JP3500682B2 - Catalyst for the production of nitriles from alkanes - Google Patents
Catalyst for the production of nitriles from alkanesInfo
- Publication number
- JP3500682B2 JP3500682B2 JP02558494A JP2558494A JP3500682B2 JP 3500682 B2 JP3500682 B2 JP 3500682B2 JP 02558494 A JP02558494 A JP 02558494A JP 2558494 A JP2558494 A JP 2558494A JP 3500682 B2 JP3500682 B2 JP 3500682B2
- Authority
- JP
- Japan
- Prior art keywords
- diffraction
- intensity
- catalyst
- oxygen
- ray diffraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 45
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims description 27
- 150000002825 nitriles Chemical class 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000007789 gas Substances 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 238000002441 X-ray diffraction Methods 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052714 tellurium Inorganic materials 0.000 claims description 8
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Chemical group 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Chemical group 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000010586 diagram Methods 0.000 claims 4
- 238000006243 chemical reaction Methods 0.000 description 19
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000013078 crystal Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- -1 l 5 Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035943 smell Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000004685 tetrahydrates Chemical class 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000021312 gluten Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle 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
- 230000005855 radiation Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 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】[0001]
【産業上の利用分野】本発明はニトリルを製造するため
に使用される触媒に関するものである。詳しくは、アル
カンを原料とする改良されたニトリル製造のための触
媒、およびそれを使用したニトリルの製造方法に関する
ものである。アクリロニトリル、メタクリロニトリルな
どのニトリル類は、繊維、合成樹脂、合成ゴムなどの重
要な中間体として工業的に製造されている。FIELD OF THE INVENTION This invention relates to catalysts used to produce nitriles. More particularly, it relates to an improved catalyst for producing nitrile using an alkane as a raw material and a method for producing nitrile using the catalyst. Nitriles such as acrylonitrile and methacrylonitrile are industrially produced as important intermediates for fibers, synthetic resins and synthetic rubbers.
【０００２】[0002]
【従来の技術】ニトリルの製造方法としては、従来は、
プロピレン、イソブテン等のオレフィンを、触媒の存在
下でアンモニアおよび酸素と気相において高温で接触反
応させる、いわゆるアンモ酸化法方法が最も一般的な方
法として知られている。一方、最近、原料として安価な
プロパン、イソブタンなどの低級アルカンを出発原料と
したアンモ酸化法によるニトリルの製造方法も報告され
ている。2. Description of the Related Art As a method for producing nitrile, conventionally,
The so-called ammoxidation method in which an olefin such as propylene or isobutene is catalytically reacted with ammonia and oxygen in the gas phase at high temperature in the presence of a catalyst is known as the most general method. On the other hand, recently, a method for producing a nitrile by an ammoxidation method using a cheaper alkane such as propane or isobutane as a starting material as a starting material has also been reported.
【０００３】これらのアルカンからのアンモ酸化法多く
は触媒に関する内容であり、具体的には、Ｍｏ−Ｂｉ−
Ｐ−Ｏ系触媒（特開昭４８−１６８８７号）、Ｖ−Ｓｂ
−Ｏ系触媒（特開昭４７−３３７８３号、特公昭５０−
２３０１６号 、特開平１−２６８６６８号、特開平２
−１８０６３７号）、Ｓｂ−Ｕ−Ｖ−Ｎｉ−Ｏ系触媒
（特公昭４７−１４３７１号）、Ｓｂ−Ｓｎ−Ｏ系触媒
（特公昭５０−２８９４０号）、Ｖ−Ｓｂ−Ｗ−Ｐ−Ｏ
系触媒（特開平２−９５４３９号）、Ｖ−Ｓｂ−Ｗ−Ｏ
系酸化物とＢｉ−Ｃｅ−Ｍｏ−Ｗ−Ｏ系酸化物を機械的
に混合して得た触媒（特開昭６４−３８０５１号）、Ｖ
−Ｓｎ−Ｓｂ−Ｃｕ−Ｏ系触媒（特開平４−２７５２６
６号）、Ａｇ−Ｂｉ−Ｖ−Ｍｏ−Ｏ系触媒（特開平３−
５８９６１号）、Ｓｎ−Ｖ−Ｍｏ−Ｂｉ−Ｏ系触媒（特
開平４−２４７０６０号）、Ｃｒ−Ｍｏ−Ｔｅ−Ｍ−Ｏ
系触媒（米国特許５，１７１，８７６号）などが知られ
ている。また、本出願人もＭｏ−Ｖ−Ｔｅ−Ｎｂ−Ｏ系
触媒（特開平２−２５７号、特開平４−２３５１５３
号）、Ｍｏ−Ｖ−Ｔｅ−Ｎｂ−Ｘ−Ｏ系触媒（特開平５
−１４８２１２号）、特定の結晶構造を有するＭｏ−Ｖ
−Ｔｅ−Ｘ−Ｏ系触媒（特開平５−２０８１３６号）な
どを報告している。Most of the ammoxidation methods from these alkanes are related to catalysts, and specifically, Mo-Bi-
P-O type catalyst (JP-A-48-16887), V-Sb
-O catalyst (JP-A-47-33783, JP-B-50-)
23016, JP-A-1-268668, JP-A-2
-180637), Sb-U-V-Ni-O type catalyst (Japanese Patent Publication No. 47-14371), Sb-Sn-O type catalyst (Japanese Patent Publication No. 50-28940), V-Sb-W-P-O.
-Based catalyst (JP-A-2-95439), V-Sb-W-O
Catalyst obtained by mechanically mixing a Bi-Ce-Mo-W-O-based oxide (Japanese Patent Application Laid-Open No. 64-38051), V
-Sn-Sb-Cu-O-based catalyst (JP-A-4-27526)
No. 6), Ag-Bi-V-Mo-O-based catalyst (JP-A-3-
58961), Sn-V-Mo-Bi-O-based catalyst (JP-A-4-247060), Cr-Mo-Te-MO.
