JP3534431B2 - Production of unsaturated nitrile - Google Patents
Production of unsaturated nitrileInfo
- Publication number
- JP3534431B2 JP3534431B2 JP21354293A JP21354293A JP3534431B2 JP 3534431 B2 JP3534431 B2 JP 3534431B2 JP 21354293 A JP21354293 A JP 21354293A JP 21354293 A JP21354293 A JP 21354293A JP 3534431 B2 JP3534431 B2 JP 3534431B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- component
- propylene
- methacrylonitrile
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000002825 nitriles Chemical class 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims description 45
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011268 mixed slurry Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 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 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 39
- 239000000306 component Substances 0.000 description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 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 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
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011572 manganese Substances 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- -1 rudibium Chemical compound 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 239000012808 vapor phase Substances 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、モリブデン、ビスマ
ス、鉄を含む多重促進酸化物触媒の存在下に、プロピレ
ンまたはイソブチレンをアンモニアおよび酸素と気相接
触させてアクリロニトリルまたはメタクリロニトリルを
製造する方法に関する。The present invention relates to a method for producing acrylonitrile or methacrylonitrile by vapor-phase contacting propylene or isobutylene with ammonia and oxygen in the presence of a multipromoting oxide catalyst containing molybdenum, bismuth and iron. Regarding
【０００２】[0002]
【従来の技術】プロピレンまたはイソブチレンをアンモ
ニアの存在下に分子状酸素によって気相酸化してアクリ
ロニトリルまたはメタクリロニトリルを製造する方法
は、「アンモ酸化プロセス」として広く知られ、現在工
業的規模で実施されている。この反応に使用されるモリ
ブデン、ビスマス、鉄を含む多数の触媒が発表されてい
る。例えば、特開平２−５９０４６号公報、特開平２−
２５１２５０号公報、特公昭４０−２５３２号公報、特
公昭５０−１５７７３号公報、特公昭５１−６６４９号
公報、特公昭５２−４５６９２号公報、特公昭５９−５
０６６７号公報、特公昭６０−３６８１２号公報、特公
昭６２−４２６５４号公報、米国特許第４，１６７，４
９４号、米国特許第５，０９３，２９９号などに、いわ
ゆるモリブデン、ビスマス、鉄を含む多成分酸化物触媒
が開示されている。2. Description of the Related Art A method for producing acrylonitrile or methacrylonitrile by gas phase oxidation of propylene or isobutylene with molecular oxygen in the presence of ammonia is widely known as "ammoxidation process" and is currently carried out on an industrial scale. Has been done. Numerous catalysts have been announced, including molybdenum, bismuth and iron used in this reaction. For example, JP-A-2-59046 and JP-A-2-59046
No. 251250, Japanese Patent Publication No. 40-2532, Japanese Patent Publication No. 5015773, Japanese Patent Publication No. 51-6649, Japanese Patent Publication No. 52-45692, Japanese Patent Publication No. 59-5.
No. 0667, Japanese Patent Publication No. 60-36812, Japanese Patent Publication No. 62-42654, and U.S. Pat. No. 4,167,4.
No. 94, US Pat. No. 5,093,299 and the like disclose multi-component oxide catalysts containing so-called molybdenum, bismuth and iron.
【０００３】これらは種々の利点を有する優れた触媒で
あるが、アンモ酸化の副反応の抑制が不十分であり、目
的生成物の収率は未だ満足すべきものではない。These are excellent catalysts having various advantages, but the side reaction of ammoxidation is not sufficiently suppressed, and the yield of the target product is not yet satisfactory.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、上記
の従来触媒を基に改良された触媒を用いて、より高い収
率でアクリロニトリルまたはメタクリロニトリルを製造
する方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing acrylonitrile or methacrylonitrile in a higher yield by using an improved catalyst based on the above conventional catalyst. .
【０００５】[0005]
【課題を解決するための手段】本発明方法の主たる要件
は触媒にある。本発明者は、プロピレンまたはイソブチ
レンのアンモ酸化反応に用いるモリブデン、ビスマス、
鉄を含有する触媒を鋭意検討した結果、これらの成分と
さらに特定の金属成分を複合した酸化物が、アクリロニ
トリルまたはメタクリロニトリルの収率を一層向上させ
ることを見出し、本発明を完成するに至った。The main requirement of the process according to the invention lies in the catalyst. The present inventor has proposed molybdenum, bismuth, which is used for the ammoxidation reaction of propylene or isobutylene,
As a result of diligent examination of iron-containing catalysts, it was found that an oxide in which these components and further a specific metal component were combined further improved the yield of acrylonitrile or methacrylonitrile, and the present invention was completed. It was
【０００６】本発明の触媒は、一般組成式The catalyst of the present invention has a general compositional formula.
