JP4034059B2 - Alkane oxidative dehydrogenation catalyst and olefin production method - Google Patents
Alkane oxidative dehydrogenation catalyst and olefin production method Download PDFInfo
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- JP4034059B2 JP4034059B2 JP2001321933A JP2001321933A JP4034059B2 JP 4034059 B2 JP4034059 B2 JP 4034059B2 JP 2001321933 A JP2001321933 A JP 2001321933A JP 2001321933 A JP2001321933 A JP 2001321933A JP 4034059 B2 JP4034059 B2 JP 4034059B2
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- Prior art keywords
- catalyst
- oxidative dehydrogenation
- phase
- oxygen
- reaction
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- 239000003054 catalyst Substances 0.000 title claims description 74
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims description 25
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims description 20
- 150000001336 alkenes Chemical class 0.000 title claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000011572 manganese Substances 0.000 claims description 39
- 238000002441 X-ray diffraction Methods 0.000 claims description 19
- 238000001228 spectrum Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 29
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 23
- 239000000843 powder Substances 0.000 description 20
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 16
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000001282 iso-butane Substances 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
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- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- WOMNSONGFUFOIX-UHFFFAOYSA-H chromium(3+) trisulfate tetrahydrate Chemical compound O.O.O.O.[Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WOMNSONGFUFOIX-UHFFFAOYSA-H 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical group C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing 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
- 239000011261 inert gas Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- DVLUDLYKHQIGSR-UHFFFAOYSA-N nickel(2+);dinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DVLUDLYKHQIGSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- XOTUNZWIDVULPE-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] XOTUNZWIDVULPE-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- 150000002697 manganese compounds Chemical class 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KFOCYSWVGZEOHS-UHFFFAOYSA-N potassium antimony(5+) Chemical compound [K+].[Sb+5] KFOCYSWVGZEOHS-UHFFFAOYSA-N 0.000 description 1
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Images
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】
本発明は低級アルカン酸化脱水素用触媒およびこの触媒を用いたオレフィンの製造方法に関する。詳しくは、本発明は、炭素数２〜５の低級アルカン（以下単に「低級アルカン」という場合もある。）を分子状酸素の存在下に気相酸化脱水素して対応するオレフィンを製造するに好適な触媒、およびこの触媒を用いて低級アルカンを分子状酸素により気相酸化脱水素して高収率で対応するオレフィンを製造する方法に関する。
【０００２】
【従来の技術】
エチレンはエチレンオキシド、アセトアルデヒド、酢酸などの、プロピレンはアクロレイン、アクリル酸、プロピレンオキシド、ポリプロピレンなどの、またイソブテンはメタクロレイン、メタクリル酸、メチルターシャリーブチルエーテルなどの、それぞれ重要な工業製品の原料であるが、近年いずれも需要が伸びて、価格が上昇していることから、これら低級オレフィンの安価な製造方法が求められている。
【０００３】
低級オレフィン、特にプロピレン又はイソブテンの製造方法として、近年低級アルカンの単純脱水素プロセスが工業化されている。しかし、このプロセスは、平衡の制約から、高転化率を得ることが困難で、なおかつ高温を要するという本質的な問題をかかえている。さらに、短時間での触媒の劣化が避けられず、スイッチコンバーターを用いるなどして、頻繁に触媒の再賦活を行う必要がある。このため、プラント建設費や、ユーティリティー費用が高くつき、立地条件によっては経済的になりたたず現時点での実用化は限られている。
【０００４】