System catalysts (US Pat. No. 5,171,876) and the like are known. In addition, the Applicant has also adopted a Mo-V-Te-Nb-O-based catalyst (JP-A-2-257 and JP-A-4-235153).
No.), a Mo-V-Te-Nb-X-O-based catalyst (Japanese Patent Application Laid-Open No. HEI 5)
-148212), Mo-V having a specific crystal structure
-Te-X-O based catalysts (JP-A-5-208136) are reported.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
の方法はいずれも目的とするニトリル類の収率が十分満
足できるものではない。また、ニトリル類の収率を向上
させるために、反応系に少量の有機ハロゲン化物、無機
ハロゲン化物、またはイオウ化合物を添加する方法、あ
るいは水を添加する方法等が試みられているが、前者は
反応装置の腐食の問題があり、また後者は副反応による
副生物の生成とその処理などの問題があり、いずれも工
業的実施上難点がある。更に、従来の触媒系を用いる方
法の多くは、５００℃前後ないしはそれ以上の極めて高
い反応温度を必要とするため、反応器の材質、製造コス
ト等の面で有利ではない。However, none of these methods can sufficiently satisfy the target yield of nitriles. In addition, in order to improve the yield of nitriles, a method of adding a small amount of an organic halide, an inorganic halide, or a sulfur compound to the reaction system, a method of adding water, or the like has been attempted. There is a problem of corrosion of the reactor, and the latter has problems such as generation of a by-product by side reaction and its treatment, which are both difficult in industrial implementation. Further, most of the conventional methods using a catalyst system require an extremely high reaction temperature of about 500 ° C. or higher, which is not advantageous in terms of reactor material, manufacturing cost, and the like.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、アルカン
を原料とするニトリルの製造法について種々検討した結
果、特定の結晶構造を有するモリブデン（Ｍｏ）、バナ
ジウム（Ｖ）、テルル（Ｔｅ）及びその他一定の元素か
ら成る複合酸化物触媒の存在下で、アルカンをアンモニ
アと気相接触反応させることにより、反応系にハロゲン
化物や水などを存在させることなく、しかも４００〜４
５０℃程度の比較的に低い温度において従来法より更に
高い収率で目的とするニトリルを製造し得ることを見い
出し、本発明に到達したものである。Means for Solving the Problems As a result of various studies on the production method of nitrile using alkane as a raw material, the present inventors have found that molybdenum (Mo), vanadium (V), tellurium (Te) having a specific crystal structure. And in the presence of a complex oxide catalyst composed of certain other elements, the alkane is subjected to a gas phase catalytic reaction with ammonia, thereby eliminating the presence of halide, water, etc. in the reaction system, and 400 to 4
The inventors have found that the target nitrile can be produced with a higher yield than the conventional method at a relatively low temperature of about 50 ° C. and have reached the present invention.
【０００６】以下、本発明について詳細に説明する。本
発明の、アルカンをアンモニアと気相接触酸化反応させ
ることにより、ニトリルを製造するための触媒の特徴
は、以下の点，およびに存する。 モリブデ
ン、バナジウム、テルル、酸素、およびＸ（Ｘは、ニオ
ブ、タンタル、タングステン、チタン、アルミニウム、
ジルコニウム、クロム、マンガン、鉄、ルテニウム、コ
バルト、ロジウム、ニッケル、パラジウム、白金、アン
チモン、ビスマス、ホウ素、インジウムおよびセリウム
の中から選ばれた１種以上の元素）を構成成分とし、酸
素を除く上記構成成分の合計に対する各構成成分の存在
割合が、The present invention will be described in detail below. Of the present invention, by that to ammonia and gas phase catalytic oxidation reaction alkanes, characterized in catalysts for producing nitriles, the following points, and lies. Molybdenum, vanadium, tellurium, oxygen, and X (X is niobium, tantalum, tungsten, titanium, aluminum,
One or more elements selected from zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, antimony, bismuth, boron, indium and cerium) as constituent components and excluding oxygen The existence ratio of each constituent to the total of constituents is
【０００７】[0007]
【数３】
０．２５ ＜ ｒMo ＜ ０．９８
０．００３ ＜ ｒV ＜ ０．５０
０．００３ ＜ ｒTe ＜ ０．５０
０ ≦ ｒX ＜ ０．５０
（ただし、ｒMo，ｒV，ｒTe，およびｒXは、各々酸素を
除く上記構成成分の合計に対するモリブデン、バナジウ
ム、テルルおよびＸのモル分率を表す）である複合酸化
物を主成分とすること。 の複合酸化物のＸ線回折
線において、下記に示す回折角２θにＸ線回折ピークを
示すこと。0.25 <rMo <0.98 0.003 <rV <0.50 0.003 <rTe <0.50 0 ≤ rX <0.50 (where rMo, rV, rTe, and rX are , Which represents the mole fractions of molybdenum, vanadium, tellurium, and X with respect to the total of the above-mentioned constituents excluding oxygen). In the X-ray diffraction line of the complex oxide of, an X-ray diffraction peak is shown at a diffraction angle 2θ shown below.
【０００８】[0008]
【表５】回折角 ２θ（°）
９．０±０．３
２２．１±０．３
２７．３±０．３
２９．２±０．３
３５．４±０．３
本発明の触媒の主成分は上述のに記した複合酸化物で
あって、Ｘとして上記の元素が用いられているが、好ま
しくはニオブ、タンタル、タングステン、チタンであ
り、特に好ましいのはニオブである。また、Ｍｏ、Ｖ、
Ｔｅ、およびＸのモル分率で特に好ましい範囲は以下の
通りである。[Table 5] Diffraction angle 2θ (°) 9.0 ± 0.3 22.1 ± 0.3 27.3 ± 0.3 29.2 ± 0.3 35.4 ± 0.3 For the catalyst of the present invention The main component is the complex oxide described above, and the above element is used as X, but niobium, tantalum, tungsten, and titanium are preferable, and niobium is particularly preferable. Also, Mo, V,
Particularly preferable ranges of the molar fractions of Te and X are as follows.