【０００７】[0007]
【化２】
（式中、Ｑはクロムおよびインジウムの中から選ばれる
少なくとも１種の元素、Ａはカリウム、ルジビウムおよ
びセシウムの中から選ばれる少なくとも一種の元素、Ｅ
はマンガン、マグネシウム、亜鉛、セリウム、ナトリウ
ムおよびリンの中から選ばれる少なくとも一種の元素で
あり、ｍ、ｂ、ｆ、ｎ、ｑ、ａ、ｅおよびｘはそれぞれ
モリブデン、ビスマス、鉄、ニッケル、成分Ｑ、成分
Ａ、成分Ｅおよび酸素の原子比を表わし、ｍ＝１０〜１
４、好ましくは１１〜１３、ｂ＝０．１〜３、好ましく
は０．３〜２、ｆ＝０．１〜３、好ましくは０．５〜
２．５、ｎ＝４〜１０、好ましくは５〜９、ｑ＝０．１
〜２、好ましくは０．２〜１．５、ａ＝０．０１〜０．
５、好ましくは０．１〜０．４、ｅ＝０〜３、ｘは組成
式中の金属成分の原子価を満足する酸素の原子比であ
る。）で示される組成物を４０〜６０重量％のシリカに
担持させたものである。[Chemical 2] (In the formula, Q is at least one element selected from chromium and indium, A is at least one element selected from potassium, rudibium, and cesium, E
Is at least one element selected from manganese, magnesium, zinc, cerium, sodium and phosphorus, and m, b, f, n, q, a, e and x are molybdenum, bismuth, iron, nickel and components, respectively. Represents the atomic ratio of Q, component A, component E and oxygen, m = 10 to 1
4, preferably 11-13, b = 0.1-3, preferably 0.3-2, f = 0.1-3, preferably 0.5-
2.5, n = 4-10, preferably 5-9, q = 0.1
~ 2, preferably 0.2 to 1.5, a = 0.01 to 0.
5, preferably 0.1 to 0.4, e = 0 to 3, and x is an atomic ratio of oxygen satisfying the valence of the metal component in the composition formula. ) The composition represented by (4) is supported on 40 to 60% by weight of silica.
【０００８】本発明の触媒は、効果的な作用および特性
を得るために不可欠の成分Ｑを含有することを特徴とす
る。成分Ｑのクロムとインジウムを混合して用いる場合
は、それぞれ単独で用いる場合よりも優れたアクリロニ
トリルまたはメタクリロニトリルの収率が得られる。ク
ロムを単独で用いる場合は、ｑが１を越えないことが望
ましい。また、成分Ｑの量は鉄に対する相対含量、すな
わち、ｑ／（ｑ＋ｆ）が０．７以下になるように決定す
ることが望ましい。The catalyst of the present invention is characterized in that it contains the essential component Q in order to obtain effective action and properties. When chromium and indium of the component Q are used as a mixture, a yield of acrylonitrile or methacrylonitrile which is superior to the case where they are used alone is obtained. When chromium is used alone, it is desirable that q does not exceed 1. Further, it is desirable to determine the amount of the component Q so that the relative content with respect to iron, that is, q / (q + f) is 0.7 or less.
【０００９】本発明の触媒において微量ではあるが不可
欠の成分Ａは、プロピレンまたはイソブチレンからのア
クリロニトリルまたはメタクリロニトリルへの選択率を
向上させる。成分Ａの中ではルビジウムまたはセシウム
を単独で用いる場合は、カリウムよりも少ない量でアク
リロニトリルまたはメタクリロニトリルの選択率を向上
させる。成分Ａは本発明の量範囲を越えて用いる場合
は、プロピレンまたはイソブチレンの反応活性を減じ
る。Ingredient A, although present in trace amounts in the catalyst of the present invention, improves the selectivity of propylene or isobutylene to acrylonitrile or methacrylonitrile. In the component A, when rubidium or cesium is used alone, it improves the selectivity of acrylonitrile or methacrylonitrile in an amount smaller than that of potassium. Component A reduces the reaction activity of propylene or isobutylene when used in excess of the amount range of the invention.