一方、平衡上の制約がない酸化脱水素により低級アルカンから低級オレフィンを製造する試みは、かなり以前から行われており、種々の触媒系が提案されている。例えば、Ｃｏ―Ｍｏ酸化物系触媒（ＵＳ４，１３１，６３１）、Ｖ−Ｍｇ酸化物系触媒（ＵＳ４，７７７，３１９）、Ｎｉ−Ｍｏ酸化物系触媒（ＥＰ３７９，４３３Ａ１）、ＣｅＯ2／ＣｅＦ3系触媒（ＣＮ１，０７３，８９３Ａ）、Ｍｇ−Ｍｏ系触媒（Ｎｅｆｔｅｋｈｉｍｉｙａ（１９９０），３０（２），２０７−１０）、Ｖ2Ｏ5／Ｎｂ2Ｏ5系触媒（Ｊ．Ｃｈｅｍ．Ｃｏｍｍｕｎ．（１９９１），（８），５５８−９）、希土類バナデート系触媒（Ｃａｔａｌ．Ｌｅｔｔ．（１９９６），３７，（３，４），２４１−６）、Ｂ2Ｏ3／Ａｌ2Ｏ3系触媒（ＡＣＳ Ｓｙｍｐ．Ｓｅｒ．（１９９６），６３８（Ｈｅｔｅｒｏｇｅｎｅｏｕｓ Ｈｙｄｒｏｃａｒｂｏｎ Ｏｘｉｄａｔｉｏｎ）１５５−１６９）などが知られている。しかし、これら公知の触媒は、酸化脱水素の性能がいずれも非常に低いレベルにあり、工業化にははるかに及ばない状況にある。また本発明者らも、ＣｒあるいはＭｏとＳｂおよびＷを必須とする触媒（特開２０００−０３７６２４号公報）、及びＭｎを必須成分とする触媒（特開２０００−０３７６２５号公報）を開示しているが、工業化にはさらに高いレベルが望まれている。
【０００５】
【発明が解決しようとする課題】
本発明の目的は、低級アルカンを分子状酸素により気相酸化脱水素して対応する低級オレフィンを高収率で製造できる新規な酸化脱水素用触媒を提供すること、およびこの触媒を用いて低級アルカンから高収率で対応するオレフィンを製造する方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明の上記目的は、Ｍｎを必須成分として含んでいること、並びに、回折角２θ（±０．３°）が３２．９°、５５．２°、２３．１°、３８．２°および６５．８°であるときに（すなわち結晶固有の格子面間隔，ｄ値，が２．７２Å、１．６６Å、３．８４Å、２．３５Åおよび１．４２Åであるときに）Ｘ線回折スペクトル（対陰極Ｃｕ−Ｋα）に現われるピークによって同定される結晶相（すなわちＭｎ2Ｏ3に対応する結晶相）を含んでいること、を特徴とする触媒によって達成される。炭素数２〜５の低級アルカンの気相酸化脱水素する際に、該触媒を用いることにより高収率で低級オレフィンを製造することができる。
【０００７】
【発明の実施の形態】
本発明において、炭素数２〜５の低級アルカンとは、具体的にはエタン、プロパン、ｎ−ブタン、イソブタン、ｎ−ペンタンおよびイソペンタンを意味する。これら低級アルカンは各々単独で用いても、あるいは２種以上を組み合わせた混合物として用いてもよい。
【０００８】
本発明によれば、これら低級アルカンから対応するオレフィンを高収率で製造することができ、具体的には、エタンからエチレンを、プロパンからプロピレンを、ｎ−ブタンからｎ−ブテンを、イソブタンからイソブテンを、ｎ−ペンタンからｎ−ペンテンを、そしてイソペンタンからイソペンテンを製造することができる。中でもプロパン又はイソブタンから夫々プロピレン又はイソブテンを製造するに好適に用いられる。
【０００９】
本発明の触媒は、Ｍｎを含有すること、並びに、回折角２θ（±０．３°）が３２．９°、５５．２°、２３．１°、３８．２°および６５．８°であるときにＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）に現われるピークによって同定される結晶相を含有すること、を特徴とするものであり、中でも、特に、下記一般式（１）
ＭｎaＸbＹcＯx （１）
で表される元素組成で実質的に構成されるものが好ましい。
【００１０】
上記一般式（１）において、Ｍｎはマンガンを表し、ＸはＳｂ、ＷおよびＣｒからなる群から選ばれる少なくとも１種の元素を表し、ＹはＲｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｎｂ、Ｔａ、Ｃｅ、Ｚｎ、Ｔｌ、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、ＳｒおよびＢａからなる群より選ばれる少なくとも１種の元素を表し、Ｏは酸素を表す。
【００１１】
上記一般式（１）の触媒は、Ｘ成分としてＳｂ，ＷおよびＣｒのうちの２種あるいは３種の元素を含有するものが好ましく、さらにＹ成分としてＮｉ、Ｃｏ、Ｎｂ、Ｔａ、Ｃｅ、Ｌｉ、ＮａおよびＫからなる群より選ばれる１ないし４種の元素を含有するものが特に好ましい。
【００１２】
上記一般式（１）において、ａ、ｂ、ｃおよびｘは各々Ｍｎ、Ｘ、Ｙおよび酸素の原子比を表し、ａが１のとき、ｂは０．０１〜２でｃは０〜２であり、ｘは酸素以外の元素の酸化状態によって定まる数値である。特に好ましい触媒は、ａが１のとき、ｂが０．０５〜１でｃが０〜１であるものである。
【００１３】
本発明の酸化脱水素用触媒は、さらに活性向上および物理的耐久性向上を目的として、耐火性無機物質を含むこともできる。耐火性無機物質の量は、触媒活性成分を含む全触媒量の１０〜９０質量％が好ましい。耐火性無機物質としては、公知のものを用いることができ、例えば、シリカ、アルミナ、チタニア、ジルコニア、シリカ−アルミナ、シリカ−チタニア、シリカ−ジルコニアなどを挙げることができる。なかでも、シリカ、シリカ−アルミナおよびチタニアが目的物を高収率で与える点で好ましく、シリカ−アルミナとしては、シリカの割合が１０質量％以上、１００質量％未満のものが好適に使用される。
【００１４】
本発明の触媒を製造する際、その調製法としては、最終的に上記結晶相を含有する触媒が得られれば特に限定されるものではないが、例えば、用いるマンガン原料によっては、後の工程の加熱処理条件を変更する必要があるなど、工程の組み合わせには制約が加わる場合もある。しかし、工程それぞれについては特に制限はなく、公知の方法を採用することができる。例えば、次のような工程に従うことによって、本発明の触媒を製造することができる：三酸化二マンガン［酸化マンガン（ＩＩＩ）］粉末を含むスラリーに、三酸化アンチモン粉末、メタタングステン酸アンモニウム水溶液及び硝酸クロム水溶液の少なくとも１つを添加し、また必要に応じて、Ｎｉ、Ｃｏ、Ｌｉ、Ｎａ、Ｋ、Ｒｅ、Ｆｅ、Ｎｂ、Ｔａ、Ｃｅ、Ｚｎ、Ｔｌ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、ＳｒおよびＢａから選ばれる少なくとも１種の元素の化合物の水溶液または酸化物粉末を添加し、さらに、必要によりこれにシリカ、アルミナなどのような耐火性無機物質を加える。得られたスラリーを一定時間混合攪拌した後、加熱濃縮して得られたペーストを８０℃〜３００℃で乾燥する。これを、らいかいし、成型し、必要により破砕してサイズ調整したのち、８０〜３００℃で再乾燥し、あるいは必要に応じてさらに３００℃〜８００℃で焼成する。
【００１５】
上記の乾燥及び焼成は、大気中、高酸素濃度雰囲気中、低酸素濃度雰囲気中、還元性雰囲気中、不活性ガス（窒素、ヘリウム、アルゴン等）雰囲気中あるいは真空中のいずれでも行うことができる。本発明の触媒は、高温、例えば上記３００〜８００℃、での焼成を行わず、３００℃以下の温度、例えば上記８０〜３００℃、での乾燥処理後にそのままアルカンおよび酸素を含む反応ガスに接触させることもでき、その際、直接所定の反応温度で反応を開始しても、また所定の反応温度以上の温度で前処理を兼ねた反応をおこなってもよい。この場合、反応初期には活性の変化が観測されることがあるが、通常１時間以内に活性は安定する。このように直接反応ガスで処理を行う方が、反応ガス以外の雰囲気下で３００℃以上、例えば３００〜８００℃、での高温焼成を行った場合に比べ、活性及び選択性が向上する傾向にあるので、特に好ましい。
【００１６】
上記触媒の調製に用いられる原料には特に制限はなく、各金属の硝酸塩、硫酸塩、酸化物、水酸化物、塩化物、炭酸塩、酢酸塩、酸素酸、酸素酸アンモニウム塩などを使用することができる。
【００１７】
マンガン原料としては各種酸化物粉末又は成型品がそのまま使用できるほか、硝酸マンガン等の水溶液をアンモニア水溶液等で処理して得られる水酸化マンガンスラリー、マンガン化合物及び他の成分元素の化合物を含む、水溶液からの共沈物、など一般的手法により調製されるものはすべて使用できる。好ましいのはＭｎ2Ｏ3含有物である。特に好ましいのは、実質的にＭｎ2Ｏ3のみからなるマンガン酸化物である。このようなマンガン酸化物のＸ線回折スペクトルには、Ｍｎ2Ｏ3に対応する結晶相に帰属されるピークのみが現われる。
【００１８】