【０００９】[0009]
【数４】
０．２５ ＜ ｒMo ＜ ０．９８
０．０１ ＜ ｒV ＜ ０．３７
０．００５＜ ｒTe ＜ ０．２７
０．００１＜ ｒX ＜ ０．３５
該複合酸化物は、ただ単にに記した組成を満足するの
みでは触媒としては十分でなく、特定の結晶構造を有す
ることが重要である。本発明者等は、すでに特開平５−
２０８１３６号において特定の結晶構造を有するＭｏ−
Ｖ−Ｔｅ−Ｘ−Ｏ系複合酸化物触媒がアルカンからニト
リルを製造する際に良好な触媒となることを報告してい
るが、本発明での複合酸化物は、特開平５−２０８１３
６号で規定したものとはまた別の新規な結晶構造を有す
るものであって、アルカンからニトリルを製造するため
の触媒として極めて有用なるものである。0.25 <rMo <0.980.01 <rV <0.370.005 <rTe <0.270.001 <rX <0.35 The complex oxide is simply described as follows. Only satisfying the above composition is not sufficient as a catalyst, and it is important to have a specific crystal structure. The inventors of the present invention have already disclosed in Japanese Unexamined Patent Publication No.
No. 208136, Mo-having a specific crystal structure
It has been reported that the V-Te-X-O-based composite oxide catalyst is a good catalyst when producing a nitrile from an alkane, but the composite oxide of the present invention is disclosed in JP-A-5-20813.
It has a novel crystal structure different from that defined in No. 6 and is extremely useful as a catalyst for producing a nitrile from an alkane.
【００１０】 本発明触媒として用いる複合酸化物が
特定の結晶構造を有することを示す指標は粉末Ｘ線回折
のパターンである。該複合酸化物のＸ線回折ピーク（Ｘ
線源としてＣｕ−Ｋα線を使用）のパターンの特徴は特
定の回折角２θにおいて、以下に示す５つの主要回折ピ
ークが認められることにある。[0010] The composite oxide used as the catalyst of the present invention is
Powder X-ray diffraction is an index indicating that it has a specific crystal structure.
Pattern. X-ray diffraction peak (X
Cu-Kα ray is used as a radiation source)
At the constant diffraction angle 2θ, the five main diffraction
Is recognized.
【００１１】[0011]
【表６】 Ｘ線格子面 回折角 ２θ（゜） 間隔中央値（Ａ） 相対強度 ９．０±０．３ ９．８３ ０．５〜 ３０ ２２．１±０．３ ４．００ １００ ２７．３±０．３ ３．２７ ２５ 〜１４０ ２９．２±０．３ ３．０６ ０．５〜 ４０ ３５．４±０．３ ２．５４ ０．５〜 ４０Table 6 X-ray lattice plane diffraction angle 2θ (°) Interval median value (A) Relative intensity 9.0 ± 0.3 9.83 0.5 to 30 22.1 ± 0.3 4.00 100 27. 3 ± 0.3 3.27 25 ~ 140 29.2 ± 0.3 3.06 0.5 ~ 40 35.4 ± 0.3 2.54 0.5 ~ 40
【００１２】Ｘ線回折ピーク強度は各結晶の測定条件に
よってずれる場合があるが、２θ＝２２．１゜の回折ピ
ーク強度を１００とした場合の相対強度は通常上記の範
囲にある。上記の５本の回折ピークのうち、特に２θ＝
２２．１゜，２７．３゜の回折ピークの強度が大きく、
２θ＝２２．１゜の回折ピーク強度を１００としたとき
の２７．３゜の回折ピークの強度が２５〜１４０である
場合が特に好ましい。The X-ray diffraction peak intensity may deviate depending on the measurement conditions of each crystal, but the relative intensity is usually in the above range when the diffraction peak intensity at 2θ = 22.1 ° is 100. Of the above five diffraction peaks, 2θ =
The intensity of the diffraction peaks at 22.1 ° and 27.3 ° is large,
It is particularly preferable that the intensity of the diffraction peak at 27.3 ° is 25 to 140 when the intensity of the diffraction peak at 2θ = 22.1 ° is 100.
【００１３】また、上記５本の回折ピークを認める限り
該５本の回折ピーク以外の２θにピークを有するものが
あっても基本的な結晶構造には支障はなく、本発明に好
適に用いることができる。特に、既に特開平５−２０８
１３６号で報告されている触媒成分が共存していても特
に問題なく反応に使用することができる。この特定の結
晶構造を有する複合酸化物の調製方法は次のようであ
る。例えば、モリブデン、バナジウム、テルル及びニオ
ブからなる複合酸化物を調製する場合、まず、所定量の
メタバナジン酸アンモニウム塩を含む水溶液に、テルル
酸の水溶液、シュウ酸ニオブアンモニウム塩の水溶液お
よびパラモリブデン酸アンモニウム塩の溶液またはスラ
リ−を各々の金属元素の原子比が所定の割合となるよう
な量比で順次添加する。このとき、必要に応じて、シュ
ウ酸、酒石酸、クエン酸などの有機酸を添加してもよ
い。得られた溶液、またはスラリーを蒸発乾固法、噴霧
乾燥法、真空乾燥法、凍結乾燥法等で乾燥させ、最後
に、残った乾燥物を通常３５０〜７００℃、好ましくは
４００〜６５０℃の温度で通常０．５〜３０時焼成して
目的の複合酸化物とする。また、焼成を効率よく行なう
ためには、最終の焼成前に、上記乾燥物を、空気中、あ
るいは窒素、アルゴンなどの不活性ガス雰囲気中、１５
０〜３５０℃程度で加熱分解してもよい。As long as the above-mentioned 5 diffraction peaks are recognized, even if there are peaks at 2θ other than the 5 diffraction peaks, there is no problem in the basic crystal structure and they are preferably used in the present invention. You can In particular, Japanese Patent Laid-Open No. 5-208
Even if the catalyst component reported in No. 136 coexists, it can be used for the reaction without any particular problem. The method for preparing the composite oxide having this specific crystal structure is as follows. For example, when preparing a composite oxide composed of molybdenum, vanadium, tellurium and niobium, first, an aqueous solution containing a predetermined amount of ammonium metavanadate, an aqueous solution of telluric acid, an aqueous solution of niobium ammonium oxalate and ammonium paramolybdate. The salt solution or the slurry is sequentially added in such an amount ratio that the atomic ratio of each metal element becomes a predetermined ratio. At this time, if necessary, an organic acid such as oxalic acid, tartaric acid, or citric acid may be added. The obtained solution or slurry is dried by an evaporation dryness method, a spray drying method, a vacuum drying method, a freeze drying method or the like, and finally the remaining dried product is usually 350 to 700 ° C, preferably 400 to 650 ° C. It is usually fired at a temperature for 0.5 to 30 hours to obtain the target composite oxide. Further, in order to perform the firing efficiently, the above dried product is treated in air or in an atmosphere of an inert gas such as nitrogen or argon before the final firing.