【００１０】任意成分Ｅは反応活性、触媒物性などの調
整のために適宜選択して用いることができる。任意成分
Ｅのリンは、触媒の耐摩耗性を向上させる場合がある。The optional component E can be appropriately selected and used in order to adjust the reaction activity and the physical properties of the catalyst. Optional component
The phosphorus of E may improve the wear resistance of the catalyst.
【００１１】シリカは触媒の担体である。本発明のシリ
カ担持された触媒は、流動層アンモ酸化反応において優
れた流動性を有する。シリカの使用量が４０重量％以上
で優れた耐摩耗性が得られる。しかし、６０重量％を越
えて用いる場合は、触媒成分が稀釈され、十分な活性が
得られないばかりでなく、大きく選択率も減少する。本
発明の触媒は、先ず原料混合スラリーを調製し、次いで
該スラリーを噴霧乾燥し、最後に該乾燥品を焼成すると
いう三つの工程を経て好適に製造することができる。Silica is a catalyst carrier. The silica-supported catalyst of the present invention has excellent fluidity in a fluidized bed ammoxidation reaction. When the amount of silica used is 40% by weight or more, excellent wear resistance can be obtained. However, when it is used in an amount of more than 60% by weight, not only is the catalyst component diluted, sufficient activity is not obtained, but the selectivity is also greatly reduced. The catalyst of the present invention can be suitably produced through three steps of first preparing a raw material mixed slurry, then spray drying the slurry, and finally calcining the dried product.
【００１２】本発明の触媒の各成分は、水または硝酸に
可溶な塩の形で用いることが望ましい。モリブデン源と
しては、七モリブデン酸アンモニウムを用いることがで
きる。ビスマス、鉄、ニッケル、クロム、インジウム、
マンガン、マグネシウム、亜鉛、セリウムおよびナトリ
ウム源としては、それぞれの硝酸塩を用いることができ
る。リン源としてはリン酸、そして、シリカ源としては
シリカゾルが好適である。用いるシリカゾルは、できる
だけアルミニウム含量の少ない高純度であることが望ま
しい。Each component of the catalyst of the present invention is preferably used in the form of a salt soluble in water or nitric acid. As the molybdenum source, ammonium heptamolybdate can be used. Bismuth, iron, nickel, chromium, indium,
As the manganese, magnesium, zinc, cerium and sodium sources, respective nitrates can be used. Phosphoric acid is preferable as the phosphorus source, and silica sol is preferable as the silica source. It is desirable that the silica sol used is of high purity with as little aluminum content as possible.
【００１３】原料混合スラリーの調製は、先ずシリカゾ
ルに攪拌しながらリン酸を、次いで七モリブデン酸アン
モニウムの水溶液を加え、最後にその他の成分の硝酸塩
の混合液を加えることによって、好適に行なうことがで
きる。ここに得られる原料混合スラリーのｐＨを２以下
とする。このとき、優れた物性を有する触媒が得られ
る。原料混合スラリーを噴霧乾燥することによって流動
層反応に適した球形微粒子を得ることができる。The raw material-mixed slurry is preferably prepared by first adding phosphoric acid to the silica sol while stirring, then adding an aqueous solution of ammonium heptamolybdate, and finally adding a mixed solution of nitrates of other components. it can. The pH of the raw material mixed slurry obtained here is 2 or less.
And At this time, a catalyst having excellent physical properties is obtained. By spray-drying the raw material mixed slurry, spherical fine particles suitable for fluidized bed reaction can be obtained.
【００１４】噴霧乾燥粒子は焼成の前に脱硝処理するこ
とが望ましい。脱硝処理は３５０〜４５０℃で０．５〜
２．０時間熱処理することによって行なうことができ
る。脱硝処理品は最後に５００〜６５０℃、好ましくは
５５０〜６３０℃にて焼成して触媒を得る。触媒の焼成
温度が低過ぎるとプロピレンまたはイソブチレンの反応
活性は大きいが、アクリロニトリルまたはメタクリロニ
トリルへの選択率が小さくなるだけではなく、耐摩耗性
も減少する。一方、焼成温度が高過ぎる場合はプロピレ
ンまたはイソブチレンの反応活性が減少し、かつ次式に
よるアンモニアの燃焼が増大する。Desirably, the spray-dried particles are subjected to a denitration treatment before firing. Denitration treatment is from 350 to 450 ℃ and 0.5 to
It can be performed by heat treatment for 2.0 hours. Finally, the denitration treated product is calcined at 500 to 650 ° C, preferably 550 to 630 ° C to obtain a catalyst. If the calcination temperature of the catalyst is too low, the reaction activity of propylene or isobutylene is high, but the reaction temperature of acrylonitrile or methacrylonitrile is high.