最終的に得られる触媒は、回折角２θ（±０．３°）が３２．９°、５５．２°、２３．１°、３８．２°および６５．８°であるときに（すなわちｄ値が２．７２Å、１．６６Å、３．８４Å、２．３５Åおよび１．４２Åであるときに）Ｘ線回折スペクトル（対陰極Ｃｕ−Ｋα）に現われるピークによって同定される結晶相（すなわちＭｎ2Ｏ3に対応する結晶相）を含むものでなければならない。そのためには、Ｍｎ原料としてＭｎ2Ｏ3を使用し、最終的にＭｎ2Ｏ3相が維持される調製条件をとるか、あるいは原料にＭｎ2Ｏ3を含まなくても、調製過程でＭｎ2Ｏ3相が形成されるような調製条件をとればよい。より好ましくはＭｎ2Ｏ3を原料として使用し、３００℃以上の熱処理を行わない調製方法である。
【００１９】
原料としてＭｎ酸化物を使用する場合、その比表面積は０．５〜１０ｍ2／ｇのものが好ましい。この範囲を越えると、得られる触媒の完全酸化活性が強くなり、高い部分選択性が得られなくなる。またこの範囲を下回ると、活性が低いものとなる。
【００２０】
Ｓｂ原料としては、Ｓｂ2Ｏ3、Ｓｂ2Ｏ4、Ｓｂ2Ｏ5などのような酸化物の粉末、Ｓｂ酸化物を酒石酸水溶液に溶解させたもの、アンチモン酸（五酸化アンチモン水和物）ゾルなどが好適に使用できる。このうちアンチモン酸ゾルまたはＳｂ2Ｏ3粉末が触媒調製での均一性及び得られた触媒の性能面で好ましい。アンチモン酸ゾルは、市販のものもあるが、各種の安定化剤が添加されているため、触媒原料としては適さない物が多い。アンチモン（Ｖ）酸カリウム水溶液を強酸性陽イオン交換樹脂に通してイオン交換することによって得られるアンチモン酸ゾルが、不純物を含まない点で好ましい。
【００２１】
また、他の元素の原料に関しては、一般的に水溶性原料を使用する事が好ましいが、元素の種類によっては酸化物などのような水不溶性の原料も使用できる。
【００２２】
本発明において使用される耐火性無機物質は、その使用形態についても特に制限はなく、成型体、粉末、ゲル、ゾルなど、多様な形態のものを、触媒の使用形態にあわせて使い分けることができる。
【００２３】
本発明の気相酸化脱水素反応を行う際の原料ガスとしては、低級アルカンおよび分子状酸素のほかに、必要に応じて、希釈ガスを用いることができる。分子状酸素源としては、空気または純酸素が使用される。希釈ガスとしては、窒素、ヘリウム、炭酸ガスなどのような不活性ガスや水蒸気などが好適に用いられる。分子状酸素は、通常、アルカン１モルに対して、０．１〜５モルの割合で用いればよい。
【００２４】
本発明の気相酸化脱水素反応を実施する際の反応条件には特に制限はなく、例えば、空間速度３００〜３００００ｈｒ-1及び反応温度２５０〜６５０℃の条件下に上記原料ガスを本発明の酸化脱水素用触媒に接触させればよい。
【００２５】
上記反応は通常、常圧下で行うが、減圧下または加圧下でも実施することができる。反応方式についても特に制限はなく、固定床式、移動床式または流動床式のいずれでもよい。また、単流方式でもリサイクル方式でもよい。
【００２６】
【実施例】
以下実施例を挙げて本発明をさらに具体的に説明する。尚、転化率、単流収率、および選択率はそれぞれ以下のように定義される。
転化率（モル％）＝（反応したアルカンのモル数／供給したアルカンのモル数）×１００
選択率（モル％）＝（生成した各化合物のモル数／反応したアルカンのモル数）×１００
単流収率（モル％）＝（生成した各化合物のモル数／供給したアルカンのモル数）×１００
図１は、全ての実施例でＭｎ原料として使用した三酸化二マンガン［酸化マンガン（ＩＩＩ）］粉末のＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）である。横軸は回折角２θであり、縦軸はピーク強度（ｃｐｓ）である。
【００２７】
主要５ピークＡ、Ｂ、Ｃ、Ｄ及びＥ並びにその他の微小ピークもすべてＭｎ2Ｏ3相に帰属されるピークである。
【００２８】
図２は、実施例１で得られた触媒のＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）である。横軸および縦軸は図１と同じである。
【００２９】
Ａ、Ｂ、Ｃ、Ｄ及びＥはＭｎ2Ｏ3相の主要５ピークに帰属される。
【００３０】
２θが１４．８°、２９．９°及び２８．６°であるときに現われているピークはＨ14Ｓｂ14Ｏ21（ＯＨ）42に帰属される。
【００３１】
図３は、実施例１６で得られた触媒のＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）である。横軸および縦軸は図１と同じである。
【００３２】
Ａ、Ｂ、Ｃ、Ｄ及びＥはＭｎ2Ｏ3相の主要５ピークに帰属される。
【００３３】
２θが１５．２°、３０．６°及び２９．３°であるときに現われているピークはＳｂ2Ｏ5・４Ｈ2Ｏに帰属される。
【００３４】
図４は、比較例１で得られた触媒のＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）である。横軸および縦軸は図１と同じである。
【００３５】
Ｍｎ2Ｏ3相に帰属されるピークはなく、２θが２１．８°、３５．１°、３６．８°、５５．３°および３８．４°であるときにＭｎＯ2相に帰属されるピークが現われ、２θが１４．８°、２９．９°及び２８．６°であるときにＨ14Ｓｂ14Ｏ21（ＯＨ）42に帰属されるピークが現われている。
実施例１
Ｍｎ原料として使用する三酸化二マンガン［酸化マンガン（ＩＩＩ）］粉末を以下のように調製した。
【００３６】
二酸化マンガン［酸化マンガン（ＩＶ）］粉末（比表面積４１ｍ2／ｇ）１００ｇを坩堝に入れ、大気下のマッフル炉で、６００℃で３時間焼成した。得られた粉末のＸ線回折（対陰極Ｃｕ−Ｋα）を測定したところ、回折角２θ（±０．３°）が３２．９°、５５．２°、２３．１°、３８．２°及び６５．８°であるときに（すなわちｄ値が２．７２Å、１．６６Å、 ３．８４Å、２．３５Å及び１．４２Åであるとき）にＭｎ2Ｏ3に対応する結晶相の存在を示す主要ピークが確認されたが、他の結晶相は確認できなかった（図１）。この三酸化二マンガン［酸化マンガン（ＩＩＩ）］粉末の比表面積は５．０ｍ2／ｇであった。
【００３７】
Ｓｂ原料となるアンチモン酸ゾルを以下のように調製した：ヘキサヒドロキソアンチモン（Ｖ）酸カリウム４３．８ｇを２リットルの水に加熱溶解し、不溶物をろ過した。このろ液を強酸性陽イオン交換樹脂（ＤＯＷＥＸ ５０Ｗ×４）５００ｇを充填したカラムに１５ｍｌ／分の速度で流通し、イオン交換処理を行った。得られた液はほぼ透明な溶液であったが、一日後、やや白濁したゾル状態となり、ゾル中のＳｂ濃度をＩＣＰ発光分析測定装置で求めると０．０６７ｍｍｏｌ／ｇであった。イオン交換率は９９．５％であり、ゾル中の残存Ｋ量は無視できる量であった。
【００３８】
５００ｍｌビーカーに、上記の三酸化二マンガン［酸化マンガン（ＩＩＩ）］粉末３．９５ｇ及びアンチモン酸ゾル２２３．９ｇを加え、加熱攪拌を開始した。約８０℃に到達後、２時間のあいだにわたって液量を保ちながら攪拌を行った。この後、９０℃の温度で加熱しながら攪拌を約４時間続けて水分を蒸発させることによって濃縮した。得られたペーストを１２０℃で１４時間乾燥した後、らいかいし、成型し、さらに破砕することによって、９〜２０メッシュに大きさを揃えた。
【００３９】
得られた触媒の組成は、Ｍｎ1Ｓｂ0.3Ｏxであった。このもののＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）では、回折角２θ（±０．３°）が３２．９°、５５．２°、２３．１°、３８．２°および６５．８°であるときにＭｎ2Ｏ3相に帰属される主要ピークが観測された。そのほかには、Ｈ14Ｓｂ14Ｏ21（ＯＨ）42に帰属される結晶相のピークが観測されたのみであった（図２）。
【００４０】
この触媒を通常の流通式反応装置に充填し、下記条件下で反応を行った。反応開始から１時間後の反応結果を表１に示す。
触媒量：１．５ｇ
反応ガス：Ｃ3Ｈ8／Ｏ2／Ｎ2＝１／１／８（モル比）
反応ガス供給速度：１１２．５ｍｌ（標準状態）／ｍｉｎ
反応温度：４９０℃
以下の実施例でも一部反応温度を変更した以外は同様の条件で反応を行った。それぞれの触媒の組成及び反応開始から１時間後の反応結果を表１に示す。
実施例２及び３
実施例１において、アンチモン酸ゾルの量を、それぞれ、３７３．２ｇ及び７４．６ｇに変更した以外は実施例1と同様に触媒を調製した。
実施例４及び５