You may heat-decompose at about 0-350 degreeC.
【００１４】なお、上記の複合酸化物の原料は前述した
ものに限定されるのではなく、例えばＭｏＯ3，Ｖ2Ｏ
5 ，Ｖ2Ｏ3 ，ＴｅＯ2，Ｎｂ2Ｏ5などの酸化物、ＭｏＣ
ｌ5 ，ＶＣｌ4，ＶＯＣｌ3，ＮｂＣｌ5などのハロゲン
化物、またはオキシハロゲン化物、Ｍｏ（ＯＣ2Ｈ5）
5 ，Ｎｂ（ＯＣ2Ｈ5）5 ，ＶＯ（ＯＣ2Ｈ5）3，モリブ
デナセチルアセトナ−トなどのアルコキシド、有機金属
化合物など広範に使用可能である。The raw materials for the above complex oxides are not limited to those described above, but may be, for example, MoO 3 , V 2 O.
5 , oxides such as V 2 O 3 , TeO 2 and Nb 2 O 5 , MoC
halides such as l 5 , VCl 4 , VOCl 3 , and NbCl 5 , or oxyhalides, Mo (OC 2 H 5 ).
5 , Nb (OC 2 H 5 ) 5 , VO (OC 2 H 5 ) 3 , alkoxides such as molybdenacetyl acetonate, and organometallic compounds can be widely used.
【００１５】このようにして得られた複合酸化物は、単
独でも固体触媒として用いられるが、周知の担体、例え
ば、シリカ、アルミナ、チタニア、アルミノシリケ−
ト、珪藻土、ジルコニアなどと共に使用することもでき
る。また、反応の規模、方式等により適宜の形状および
粒径に成型される。上述の触媒の存在下、アルカンをア
ンモニアと気相接触酸化反応させることにより、ニトリ
ルを効率よく製造することができる。反応器方式として
は特に制限はなく、流動層、固定床、移動床などを採用
することができる。The composite oxide thus obtained can be used alone as a solid catalyst, but it is a well-known carrier such as silica, alumina, titania or aluminosilicate.
It can also be used with gluten, diatomaceous earth, zirconia and the like. Further, it is molded into an appropriate shape and particle size depending on the scale of reaction, method, and the like. Nitriles can be efficiently produced by subjecting an alkane to a gas phase catalytic oxidation reaction with ammonia in the presence of the above-mentioned catalyst. The reactor system is not particularly limited, and a fluidized bed, fixed bed, moving bed or the like can be adopted.
【００１６】原料のアルカンとしては、特に限られるも
のではなく、例えばメタン、エタン、プロパン、ｎ−ブ
タン、イソブタン、ペンタン、ヘキサン、ヘプタン、シ
クロヘキサン等が挙げられるが、得られるニトリルの工
業的用途を考慮すると炭素数１〜４の低級アルカン、特
にプロパン、ブタンを用いるのがよい。本発明での酸化
反応機構の詳細は明らかではないが、上述の酸化物中に
存在する酸素原子、あるいは供給ガス中に存在させる分
子状酸素によって行なわれる。供給ガス中に分子状酸素
を存在させる場合、分子状酸素は純酸素ガスでもよい
が、特に純度は要求されないので、一般には空気のよう
な酸素含有ガスを使用するのが経済的である。供給ガス
としては、通常、アルカン、アンモニアと酸素含有ガス
の混合ガスを使用するが、アルカンとアンモニアの混合
ガスと酸素含有ガスとを交互に供給してもよい。The alkane as a raw material is not particularly limited, and examples thereof include methane, ethane, propane, n-butane, isobutane, pentane, hexane, heptane, cyclohexane, and the like. Considering this, it is preferable to use a lower alkane having 1 to 4 carbon atoms, particularly propane or butane. Although the details of the oxidation reaction mechanism in the present invention are not clear, it is carried out by oxygen atoms present in the above oxides or molecular oxygen present in the feed gas. When molecular oxygen is present in the feed gas, the molecular oxygen may be pure oxygen gas, but it is economical to use an oxygen-containing gas such as air since purity is not particularly required. Alkane, a mixed gas of ammonia and an oxygen-containing gas is usually used as the supply gas, but a mixed gas of an alkane and ammonia and an oxygen-containing gas may be alternately supplied.
【００１７】また、実質的に分子状酸素がアルカンをニ
トリルに転化させる化学量論量以下、場合によっては、
分子状酸素を存在させずアルカンとアンモニアのみを供
給ガスとして気相接触反応させることもできる。この様
な場合は、反応帯域より触媒の一部を適宜、抜き出し
て、該触媒を酸化再生器に送り込み、再生後、触媒を反
応帯域に再供給する方法が好ましい。触媒の再生方法と
しては、触媒を酸素、空気、酸化窒素等の酸化性ガスを
再生器内の触媒に対して、通常３００〜６００℃で流通
させる方法が例示される。Further, substantially molecular oxygen is less than the stoichiometric amount for converting the alkane to the nitrile, and in some cases,
It is also possible to carry out a gas phase catalytic reaction using only alkane and ammonia as feed gases without the presence of molecular oxygen. In such a case, it is preferable that a part of the catalyst is appropriately withdrawn from the reaction zone, the catalyst is fed into an oxidation regenerator, and after regeneration, the catalyst is re-supplied to the reaction zone. Examples of the method for regenerating the catalyst include a method in which an oxidizing gas such as oxygen, air, or nitric oxide is passed through the catalyst in the regenerator at 300 to 600 ° C.
