quartz tube with an inner diameter of 20 mm and baked at 550 ° C. for 2 hours under a nitrogen gas flow of 500 Nml · min −1. Thus, an oxide catalyst was obtained. Nitrogen gas is the same as the catalyst preparation of Example 1.
<Propane Ammoxidation Test>
The obtained oxide catalyst was subjected to a propane ammoxidation reaction test under the same conditions as in Example 1. The obtained results are shown in Table 1.
[0028]
[Example 4]
<Catalyst preparation>
1.5 g of the oxide obtained in Example 3 was added and suspended in 50 g of a 2 wt% aqueous ammonia solution and stirred at 25 ° C. for 6 hours to obtain a suspension. The obtained suspension was subjected to suction filtration to separate oxides, and then the oxides were washed by pouring 50 ml of pure water four times. Next, it was dried in a constant temperature bath at 200 ° C. under air flow, and the total amount of the obtained powder was further filled into a quartz tube with an inner diameter of 20 mm, and baked at 550 ° C. for 2 hours under a nitrogen gas flow of 500 Nml · min −1 Thus, an oxide catalyst was obtained. Nitrogen gas is the same as the catalyst preparation of Example 1.
<Propane Ammoxidation Test>
The obtained oxide catalyst was subjected to a propane ammoxidation reaction test under the same conditions as in Example 1. The obtained results are shown in Table 1.
[0029]
[Comparative Example 2]
The oxide obtained in the oxide preparation of Example 3 was used as it was.
<Propane Ammoxidation Test>
The obtained oxide was subjected to a propane ammoxidation reaction test under the same conditions as in Example 1. The obtained results are shown in Table 1.
[0030]
[Example 5]
Of the oxide catalyst obtained in Example 1, 1.5 g was added to and suspended in 25 g of a 5 wt% aqueous ammonia solution, and stirred at 25 ° C. for 6 hours to obtain a suspension. The resulting suspension was filtered with suction to remove the oxide catalyst, and then the oxide catalyst was washed by pouring 50 ml of pure water four times. Next, it was dried in a constant temperature bath at 200 ° C. under air flow, and the resulting powder was filled in a quartz tube with an inner diameter of 20 mm and baked at 550 ° C. for 2 hours under a nitrogen gas flow of 500 Nml · min −1. Thus, an oxide catalyst was obtained. Nitrogen gas is the same as the catalyst preparation of Example 1.
<Propane Ammoxidation Test>
For the obtained oxide catalyst, the catalyst weight used was 0.1 g, the mixed gas flow rate F = 12.0 Nml · min −1 , and the contact time was 0.58 (g · s / ml). The propane ammoxidation test was conducted under the same conditions as in Example 1. The obtained results are shown in Table 1.
[0031]
[Comparative Example 3]
1.5 g of the oxide obtained in Example 3 was added to and suspended in 25 g of distilled water, and stirred at 25 ° C. for 6 hours to obtain a suspension. The obtained suspension was subjected to suction filtration to separate oxides, and then the oxides were washed by pouring 50 ml of pure water four times. Next, it was dried in a constant temperature bath at 200 ° C. under air flow, and the resulting powder was filled in a quartz tube with an inner diameter of 20 mm and baked at 550 ° C. for 2 hours under a nitrogen gas flow of 500 Nml · min −1. The catalyst was obtained. Nitrogen gas is the same as the catalyst preparation of Example 1.
<Propane Ammoxidation Test>
The obtained oxide was subjected to a propane ammoxidation reaction test under the same conditions as in Example 1. The obtained results are shown in Table 1.
[0032]
[Table 1]
【The invention's effect】
When the oxide catalyst obtained by the method of the present invention is used, an unsaturated nitrile is obtained in a high yield and a space-time yield from propane or isobutane at a relatively low temperature by a catalyst containing antimony which is a component with low scattering property. Can be manufactured. Moreover, the decomposition | disassembly from ammonia to nitrogen can be suppressed, an unsaturated nitrile can be manufactured efficiently, and the utilization efficiency of ammonia can be improved.