実施例１において、アンチモン酸ゾルのかわりに、それぞれ、メタタングステン酸アンモニウム水溶液（ＷＯ3として５０質量％含有）２．３２ｇを２００ｍｌの水で希釈したもの、及び硫酸クロム四水和物１．１１ｇを２００ｍｌの水で加熱溶解させたもの、を使用した以外は実施例１と同様に触媒を調製した。
実施例６
実施例１においてアンチモン酸ゾルを添加した後、さらに硝酸クロム九水和物４．００ｇを５０ｍｌの水で溶解させたもの、を添加した以外は実施例１と同様に触媒を調製した。
実施例７
実施例６においてアンチモン酸ゾルのかわりに、メタタングステン酸アンモニウム水溶液２．３２ｇを５０ｍｌの水で希釈したもの、を添加した以外は実施例６と同様に触媒を調製した。
実施例８
実施例１においてアンチモン酸ゾルを添加した後、メタタングステン酸アンモニウム水溶液２．３２ｇを５０ｍｌの水で希釈したもの、および硝酸クロム九水和物４．００ｇを５０ｍｌの水で溶解させたもの、を添加した以外は実施例１と同様に触媒を調製した。
実施例９
実施例８において、アンチモン酸ゾルに代えて三酸化アンチモン粉末２．１９ｇを用い、かつ、硝酸クロム水溶液に代えて硫酸クロム四水和物２．２２ｇを２００ｍｌの水で溶解させたものを用いた以外は、実施例８と同様に触媒を調製した。
実施例１０−１３
実施例８において、さらに硝酸ニッケル九水和物２．９１ｇを５０ｍｌの水で溶解させたもの（実施例１０）、硝酸コバルト九水和物２．９２ｇを５０ｍｌの水で溶解させたもの（実施例１１）、０．１ｍｏｌ／Ｌ濃度の水酸化カリウム水溶液５ｍｌ（実施例１２）、０．４ｍｏｌ／Ｌ濃度の水酸化リチウム水溶液２．５ｍｌ（実施例１３）を夫々加えた以外は実施例８と同様に触媒を調製した。
実施例１４
実施例８において、さらに０．４ｍｏｌ／Ｌ濃度の水酸化リチウム水溶液２．５ｍｌおよび０．１ｍｏｌ／Ｌ濃度の水酸化カリウム水溶液５ｍｌを加えた以外は実施例８と同様に触媒を調製した。
実施例１５
実施例１４において、さらに硝酸ニッケル九水和物２．９１ｇを５０ｍｌの水で溶解させたもの、を加えた以外は実施例１４と同様に触媒を調製した。
実施例１６
実施例１５において、硝酸クロム水溶液に代えて硫酸クロム四水和物１．２８ｇを５０ｍｌの水で溶解させたもの、を加えた以外は実施例１５と同様に触媒を調製した。
実施例１７
実施例１６において、アンチモン酸ゾルのかわりに三酸化アンチモン粉末２．１９ｇ及び水２００ｍｌを添加した以外は実施例１６と同様に触媒を調製した。
実施例１８
０．１ｍｏｌ／Ｌ濃度の水酸化カリウム水溶液の添加量を１２．５ｍｌに変更した以外は実施例１７と同様に触媒を調製した。
実施例１９、２０及び２１
実施例１８において、五酸化ニオブ（Ｎｂ2Ｏ5）粉末１．００ｇ（実施例１９）、酸化タンタル（Ｔａ2Ｏ5）粉末１．６６ｇ（実施例２０）または酸化セリウム（ＣｅＯ2）粉末１．２９ｇ（実施例２１）を、それぞれ追加使用したこと以外は、実施例１８と同様に触媒を調製した。
【００４１】
以上すべての実施例の触媒は、反応に使用される前のＸ線回折（対陰極Ｃｕ−Ｋα）において、回折角２θ（±０．３°）が３２．９°、５５．２°、２３．１°、３８．２°および６５．８°であるときに（ｄ値が２．７２Å、１．６６Å、３．８４Å、２．３５Åおよび１．４２Åであるときに）Ｍｎ2Ｏ3相に相当するピークが観測された。それ以外のＭｎ単独酸化物相は観測されなかった。
【００４２】
実施例１６で得られた触媒のＸ線回折スペクトルを図３に示す。
比較例１−９
三酸化二マンガン［酸化マンガン（ＩＩＩ）］粉末のかわりに二酸化マンガン［酸化マンガン（ＩＶ）］粉末（比表面積４１ｍ2／ｇ）４．３５ｇを使用した以外はそれぞれ実施例１、４、５、８、９、１０、１４、１６および１９と同様に触媒を調製した。すべての比較例の触媒は、反応に使用される前のＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）において、ＭｎＯ2相が観測されたのみで、Ｍｎ2Ｏ3相が観測されなかった。
【００４３】
比較例１で得られた触媒のＸ線回折スペクトルを図４に示す。
【００４４】
実施例１−２１及び比較例１〜９の各触媒を使用してプロパンの酸化脱水素反応を行なった。反応温度並びに反応開始から１時間後の反応結果を表１に示す。
【００４５】
【表１】
実施例２２
実施例１６においてプロパンのかわりにイソブタンを使用し且つ反応温度を５３０℃から４９０℃に変えた以外は実施例１６と同様にイソブタンの酸化脱水素反応を行った。反応開始から１時間後の反応結果は、イソブタン転化率が３５．７モル％、イソブテン選択率が３２．５モル％、メタクロレイン選択率が１．０モル％、そしてイソブテン単流収率が１１．６モル％であった。
比較例１０
実施例２２において比較例８と同じ触媒を使用した以外は実施例２２と同様にイソブタンの酸化脱水素反応を行った。反応開始から１時間後の反応結果は、イソブタン転化率が２８．３モル％、イソブテン選択率が２７．６モル％、メタクロレイン選択率が０．８モル％、そしてイソブテン単流収率が７．８モル％であった。
【００４７】
【発明の効果】
本発明の低級アルカン酸化脱水素用触媒は酸化脱水素能に優れ、低級アルカンから対応するオレフィンを高収率で製造することができる。
【図面の簡単な説明】
【図１】全ての実施例でＭｎ原料として使用した三酸化二マンガン粉末のＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）である。横軸は回折角２θであり、縦軸はピーク強度（ｃｐｓ）である。主要ピークＡ、Ｂ、Ｃ、Ｄ及びＥ並びにその他の微小ピークもすべてＭｎ2Ｏ3相に帰属されるピークである。
【図２】実施例１で得られた触媒のＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）である。横軸および縦軸は図１と同じである。Ａ、Ｂ、Ｃ、Ｄ及びＥはＭｎ2Ｏ3相の主要５ピークに帰属される。２θが１４．８°、２９．９°及び２８．６°であるときに現われているピークはＨ14Ｓｂ14Ｏ21（ＯＨ）42に帰属される。
【図３】実施例１６で得られた触媒のＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）である。横軸および縦軸は図１と同じである。Ａ、Ｂ、Ｃ、Ｄ及びＥはＭｎ2Ｏ3相の主要５ピークに帰属される。２θが１５．２°、３０．６°及び２９．３°であるときに現われているピークはＳｂ2Ｏ5・４Ｈ2Ｏに帰属される。
【図４】比較例１で得られた触媒のＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）である。横軸および縦軸は図１と同じである。Ｍｎ2Ｏ3相に帰属されるピークはなく、２θが２１．８°、３５．１°、３６．８°、５５．３°及び３８．４°であるときにＭｎＯ2相に帰属されるピークが現われ、２θが１４．８°、２９．９°及び２８．６°であるときにＨ14Ｓｂ14Ｏ21（ＯＨ）42に帰属されるピークが現われている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lower alkane oxidative dehydrogenation catalyst and an olefin production method using the catalyst. Specifically, the present invention provides a corresponding olefin by gas phase oxidative dehydrogenation of a lower alkane having 2 to 5 carbon atoms (hereinafter sometimes referred to simply as “lower alkane”) in the presence of molecular oxygen. The present invention relates to a suitable catalyst and a process for producing a corresponding olefin in high yield by gas phase oxidative dehydrogenation of lower alkanes with molecular oxygen using this catalyst.