【００１８】アルカンとしてプロパンを、酸素源として
空気を使用する場合について、本発明をさらに詳細に説
明する。反応に供給する空気の割合は、生成するアクリ
ロニトリルの選択率に関して重要であり、空気は通常プ
ロパンに対して２５モル倍量以下、特に１〜１８モル倍
量の範囲が高いアクリロニトリル選択率を示す。また、
反応に供与する全アンモニアの割合は、プロパンに対し
て０．２〜５モル倍量、特に０．５〜３モル倍量の範囲
が好適である。なお、本反応は通常大気圧下で実施され
るが、加圧下または減圧下で行なうこともできる。他の
アルカンについても、プロパンの場合に準じて供給ガス
の組成が選択される。The present invention will be described in more detail in the case where propane is used as the alkane and air is used as the oxygen source. The ratio of air supplied to the reaction is important with respect to the selectivity of acrylonitrile to be produced, and air usually has a high acrylonitrile selectivity in the range of 25 mol times or less, particularly 1 to 18 mol times. Also,
The proportion of total ammonia supplied to the reaction is preferably in the range of 0.2 to 5 times by mole, particularly 0.5 to 3 times by mole, with respect to propane. The reaction is usually carried out under atmospheric pressure, but it may be carried out under pressure or under reduced pressure. For other alkanes, the composition of the feed gas is selected according to the case of propane.
【００１９】本発明においては、従来のアルカンのアン
モ酸化反応におけるよりも低い反応温度、例えば、３６
０〜４８０℃で実施することができ、特に好ましいのは
３８０〜４６０℃程度である。このような低温において
も従来からの技術に比べ、高い収率でニトリル類を製造
することができる。また、気相反応におけるガス空間速
度ＳＶは、通常１００〜１００００ｈ-1、好ましくは３
００〜２０００ｈ-1の範囲である。なお、空間速度と酸
素分圧を調整するための希釈ガスとして、窒素、アルゴ
ン、ヘリウムなど反応に不活性なガスを用いることがで
きる。In the present invention, the reaction temperature is lower than that in the conventional ammoxidation reaction of alkane, for example, 36.
It can be carried out at 0 to 480 ° C, particularly preferably at about 380 to 460 ° C. Even at such a low temperature, nitriles can be produced in a higher yield than conventional techniques. The gas space velocity SV in the gas phase reaction is usually 100 to 10,000 h −1 , preferably 3
The range is from 00 to 2000 h -1 . As a diluent gas for adjusting the space velocity and the oxygen partial pressure, a gas inert to the reaction such as nitrogen, argon or helium can be used.
【００２０】[0020]
【実施例】以下、本発明を、実施例および比較例を挙げ
てさらに詳細に説明するが、本発明はその要旨を超えな
いかぎりこれらの実施例に限定されるものではない。な
お、以下の実施例における転化率（％）、選択率（％）
および収率（％）は、各々次式で示される。The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless it exceeds the gist. The conversion rate (%) and the selectivity rate (%) in the following examples
The yield (%) and the yield (%) are respectively represented by the following equations.
【００２１】[0021]
【数５】アルカンの転化率（％）＝（消費アルカンのモ
ル数／供給アルカンのモル数）×１００
目的ニトリルの選択率（％）＝（生成目的ニトリルのモ
ル数／消費アルカンのモル数）×１００
目的ニトリルの収率（％）＝（生成目的ニトリルのモル
数／供給アルカンのモル数）×１００[Formula 5] Alkane conversion rate (%) = (mol number of consumed alkane / mol number of supplied alkane) × 100 Selectivity of target nitrile (%) = (mol number of nitrile for production / mol number of consumed alkane) × 100 Yield (%) of target nitrile = (mol number of nitrile for production / mol number of alkane supplied) × 100
【００２２】実施例１
実験式Ｍｏ1Ｖ0.19Ｔｅ0.12Ｎｂ0.04Ｏnを有する触媒を
次のように調製した。温水３２５ｍｌにパラモリブデン
酸アンモニウム塩（４水和物）７８．９ｇ、メタバナジ
ン酸アンモニウム塩９．９４ｇ、テルル酸１２．３ｇを
溶解し、均一な水溶液を調製した。次に、ニオブの濃度
が０．４５６ｍｏｌ／ｋｇのシュウ酸ニオブアンモニウ
ム水溶液３９．２ｇを混合し、スラリ−を調製した。こ
のスラリ−を加熱処理することにより水分を除去し、固
体を得た。この固体をアンモニア臭がなくなるまで３０
０℃で加熱処理した後、窒素気流中６００℃で２時間焼
成した。このようにして得た酸化物の粉末Ｘ線回折測定
（Ｘ線源：Ｃｕ−Ｋα線）を行ない、その主要回折線ピ
ーク強度を表−１に示す。Example 1 A catalyst having the empirical formula Mo 1 V 0.19 Te 0.12 Nb 0.04 O n was prepared as follows. 78.9 g of ammonium paramolybdate (tetrahydrate), 9.94 g of metavanadate ammonium salt, and 12.3 g of telluric acid were dissolved in 325 ml of warm water to prepare a uniform aqueous solution. Next, a slurry was prepared by mixing 39.2 g of an aqueous solution of ammonium niobium oxalate having a niobium concentration of 0.456 mol / kg. The slurry was heat-treated to remove water and obtain a solid. 30 times until the solid smells of ammonia
After heat treatment at 0 ° C., firing was performed at 600 ° C. for 2 hours in a nitrogen stream. The powder X-ray diffraction measurement (X-ray source: Cu-Kα ray) of the oxide thus obtained was carried out, and the main diffraction line peak intensities thereof are shown in Table 1.