Claims (3)
Ｍｏ１ＶａＳｂｂＺｃＯｎ（Ｉ）
（式（Ｉ）において、ＺはＮｂ、Ｗ、Ｃｒ、Ｔｉ、Ｔａ、Ｚｒ、Ｈｆ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ｚｎ、Ｂ、Ｇａ、Ｉｎ、Ｇｅ、Ｓｎ、Ｐ、Ｐｂ、Ｂｉ、Ｙ、希土類元素およびアルカリ土類金属から選ばれる少なくとも１種類以上の元素であり、ａ、ｂ、ｃおよびｎはＭｏ１原子あたりの原子比を表し、０．１≦ａ≦１、０．０１≦ｂ≦０．６、０≦ｃ≦１、そしてｎは構成金属の酸化状態によって決まる原子比である。）In a method for producing an oxide catalyst used for producing an unsaturated nitrile by vapor-phase catalytic ammoxidation of propane or isobutane, an oxide having a component composition represented by the following formula (I) is brought into contact with an aqueous ammonia solution to form ammonia. A method for producing an oxide catalyst, comprising separating and removing an aqueous solution and calcining in the absence of oxygen .
Mo 1 V a Sb b Z c O n (I)
(In the formula (I), Z is Nb, W, Cr, Ti, Ta, Zr, Hf, Mn, Re, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, B, Ga. , In, Ge, Sn, P, Pb, Bi, Y, at least one element selected from rare earth elements and alkaline earth metals, a, b, c and n represent the atomic ratio per Mo atom 0.1 ≦ a ≦ 1, 0.01 ≦ b ≦ 0.6, 0 ≦ c ≦ 1, and n is an atomic ratio determined by the oxidation state of the constituent metals.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26795898A JP4187839B2 (en) | 1998-09-22 | 1998-09-22 | Method for producing oxide catalyst and method for producing unsaturated nitrile using the catalyst |
| AU54455/99A AU5445599A (en) | 1998-08-28 | 1999-08-30 | Method for producing oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| DE19983250T DE19983250T1 (en) | 1998-08-28 | 1999-08-30 | Process for the preparation of an oxide catalyst for use in the production of acrylonitrile or methacrylonitrile from propane or isobutane |
| IDW20002422A ID28876A (en) | 1998-08-28 | 1999-08-30 | PROCESS TO PRODUCE OXIDE CATALYST FOR USE IN PRODUCING ACRYLONITRIL OR METACRILONITRIL FROM PROPANA AND ISOBUTANA |
| KR10-2000-7013056A KR100373895B1 (en) | 1998-08-28 | 1999-08-30 | Method for producing oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| CNB998065382A CN1166452C (en) | 1998-08-28 | 1999-08-30 | Method for producing oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| US09/674,736 US6514902B1 (en) | 1998-08-28 | 1999-08-30 | Method for producing an oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| PCT/JP1999/004686 WO2000012209A1 (en) | 1998-08-28 | 1999-08-30 | Method for producing oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| SA99200710A SA99200710B1 (en) | 1998-08-28 | 1999-10-30 | Method for producing an oxide catalyst for use in the production of acrylontrile or methacrylontrile from propane or oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26795898A JP4187839B2 (en) | 1998-09-22 | 1998-09-22 | Method for producing oxide catalyst and method for producing unsaturated nitrile using the catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000093796A JP2000093796A (en) | 2000-04-04 |
| JP4187839B2 true JP4187839B2 (en) | 2008-11-26 |
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| JP26795898A Expired - Lifetime JP4187839B2 (en) | 1998-08-28 | 1998-09-22 | Method for producing oxide catalyst and method for producing unsaturated nitrile using the catalyst |
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| Country | Link |
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| JP (1) | JP4187839B2 (en) |
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