[0002]
[Prior art]
Ethylene is an important raw material for industrial products such as ethylene oxide, acetaldehyde, and acetic acid, propylene is acrolein, acrylic acid, propylene oxide, and polypropylene, and isobutene is a material such as methacrolein, methacrylic acid, and methyl tertiary butyl ether. In recent years, demand has increased and prices have risen, and therefore, an inexpensive method for producing these lower olefins has been demanded.
[0003]
As a process for producing lower olefins, particularly propylene or isobutene, a simple dehydrogenation process of lower alkanes has recently been industrialized. However, this process has an essential problem that it is difficult to obtain a high conversion rate due to equilibrium constraints and still requires a high temperature. Furthermore, catalyst deterioration is unavoidable in a short time, and it is necessary to re-activate the catalyst frequently by using a switch converter. For this reason, plant construction costs and utility costs are high, and depending on the location conditions, it is not economical and practical use is limited at this time.
[0004]
On the other hand, attempts to produce lower olefins from lower alkanes by oxidative dehydrogenation without equilibrium restrictions have been made for a long time, and various catalyst systems have been proposed. For example, Co-Mo oxide catalyst (US 4,131,631), V-Mg oxide catalyst (US 4,777,319), Ni-Mo oxide catalyst (EP 379,433 A1), CeO 2 / CeF 3 Catalyst (CN1,073,893A), Mg-Mo catalyst (Neftekhimiya (1990), 30 (2), 207-10), V 2 O 5 / Nb 2 O 5 catalyst (J. Chem. Commun. 1991), (8), 558-9), rare earth vanadate catalysts (Cataly. Lett. (1996), 37, (3,4), 241-6), B 2 O 3 / Al 2 O 3 catalysts ( ACS Symp. Ser. (1996), 638 (Heterogeneous Hydrocarbon Oxidation) 155-169) are known. However, these known catalysts all have very low levels of oxidative dehydrogenation performance and are far from being industrialized. In addition, the present inventors also disclosed a catalyst containing Cr or Mo and Sb and W (Japanese Patent Laid-Open No. 2000-037624) and a catalyst containing Mn as an essential component (Japanese Patent Laid-Open No. 2000-037625). However, a higher level is desired for industrialization.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel catalyst for oxidative dehydrogenation capable of producing a corresponding lower olefin in a high yield by gas phase oxidative dehydrogenation of a lower alkane with molecular oxygen, and using this catalyst, The object is to provide a process for producing the corresponding olefin from alkanes in high yield.
[0006]
[Means for Solving the Problems]
The object of the present invention is to contain Mn as an essential component and to have a diffraction angle 2θ (± 0.3 °) of 32.9 °, 55.2 °, 23.1 °, 38.2 ° and X-ray diffraction spectrum (when the crystal lattice spacing, d value is 2.72Å, 1.66Å, 3.84Å, 2.35Å and 1.42Å) when it is 65.8 [deg.] It is achieved by a catalyst characterized in that it contains a crystalline phase identified by a peak appearing in the counter-cathode Cu-Kα) (ie a crystalline phase corresponding to Mn 2 O 3 ). When the gas phase oxidative dehydrogenation of a lower alkane having 2 to 5 carbon atoms is used, a lower olefin can be produced in a high yield by using the catalyst.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the lower alkane having 2 to 5 carbon atoms specifically means ethane, propane, n-butane, isobutane, n-pentane and isopentane. These lower alkanes may be used alone or in a mixture of two or more.
[0008]
According to the present invention, the corresponding olefin can be produced from these lower alkanes in high yield. Specifically, from ethane to ethylene, from propane to propylene, from n-butane to n-butene, from isobutane. Isobutene can be produced from n-pentane, n-pentene, and isopentane. Among them, it is preferably used for producing propylene or isobutene from propane or isobutane, respectively.
[0009]
The catalyst of the present invention contains Mn and has diffraction angles 2θ (± 0.3 °) of 32.9 °, 55.2 °, 23.1 °, 38.2 ° and 65.8 °. It is characterized by containing a crystal phase identified by a peak appearing in an X-ray diffraction spectrum (counter-cathode Cu-Kα) at certain times, and in particular, the following general formula (1)
Mn a X b Y c O x (1)
What is substantially comprised by the elemental composition represented by these is preferable.
[0010]
In the general formula (1), Mn represents manganese, X represents at least one element selected from the group consisting of Sb, W and Cr, and Y represents Re, Fe, Co, Ni, Nb, Ta, Ce Represents at least one element selected from the group consisting of Zn, Tl, Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba, and O represents oxygen.
[0011]
The catalyst of the general formula (1) preferably contains 2 or 3 elements of Sb, W and Cr as the X component, and Ni, Co, Nb, Ta, Ce and Li as the Y component. Particularly preferred are those containing 1 to 4 elements selected from the group consisting of Na and K.
[0012]
In the general formula (1), a, b, c and x each represent an atomic ratio of Mn, X, Y and oxygen, and when a is 1, b is 0.01 to 2 and c is 0 to 2. X is a numerical value determined by the oxidation state of elements other than oxygen. Particularly preferred catalysts are those in which when a is 1, b is 0.05 to 1 and c is 0 to 1.
[0013]
The oxidative dehydrogenation catalyst of the present invention can also contain a refractory inorganic substance for the purpose of further improving the activity and improving the physical durability. The amount of the refractory inorganic substance is preferably 10 to 90% by mass based on the total amount of the catalyst including the catalytically active component. As the refractory inorganic material, known materials can be used, and examples thereof include silica, alumina, titania, zirconia, silica-alumina, silica-titania, silica-zirconia and the like. Among these, silica, silica-alumina and titania are preferable in that they give the desired product in a high yield, and silica-alumina having a silica ratio of 10% by mass or more and less than 100% by mass is suitably used. .