【００２３】以上の触媒０．５ｇを固定床流通型反応器
に充填し、反応温度４２０℃、ガスの全量の空間速度Ｓ
Ｖを９４０ｈ-1に固定して、プロパン：アンモニア：空
気＝１：１．２：１５のモル比でガスを供給し気相接触
反応を行なった。その結果を表−２に示す。
実施例２0.5 g of the above catalyst was charged into a fixed bed flow type reactor, the reaction temperature was 420 ° C., and the space velocity S of the total amount of gas was S.
V was fixed at 940 h −1 and gas was supplied at a molar ratio of propane: ammonia: air = 1: 1.2: 15 to carry out a gas phase catalytic reaction. The results are shown in Table-2. Example 2
【００２４】実施例１におけるテルル酸の使用量を１
５．４ｇとした以外は実施例１と同様にして実験式Ｍｏ
1Ｖ0.19Ｔｅ0.15Ｎｂ0.04Ｏnを有する触媒を調製した。
このようにして得た酸化物の粉末Ｘ線回折測定における
主要回折線ピーク強度を表−１に示す。以上の触媒を使
用し、実施例１における反応温度を４００℃とした以外
は実施例１と同様の条件でプロパンの気相接触反応を行
なった。その結果を表−２に示す。The amount of telluric acid used in Example 1 was 1
An empirical formula Mo was obtained in the same manner as in Example 1 except that 5.4 g was used.
The catalyst having a 1 V 0.19 Te 0.15 Nb 0.04 O n was prepared.
Table 1 shows the main diffraction line peak intensities in the powder X-ray diffraction measurement of the oxide thus obtained. Using the above catalyst, the gas phase catalytic reaction of propane was carried out under the same conditions as in Example 1 except that the reaction temperature in Example 1 was 400 ° C. The results are shown in Table-2.
【００２５】実施例３
実験式Ｍｏ1Ｖ0.3Ｔｅ0.12Ｏnを有する触媒を次のよう
に調製した。温水３２５ｍｌにパラモリブデン酸アンモ
ニウム塩（４水和物）７８．９ｇ、メタバナジン酸アン
モニウム塩１５．７ｇ、テルル酸１２．３ｇを溶解し、
均一な水溶液を調製した。この水溶液を加熱処理するこ
とにより水分を除去し、固体を得た。この固体をアンモ
ニア臭がなくなるまで３００℃で加熱処理した後、窒素
気流中６００℃で２時間焼成した。このようにして得た
酸化物の粉末Ｘ線回折測定における主要回折線ピーク強
度を表−１に示す。この様にして得た触媒０．５ｇを固
定床流通型反応器に充填し、反応温度４３０℃、ガスの
全量の空間速度ＳＶを１０００ｈ-1に固定して、プロパ
ン：アンモニア：空気＝１：１．２：１５のモル比でガ
スを供給し気相接触反応を行なった。その結果を表−２
に示す。Example 3 A catalyst having the empirical formula Mo 1 V 0.3 Te 0.12 O n was prepared as follows. Dissolving 78.9 g of ammonium paramolybdate (tetrahydrate), 15.7 g of ammonium metavanadate, and 12.3 g of telluric acid in 325 ml of warm water,
A homogeneous aqueous solution was prepared. Water was removed by heating this aqueous solution to obtain a solid. This solid was heat-treated at 300 ° C. until the smell of ammonia disappeared, and then calcined in a nitrogen stream at 600 ° C. for 2 hours. Table 1 shows the main diffraction line peak intensities in the powder X-ray diffraction measurement of the oxide thus obtained. 0.5 g of the catalyst thus obtained was packed in a fixed bed flow reactor, the reaction temperature was 430 ° C., the space velocity SV of the total amount of gas was fixed at 1000 h −1 , and propane: ammonia: air = 1: Gas was supplied at a molar ratio of 1.2: 15 to carry out a gas phase catalytic reaction. The results are shown in Table-2.
Shown in.
【００２６】[0026]
【表５】 [Table 5]
【００２７】[0027]
【表６】 [Table 6]
【００２８】[0028]
【発明の効果】本発明方法によれば、アルカンを原料と
して新規な複合酸化物触媒を使用することにより、反応
系にハロゲン化物や水等を存在させることなく、しかも
４００〜４５０℃程度の比較的低い温度において、高い
収率で目的とするニトリルを製造することができる。EFFECTS OF THE INVENTION According to the method of the present invention, by using a novel complex oxide catalyst using alkane as a raw material, it is possible to prevent the presence of halide, water and the like in the reaction system, and to compare at about 400 to 450 ° C. The target nitrile can be produced in high yield at extremely low temperature.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 清野 健一 神奈川県横浜市緑区鴨志田町1000番地 三菱化成株式会社総合研究所内 (72)発明者 犬丸 啓 神奈川県横浜市緑区鴨志田町1000番地 三菱化成株式会社総合研究所内 (56)参考文献 特開 平５−208136（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenichi Kiyono, 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Kasei Research Institute (72) Inventor Kei Inamaru 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Mitsubishi Kasei Research Institute, Inc. (56) Reference JP-A-5-208136 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B01J 21/00-38/74
Claims (4)
カンよりニトリルを製造するための触媒。 モリブデ
ン、バナジウム、テルル、酸素、およびＸ（Ｘは、ニオ
ブ、タンタル、タングステン、チタン、アルミニウム、
ジルコニウム、クロム、マンガン、鉄、ルテニウム、コ
バルト、ロジウム、ニッケル、パラジウム、白金、アン
チモン、ビスマス、ホウ素、インジウムおよびセリウム
の中から選ばれた１種以上の元素）を構成成分とし、酸
素を除く上記構成成分の合計に対する各構成成分の存在
割合が、 【数１】 ０．２５ ＜ ｒMo ＜ ０．９８ ０．００３ ＜ ｒV ＜ ０．５０ ０．００３ ＜ ｒTe ＜ ０．５０ ０ ≦ ｒX ＜ ０．５０ （ただし、ｒMo，ｒV，ｒTe，およびｒXは、各々酸素を
除く上記構成成分の合計に対するモリブデン、バナジウ
ム、テルルおよびＸのモル分率を表す）である複合酸化
物を主成分とすること。 の複合酸化物のＸ線回折
図において、下記に示す回折角２θにＸ線回折ピークを
示すこと。 【表１】 の複合酸化物のＸ線回折図において、回折角２θ
（゜）＝２２．１±０．３の回折ピーク強度を１００と
したとき、９．０±０．３の回折ピークの強度が ０．５
〜３０、かつ、２７．３±０．３の回折ピークの強度が
２５〜１４０の範囲であること。 1. A catalyst for producing a nitrile from an alkane satisfying the following conditions: Molybdenum, vanadium, tellurium, oxygen, and X (X is niobium, tantalum, tungsten, titanium, aluminum,
One or more elements selected from zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, antimony, bismuth, boron, indium and cerium) as constituent components, and the above oxygen is excluded. The existence ratio of each constituent with respect to the total of the constituents is as follows: 0.25 <r Mo <0.98 0.003 <r V <0.50 0.003 <r Te <0.50 0 <r X <0.50 (where r Mo , r V , r Te , and r X represent the mole fractions of molybdenum, vanadium, tellurium, and X with respect to the total of the above constituents excluding oxygen). Make things the main component. In the X-ray diffraction diagram of the complex oxide of, an X-ray diffraction peak should be shown at the diffraction angle 2θ shown below. [Table 1] In the X-ray diffraction diagram of the complex oxide of
The diffraction peak intensity at (°) = 22.1 ± 0.3 is set to 100.