[0014]
When the catalyst of the present invention is produced, the preparation method is not particularly limited as long as the catalyst containing the crystalline phase is finally obtained. For example, depending on the manganese raw material used, There are cases where restrictions are imposed on the combination of processes, such as the need to change the heat treatment conditions. However, each step is not particularly limited, and a known method can be employed. For example, the catalyst of the present invention can be produced by following the following steps: a slurry containing dimanganese trioxide [manganese (III) oxide] powder, antimony trioxide powder, ammonium metatungstate aqueous solution and At least one of chromium nitrate aqueous solution is added, and Ni, Co, Li, Na, K, Re, Fe, Nb, Ta, Ce, Zn, Tl, Rb, Cs, Mg, Ca, Sr are added as necessary. And an aqueous solution or oxide powder of a compound of at least one element selected from Ba and, if necessary, a refractory inorganic material such as silica, alumina or the like, if necessary. The obtained slurry is mixed and stirred for a certain time, and then the paste obtained by heating and concentrating is dried at 80 ° C to 300 ° C. This is crushed, molded, crushed as necessary, adjusted in size, re-dried at 80 to 300 ° C, or further baked at 300 to 800 ° C as necessary.
[0015]
The above drying and firing can be performed in the air, in a high oxygen concentration atmosphere, in a low oxygen concentration atmosphere, in a reducing atmosphere, in an inert gas (nitrogen, helium, argon, etc.) atmosphere or in a vacuum. . The catalyst of the present invention does not undergo calcination at a high temperature, for example, 300 to 800 ° C., and directly contacts a reaction gas containing alkane and oxygen after drying at a temperature of 300 ° C. or less, for example, 80 to 300 ° C. In this case, the reaction may be started directly at a predetermined reaction temperature, or a reaction that also serves as a pretreatment may be performed at a temperature equal to or higher than the predetermined reaction temperature. In this case, a change in activity may be observed at the beginning of the reaction, but the activity is usually stabilized within 1 hour. In this way, the direct treatment with the reaction gas tends to improve the activity and selectivity as compared with the case where high temperature firing is performed at 300 ° C. or higher, for example, 300 to 800 ° C. in an atmosphere other than the reaction gas. This is particularly preferable.
[0016]
There are no particular restrictions on the raw materials used in the preparation of the catalyst, and nitrates, sulfates, oxides, hydroxides, chlorides, carbonates, acetates, oxyacids, ammonium oxyacids, etc. of each metal are used. be able to.
[0017]
As manganese raw materials, various oxide powders or molded products can be used as they are, and an aqueous solution containing a manganese hydroxide slurry obtained by treating an aqueous solution of manganese nitrate or the like with an aqueous ammonia solution, a manganese compound and compounds of other component elements. Any of those prepared by general techniques such as coprecipitates from can be used. Preferred are those containing Mn 2 O 3 . Particularly preferred is a manganese oxide consisting essentially of Mn 2 O 3 . In such an X-ray diffraction spectrum of manganese oxide, only a peak attributed to a crystal phase corresponding to Mn 2 O 3 appears.
[0018]
The final catalyst is obtained when the diffraction angle 2θ (± 0.3 °) is 32.9 °, 55.2 °, 23.1 °, 38.2 ° and 65.8 ° (ie d). The crystalline phase (ie Mn 2 ) identified by the peak appearing in the X-ray diffraction spectrum (counter-cathode Cu-Kα) when the values are 2.72Å, 1.66Å, 3.84Å, 2.35Å and 1.42Å. Crystal phase corresponding to O 3 ). For that purpose, Mn 2 O 3 is used as the Mn raw material, and the preparation conditions are finally maintained so that the Mn 2 O 3 phase is maintained, or even if the raw material does not contain Mn 2 O 3 , The preparation conditions should be such that a 2 O 3 phase is formed. More preferably, the preparation method uses Mn 2 O 3 as a raw material and does not perform heat treatment at 300 ° C. or higher.
[0019]
When using Mn oxide as a raw material, the specific surface area is preferably 0.5 to 10 m 2 / g. Beyond this range, the complete oxidation activity of the resulting catalyst becomes strong and high partial selectivity cannot be obtained. On the other hand, below this range, the activity is low.
[0020]
Sb raw materials include oxide powders such as Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Sb oxide dissolved in tartaric acid aqueous solution, antimonic acid (antimony pentoxide hydrate) A sol or the like can be preferably used. Of these, antimonic acid sol or Sb 2 O 3 powder is preferable in terms of uniformity in catalyst preparation and performance of the obtained catalyst. Some antimonic acid sols are commercially available, but many of them are not suitable as catalyst raw materials because various stabilizers are added. An antimonic acid sol obtained by ion exchange of an aqueous solution of potassium antimony (V) through a strongly acidic cation exchange resin is preferred in that it does not contain impurities.
[0021]
In addition, with respect to other element materials, it is generally preferable to use water-soluble materials, but water-insoluble materials such as oxides can also be used depending on the type of element.
[0022]
The refractory inorganic substance used in the present invention is not particularly limited in its usage form, and various forms such as molded bodies, powders, gels, sols and the like can be properly used according to the usage form of the catalyst. .
[0023]
As a raw material gas for carrying out the gas phase oxidative dehydrogenation reaction of the present invention, a diluent gas can be used as required in addition to the lower alkane and molecular oxygen. Air or pure oxygen is used as the molecular oxygen source. As the dilution gas, an inert gas such as nitrogen, helium, carbon dioxide, water vapor, or the like is preferably used. Molecular oxygen may be usually used at a ratio of 0.1 to 5 mol with respect to 1 mol of alkane.
[0024]
There are no particular limitations on the reaction conditions for carrying out the gas phase oxidative dehydrogenation reaction of the present invention. For example, the above raw material gas is used under the conditions of a space velocity of 300 to 30000 hr −1 and a reaction temperature of 250 to 650 ° C. What is necessary is just to contact the catalyst for oxidative dehydrogenation.
[0025]
The above reaction is usually carried out under normal pressure, but can also be carried out under reduced pressure or under pressure. There is no restriction | limiting in particular also about the reaction system, Any of a fixed bed type, a moving bed type, or a fluidized bed type may be sufficient. Further, a single flow method or a recycling method may be used.
[0026]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. The conversion rate, single flow yield, and selectivity are defined as follows.
Conversion (mol%) = (number of moles of reacted alkane / number of moles of supplied alkane) × 100
Selectivity (mol%) = (number of moles of each compound produced / number of moles of reacted alkane) × 100
Single stream yield (mol%) = (number of moles of each compound produced / number of moles of supplied alkane) × 100
FIG. 1 is an X-ray diffraction spectrum (counter cathode Cu—Kα) of dimanganese trioxide [manganese (III) oxide] powder used as a Mn raw material in all Examples. The horizontal axis is the diffraction angle 2θ, and the vertical axis is the peak intensity (cps).
[0027]
The main five peaks A, B, C, D and E and other minute peaks are all peaks attributed to the Mn 2 O 3 phase.
[0028]
FIG. 2 is an X-ray diffraction spectrum (counter cathode Cu—Kα) of the catalyst obtained in Example 1. The horizontal and vertical axes are the same as in FIG.
[0029]
A, B, C, D and E are attributed to the main 5 peaks of the Mn 2 O 3 phase.
[0030]
The peaks appearing when 2θ is 14.8 °, 29.9 ° and 28.6 ° are attributed to H 14 Sb 14 O 21 (OH) 42 .
[0031]
FIG. 3 is an X-ray diffraction spectrum (counter cathode Cu—Kα) of the catalyst obtained in Example 16. The horizontal and vertical axes are the same as in FIG.
[0032]
A, B, C, D and E are attributed to the main 5 peaks of the Mn 2 O 3 phase.
[0033]
The peaks that appear when 2θ is 15.2 °, 30.6 °, and 29.3 ° are attributed to Sb 2 O 5 .4H 2 O.
[0034]
4 is an X-ray diffraction spectrum (counter cathode Cu—Kα) of the catalyst obtained in Comparative Example 1. FIG. The horizontal and vertical axes are the same as in FIG.
[0035]
There is no peak attributed to the Mn 2 O 3 phase and it is attributed to the MnO 2 phase when 2θ is 21.8 °, 35.1 °, 36.8 °, 55.3 ° and 38.4 °. A peak appears, and peaks attributable to H 14 Sb 14 O 21 (OH) 42 appear when 2θ is 14.8 °, 29.9 °, and 28.6 °.
Example 1
Manganese trioxide [manganese (III) oxide] powder used as a Mn raw material was prepared as follows.
[0036]
100 g of manganese dioxide [manganese (IV) oxide] powder (specific surface area 41 m 2 / g) was put in a crucible and fired at 600 ° C. for 3 hours in a muffle furnace under the atmosphere. When the X-ray diffraction (counter cathode Cu-Kα) of the obtained powder was measured, the diffraction angle 2θ (± 0.3 °) was 32.9 °, 55.2 °, 23.1 °, 38.2 °. And the presence of a crystalline phase corresponding to Mn 2 O 3 when the d value is 2.72 °, 1.66 °, 3.84 °, 2.35 ° and 1.42 °. Although the main peak shown was confirmed, other crystal phases could not be confirmed (FIG. 1). The specific surface area of the dimanganese trioxide [manganese (III) oxide] powder was 5.0 m 2 / g.
[0037]
An antimonic acid sol as a Sb raw material was prepared as follows: 43.8 g of potassium hexahydroxoantimony (V) was dissolved in 2 liters of water by heating, and insoluble matters were filtered. This filtrate was circulated at a rate of 15 ml / min through a column packed with 500 g of a strongly acidic cation exchange resin (DOWEX 50W × 4) for ion exchange treatment. The obtained liquid was an almost transparent solution, but after a day, it became a slightly cloudy sol state, and the Sb concentration in the sol was 0.067 mmol / g when determined by an ICP emission analysis measurement apparatus. The ion exchange rate was 99.5%, and the amount of residual K in the sol was negligible.
[0038]
To a 500 ml beaker, 3.95 g of the above-mentioned dimanganese trioxide [manganese (III) oxide] powder and 223.9 g of antimonic acid sol were added, and heating and stirring were started. After reaching about 80 ° C., stirring was performed while maintaining the liquid amount for 2 hours. This was followed by stirring for about 4 hours while heating at a temperature of 90 ° C. to evaporate the water. The obtained paste was dried at 120 ° C. for 14 hours, then crushed, molded, and further crushed to obtain a size of 9 to 20 mesh.
[0039]
The composition of the obtained catalyst was Mn 1 Sb 0.3 O x . In the X-ray diffraction spectrum (anti-cathode Cu-Kα), the diffraction angle 2θ (± 0.3 °) is 32.9 °, 55.2 °, 23.1 °, 38.2 ° and 65.8 °. A major peak attributed to the Mn 2 O 3 phase was observed. In addition, only the peak of the crystal phase attributed to H 14 Sb 14 O 21 (OH) 42 was observed (FIG. 2).
[0040]
The catalyst was charged into a normal flow reactor and reacted under the following conditions. Table 1 shows the reaction results after 1 hour from the start of the reaction.
Catalyst amount: 1.5g
Reaction gas: C 3 H 8 / O 2 / N 2 = 1/1/8 (molar ratio)
Reaction gas supply rate: 112.5 ml (standard state) / min
Reaction temperature: 490 ° C
In the following examples, the reaction was performed under the same conditions except that the reaction temperature was partially changed. Table 1 shows the composition of each catalyst and the reaction results one hour after the start of the reaction.
Examples 2 and 3
A catalyst was prepared in the same manner as in Example 1 except that the amount of antimonic acid sol in Example 1 was changed to 373.2 g and 74.6 g, respectively.
Examples 4 and 5
In Example 1, instead of the antimonic acid sol, 2.32 g of an ammonium metatungstate aqueous solution (containing 50% by mass as WO 3 ) diluted with 200 ml of water and 1.11 g of chromium sulfate tetrahydrate, respectively A catalyst was prepared in the same manner as in Example 1 except that a solution obtained by heating and dissolving with 200 ml of water was used.
Example 6
A catalyst was prepared in the same manner as in Example 1 except that after adding the antimonic acid sol in Example 1, 4.00 g of chromium nitrate nonahydrate was dissolved in 50 ml of water.
Example 7
A catalyst was prepared in the same manner as in Example 6 except that instead of the antimonic acid sol, 2.32 g of an aqueous ammonium metatungstate solution diluted with 50 ml of water was added.
Example 8
After adding antimonic acid sol in Example 1, 2.32 g of an aqueous ammonium metatungstate solution diluted with 50 ml of water, and 4.00 g of chromium nitrate nonahydrate dissolved in 50 ml of water, A catalyst was prepared in the same manner as in Example 1 except that it was added.
Example 9
In Example 8, 2.19 g of antimony trioxide powder was used instead of the antimonic acid sol, and 2.22 g of chromium sulfate tetrahydrate was dissolved in 200 ml of water instead of the chromium nitrate aqueous solution. Except for the above, a catalyst was prepared in the same manner as in Example 8.
Examples 10-13
In Example 8, nickel nitrate nonahydrate 2.91 g dissolved in 50 ml of water (Example 10), cobalt nitrate nonahydrate 2.92 g dissolved in 50 ml of water (implementation) Example 8) Example 8 except that 5 ml of a 0.1 mol / L aqueous potassium hydroxide solution (Example 12) and 2.5 ml of a 0.4 mol / L aqueous lithium hydroxide solution (Example 13) were added, respectively. A catalyst was prepared in the same manner as above.
Example 14
In Example 8, a catalyst was prepared in the same manner as in Example 8, except that 2.5 ml of a 0.4 mol / L aqueous lithium hydroxide solution and 5 ml of a 0.1 mol / L aqueous potassium hydroxide solution were further added.
Example 15
In Example 14, a catalyst was prepared in the same manner as in Example 14 except that 2.91 g of nickel nitrate nonahydrate was dissolved in 50 ml of water.
Example 16
In Example 15, a catalyst was prepared in the same manner as in Example 15 except that 1.28 g of chromium sulfate tetrahydrate was dissolved in 50 ml of water instead of the chromium nitrate aqueous solution.