The intensity of the diffraction peak at 9.0 ± 0.3 is 0.5
~ 30 and the intensity of the diffraction peak at 27.3 ± 0.3
It should be in the range of 25 to 140.
角２θ（゜）＝２２．１±０．３の回折ピーク強度を１
００としたとき、他の回折ピークの強度が下記に示す範
囲であることを特徴とする請求項１に記載の触媒。 【表２】 回折角 ２θ（゜） ピーク強度 ９．０±０．３ ０．５〜 ３０ ２７．３±０．３ ２５ 〜１４０ ２９．２±０．３ ０．５〜 ４０ ３５．４±０．３ ０．５〜 ４０2. In the X-ray diffraction pattern of the composite oxide, the diffraction peak intensity at a diffraction angle 2θ (°) = 22.1 ± 0.3 is 1
When set to 00, the intensity of other diffraction peaks falls within the range shown below.
The catalyst according to claim 1, which is an enclosure . [Table 2] Diffraction angle 2θ (°) Peak intensity 9.0 ± 0.3 0.5 to 30 27.3 ± 0.3 25 to 140 29.2 ± 0.3 0.5 to 40 35.4 ± 0.3 0.5-40
を満たす触媒の存在下、アンモニアと気相接触酸化反応
させることを特徴とするニトリルの製造方法。 モリ
ブデン、バナジウム、テルル、酸素、およびＸ（Ｘは、
ニオブ、タンタル、タングステン、チタン、アルミニウ
ム、ジルコニウム、クロム、マンガン、鉄、ルテニウ
ム、コバルト、ロジウム、ニッケル、パラジウム、白
金、アンチモン、ビスマス、ホウ素、インジウムおよび
セリウムの中から選ばれた１種以上の元素）を構成成分
とし、酸素を除く上記構成成分の合計に対する各構成成
分の存在割合が、 【数２】 ０．２５ ＜ ｒMo ＜ ０．９８ ０．００３ ＜ ｒV ＜ ０．５０ ０．００３ ＜ ｒTe ＜ ０．５０ ０ ≦ ｒX ＜ ０．５０ （ただし、ｒMo，ｒV，ｒTe，およびｒXは、各々酸素を
除く上記構成成分の合計に対するモリブデン、バナジウ
ム、テルルおよびＸのモル分率を表す）である複合酸化
物を主成分とすること。 の複合酸化物のＸ線回折
図において、下記に示す回折角２θにＸ線回折ピークを
示すこと。 【表３】 の複合酸化物のＸ線回折図において、回折角２θ
（゜）＝２２．１±０．３の回折ピーク強度を１００と
したとき、９．０±０．３の回折ピークの強度が０．５
〜３０、かつ、２７．３±０．３の回折ピークの強度が
２５〜１４０の範囲であること。 3. A method for producing a nitrile, which comprises subjecting an alkane to a gas phase catalytic oxidation reaction with ammonia in the presence of a catalyst satisfying the following conditions (1) and (2): Molybdenum, vanadium, tellurium, oxygen, and X (X is
One or more elements selected from niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, antimony, bismuth, boron, indium and cerium. ) and the constituents of proportions of each component to the sum of the above components excluding oxygen, Equation 2] 0.25 <r Mo <0.98 0.003 < r V <0.50 0.003 <R Te <0.50 0 ≤ r X <0.50 (where r Mo , r V , r Te , and r X are each of molybdenum, vanadium, tellurium, and X based on the total of the above-mentioned constituents except oxygen). (Representing the mole fraction) as a main component. In the X-ray diffraction diagram of the complex oxide of, an X-ray diffraction peak should be shown at the diffraction angle 2θ shown below. [Table 3] In the X-ray diffraction diagram of the complex oxide of
The diffraction peak intensity at (°) = 22.1 ± 0.3 is set to 100.
The intensity of the diffraction peak at 9.0 ± 0.3 is 0.5
~ 30 and the intensity of the diffraction peak at 27.3 ± 0.3
It should be in the range of 25 to 140.
角２θ（゜）＝２２．１±０．３の回折ピーク強度を１
００としたとき、他の回折ピークの強度が下記に示す範
囲であることを特徴とする請求項３のニトリルの製造方
法。 【表４】 回折角 ２θ（゜） ピーク強度 ９．０±０．３ ０．５〜 ３０ ２７．３±０．３ ２５ 〜１４０ ２９．２±０．３ ０．５〜 ４０ ３５．４±０．３ ０．５〜 ４０4. In the X-ray diffraction pattern of the composite oxide, the diffraction peak intensity at a diffraction angle 2θ (°) = 22.1 ± 0.3 is 1
When set to 00, the intensity of other diffraction peaks falls within the range shown below.
The method for producing a nitrile according to claim 3, wherein the nitrile is an enclosure . [Table 4] Diffraction angle 2θ (°) Peak intensity 9.0 ± 0.3 0.5 to 30 27.3 ± 0.3 25 to 140 29.2 ± 0.3 0.5 to 40 35.4 ± 0.3 0.5-40
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02558494A JP3500682B2 (en) | 1994-02-23 | 1994-02-23 | Catalyst for the production of nitriles from alkanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02558494A JP3500682B2 (en) | 1994-02-23 | 1994-02-23 | Catalyst for the production of nitriles from alkanes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07232071A JPH07232071A (en) | 1995-09-05 |
| JP3500682B2 true JP3500682B2 (en) | 2004-02-23 |
Family
ID=12169971
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02558494A Expired - Fee Related JP3500682B2 (en) | 1994-02-23 | 1994-02-23 | Catalyst for the production of nitriles from alkanes |
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| Country | Link |
|---|---|
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Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ID20720A (en) * | 1997-08-05 | 1999-02-18 | Asahi Chemical Ind | WATER SOLUTIONS THAT CONTAIN NIOBIUMS FOR USE IN THE MAKING OF OXIDE CATALYSTS CONTAINING NIOBIUM |
| DE19835247B4 (en) * | 1997-08-05 | 2022-04-28 | Asahi Kasei Kabushiki Kaisha | Ammoxidation catalyst and process for producing acrylonitrile or methacrylonitrile from propane or isobutane by ammoxidation |
| UA57721C2 (en) * | 1997-08-11 | 2003-07-15 | Асахі Касеі Кабусікі Кайся | A process for producing acrylonitrile or methacrylonitrile from propane or isobutane |
| UA51701C2 (en) * | 1997-10-15 | 2002-12-16 | Асахі Касеі Когіо Кабусікі Кайся | catalyst of ammoxidation and method of obtaining acrylonitrile or metacrylonitrile |
| JPH11169716A (en) * | 1997-12-09 | 1999-06-29 | Mitsubishi Chemical Corp | Catalyst for preparing unsaturated nitrile and/or unsaturated carboxylic acid |
| CA2271397A1 (en) * | 1998-05-21 | 1999-11-21 | Rohm And Haas Company | A process for preparing a catalyst |
| EP1260495B1 (en) * | 1998-05-21 | 2004-08-11 | Rohm And Haas Company | A process for preparing a multi-metal oxide catalyst |
| KR100303539B1 (en) | 1998-11-25 | 2001-11-30 | 김순택 | Cathode active material for lithium secondary battery and its manufacturing method |
| US6395427B1 (en) | 1999-11-04 | 2002-05-28 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and method of preparing same |
| KR100358805B1 (en) | 2000-03-07 | 2002-10-25 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery and method of preparing same |
| EP1642879B1 (en) | 2000-06-14 | 2014-05-21 | Basf Se | Method for producing acrolein and/or acrylic acid or a mixture thereof from propane and/or propene |
| DE10051419A1 (en) | 2000-10-17 | 2002-04-18 | Basf Ag | Production of acrolein or acrylic acid involves absorption of propane and propene from a gas mixture followed by desorption and oxidation, with no catalytic dehydrogenation of propane and no added oxygen |
| DE10118814A1 (en) | 2001-04-17 | 2002-10-24 | Basf Ag | Production of acrolein or acrylic acid involves absorption of propane and propene from a gas mixture followed by desorption and oxidation, with no catalytic dehydrogenation of propane and no added oxygen |
| BR0112557B1 (en) | 2000-07-18 | 2012-01-24 | process for the preparation of acrylic acid, and use of a multimetal oxide material. | |
| US7038082B2 (en) | 2002-10-17 | 2006-05-02 | Basf Aktiengesellschaft | Preparation of a multimetal oxide material |
| WO2004099081A1 (en) | 2003-05-12 | 2004-11-18 | Basf Aktiengesellschaft | Multimetal oxide materials provided in a pure i phase and containing mo, v, and alkali metal |
| FR2855516B1 (en) | 2003-05-27 | 2005-07-08 | Atofina | OXIDATION OF ACRYLIC ACID PROPANE BY USING CATALYSTS MIXED WITH CRYSTALLINE PHASES |
| US7253310B2 (en) | 2003-08-19 | 2007-08-07 | Basf Aktiengesellschaft | Preparation of (meth)acrylic acid |
| WO2005120702A1 (en) * | 2004-06-09 | 2005-12-22 | Basf Aktiengesellschaft | Method for the production of multi-metal oxide masses |
| FR2878767B1 (en) * | 2004-12-02 | 2007-07-13 | Arkema Sa | TANTAL-BASED CATALYST PREPARATION FOR SELECTIVE OXIDATION OF ACRYLIC ACID PROPANE |
| DE102017000865A1 (en) | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Synthesis of a MoVNbTe catalyst with increased specific surface area and higher activity for the oxidative dehydrogenation of ethane to ethylene |
| DE102017000861A1 (en) | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Synthesis of a MoVTeNb catalyst from inexpensive metal oxides |
| DE102017000848A1 (en) | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Process for the preparation of molybdenum-containing mixed oxide materials |
| DE102017000862A1 (en) | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Synthesis of a MoVNbTe catalyst with reduced content of niobium and tellurium and higher activity for the oxidative dehydrogenation of ethane |
| DE102017121709A1 (en) | 2017-09-19 | 2019-03-21 | Clariant International Ltd | Synthesis of a MoVNbTe coated catalyst for the oxidative dehydrogenation of ethane to ethylene |
-
1994
- 1994-02-23 JP JP02558494A patent/JP3500682B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH07232071A (en) | 1995-09-05 |
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