Example 17
In Example 16, a catalyst was prepared in the same manner as in Example 16 except that 2.19 g of antimony trioxide powder and 200 ml of water were added instead of the antimonic acid sol.
Example 18
A catalyst was prepared in the same manner as in Example 17 except that the addition amount of the 0.1 mol / L aqueous potassium hydroxide solution was changed to 12.5 ml.
Examples 19, 20 and 21
In Example 18, 1.00 g of niobium pentoxide (Nb 2 O 5 ) powder (Example 19), 1.66 g of tantalum oxide (Ta 2 O 5 ) powder (Example 20) or cerium oxide (CeO 2 ) powder 1 A catalyst was prepared in the same manner as in Example 18 except that .29 g (Example 21) was additionally used.
[0041]
The catalysts of all the examples described above have diffraction angles 2θ (± 0.3 °) of 32.9 °, 55.2 °, 23 in X-ray diffraction (counter-cathode Cu-Kα) before being used in the reaction. Mn 2 O 3 phase when .1 °, 38.2 ° and 65.8 ° (d values of 2.72, 1.66, 3.84, 2.35 and 1.42) A peak corresponding to was observed. Other Mn single oxide phases were not observed.
[0042]
The X-ray diffraction spectrum of the catalyst obtained in Example 16 is shown in FIG.
Comparative Example 1-9
Examples 1, 4, and 5, except that 4.35 g of manganese dioxide [manganese (IV) oxide] powder (specific surface area 41 m 2 / g) was used instead of dimanganese trioxide [manganese (III) oxide] powder, respectively. Catalysts were prepared as in 8, 9, 10, 14, 16 and 19. In all of the catalysts of the comparative examples, only the MnO 2 phase was observed in the X-ray diffraction spectrum (counter cathode Cu—Kα) before being used in the reaction, and the Mn 2 O 3 phase was not observed.
[0043]
The X-ray diffraction spectrum of the catalyst obtained in Comparative Example 1 is shown in FIG.
[0044]
Propane oxidative dehydrogenation was carried out using the catalysts of Examples 1-21 and Comparative Examples 1-9. Table 1 shows the reaction temperature and the reaction result 1 hour after the start of the reaction.
[0045]
[Table 1]
Example 22
In Example 16, isobutane was oxidatively dehydrogenated in the same manner as in Example 16 except that isobutane was used instead of propane and the reaction temperature was changed from 530 ° C to 490 ° C. One hour after the start of the reaction, the conversion of isobutane was 35.7 mol%, isobutene selectivity was 32.5 mol%, methacrolein selectivity was 1.0 mol%, and the isobutene single stream yield was 11 It was 6 mol%.
Comparative Example 10
An oxidative dehydrogenation reaction of isobutane was performed in the same manner as in Example 22 except that the same catalyst as in Comparative Example 8 was used in Example 22. One hour after the start of the reaction, the conversion of isobutane was 28.3 mol%, isobutene selectivity was 27.6 mol%, methacrolein selectivity was 0.8 mol%, and the isobutene single stream yield was 7 It was 8 mol%.
[0047]
【The invention's effect】
The lower alkane oxidative dehydrogenation catalyst of the present invention is excellent in oxidative dehydrogenation ability and can produce the corresponding olefin from the lower alkane in high yield.
[Brief description of the drawings]
FIG. 1 is an X-ray diffraction spectrum (counter cathode Cu—Kα) of manganite trioxide used as a Mn raw material in all Examples. The horizontal axis is the diffraction angle 2θ, and the vertical axis is the peak intensity (cps). The main peaks A, B, C, D and E and other minute peaks are all peaks attributed to the Mn 2 O 3 phase.
2 is an X-ray diffraction spectrum (counter cathode Cu-Kα) of the catalyst obtained in Example 1. FIG. The horizontal and vertical axes are the same as in FIG. A, B, C, D and E are attributed to the main 5 peaks of the Mn 2 O 3 phase. The peaks appearing when 2θ is 14.8 °, 29.9 ° and 28.6 ° are attributed to H 14 Sb 14 O 21 (OH) 42 .
3 is an X-ray diffraction spectrum (counter cathode Cu—Kα) of the catalyst obtained in Example 16. FIG. The horizontal and vertical axes are the same as in FIG. A, B, C, D and E are attributed to the main 5 peaks of the Mn 2 O 3 phase. The peaks that appear when 2θ is 15.2 °, 30.6 °, and 29.3 ° are attributed to Sb 2 O 5 .4H 2 O.
4 is an X-ray diffraction spectrum (counter cathode Cu-Kα) of the catalyst obtained in Comparative Example 1. FIG. The horizontal and vertical axes are the same as in FIG. There is no peak attributed to the Mn 2 O 3 phase, and it is attributed to the MnO 2 phase when 2θ is 21.8 °, 35.1 °, 36.8 °, 55.3 ° and 38.4 °. A peak appears, and peaks attributable to H 14 Sb 14 O 21 (OH) 42 appear when 2θ is 14.8 °, 29.9 °, and 28.6 °.
Claims (2)
Ｍｎ a Ｘ b Ｙ c Ｏ x （１）
（ここでＭｎはマンガンを表し、Ｏは酸素を表し、ＸはＳｂ、ＷおよびＣｒからなる群より選ばれる少なくとも１種の元素を表し、ＹはＲｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｎｂ、Ｔａ、Ｃｅ、Ｚｎ、Ｔｌ、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、ＳｒおよびＢａからなる群より選ばれる少なくとも１種の元素を表し、ａ、ｂ、ｃおよびｘは各々Ｍｎ、Ｘ、Ｙおよび酸素の原子数を表し、ａが１のときｂは０．０１〜２でｃは０〜２であり、ｘは酸素以外の元素の酸化状態によって定まる数値である。）
により表される元素組成で構成されたものであること、並びに、回折角２θ（±０．３°）が３２．９°、５５．２°、２３．１°、３８．２°および６５．８°であるときにＸ線回折スペクトル（対陰極Ｃｕ−Ｋα）に現れるピークによって同定される結晶相を含有していること、を特徴とする低級アルカンの酸化脱水素用触媒。A catalyst for producing a corresponding olefin by vapor-phase oxidative dehydrogenation of a lower alkane having 2 to 5 carbon atoms in the presence of molecular oxygen, which has the following general formula (1)
Mn a X b Y c O x (1)
(Where Mn represents manganese, O represents oxygen, X represents at least one element selected from the group consisting of Sb, W and Cr, Y represents Re, Fe, Co, Ni, Nb, Ta, Represents at least one element selected from the group consisting of Ce, Zn, Tl, Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba, a, b, c and x are Mn, X, Y represents the number of atoms of oxygen, and when a is 1, b is 0.01 to 2, c is 0 to 2, and x is a numerical value determined by the oxidation state of elements other than oxygen.)
It by those comprised of elemental composition represented, and the diffraction angle 2θ (± 0.3 °) is 32.9 °, 55.2 °, 23.1 ° , 38.2 ° and 65. A catalyst for oxidative dehydrogenation of a lower alkane, characterized by containing a crystal phase identified by a peak appearing in an X-ray diffraction spectrum (counter-cathode Cu-Kα) at 8 °.
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