Not only is the selectivity to the trill reduced, but the wear resistance is also reduced. On the other hand, when the firing temperature is too high, the reaction activity of propylene or isobutylene decreases and the combustion of ammonia according to the following equation increases.
【００１５】[0015]
【数１】
本発明の触媒の好適な焼成温度は、上記の５００〜６５
０℃の範囲から、アンモ酸化反応テストの結果をみて決
定することができる。通常、焼成時間は１〜５時間であ
る。[Equation 1] The preferable calcination temperature of the catalyst of the present invention is 500 to 65 above.
From the range of 0 ° C, it can be determined by looking at the result of the ammoxidation reaction test. Usually, the firing time is 1 to 5 hours.
【００１６】アンモ酸化反応の原料であるプロピレン、
イソブチレンおよびアンモニアは必ずしも高純度である
必要はなく、工業グレードのものを使用することができ
る。ターシャリーブタノールはイソブチレンの代替原料
として好適に用いることができる。酸素源としては通常
空気を用いる。プロピレンまたはイソブチレンに対する
アンモニアと空気の容積比は１：０．９〜１．３：７〜
１１、特に１：１．０〜１．２：８〜１０の範囲が好ま
しい。Propylene, which is a raw material for the ammoxidation reaction,
Isobutylene and ammonia do not necessarily need to be highly pure, and industrial grade ones can be used. Tertiary butanol can be suitably used as a substitute raw material for isobutylene. Air is usually used as the oxygen source. The volume ratio of ammonia and air to propylene or isobutylene is 1: 0.9-1.3: 7-
A range of 11, especially 1: 1.0 to 1.2: 8 to 10 is preferable.
【００１７】反応温度は４００〜４６０℃、特に４１０
〜４４０℃の範囲が好ましい。反応圧力は常圧〜３気圧
の範囲で行なうことができる。原料混合ガスと触媒との
接触時間は１〜８秒、好ましくは２〜６秒である。The reaction temperature is 400 to 460 ° C., especially 410
The range of ˜440 ° C. is preferable. The reaction pressure can be in the range of atmospheric pressure to 3 atm. The contact time between the raw material mixed gas and the catalyst is 1 to 8 seconds, preferably 2 to 6 seconds.
【００１８】[0018]
【実施例】以下、実施例により本発明を更に具体的に説
明する。The present invention will be described in more detail with reference to the following examples.
【００１９】（触媒製造実施例）５０重量％のシリカに
担持された下記の組成式を有する触媒１を以下のように
製造した。(Catalyst Production Example) A catalyst 1 having the following composition formula and supported on 50% by weight of silica was produced as follows.
【００２０】[0020]
【化３】
１６６７ｇの３０％シリカゾルに、水１２００ｇに七モ
リブデン酸アンモニウム〔（ＮＨ4 ）6 Ｍｏ7 Ｏ24・４
Ｈ2 Ｏ〕４０６．１ｇを溶解した液を攪拌下に加え、最
後に予め６００ｇの１３％硝酸に、５５．７ｇの硝酸ビ
スマス〔Ｂｉ（ＮＯ3 ）3 ・５Ｈ2 Ｏ〕、１３９．８ｇ
の硝酸第二鉄〔Ｆｅ（ＮＯ3 ）3 ・９Ｈ2 Ｏ〕、４１
９．３ｇの硝酸ニッケル〔Ｎｉ（ＮＯ3 ）2 ・６Ｈ
2 Ｏ〕、４６．２ｇの硝酸クロム〔Ｃｒ（ＮＯ3 ）3 ・
９Ｈ2 Ｏ〕および３．８７ｇの硝酸カリウム〔ＫＮ
Ｏ3 〕を溶解した混合液を加えた。ここに得られた原料
混合液はスラリー状であり、ｐＨは０．３であった。ス
ラリーの噴霧化は乾燥器上部の中央に設置されたところ
の皿型回転子を備えた遠心式噴霧化装置を用いて行なっ
た。乾燥器の入口空気温度を２５０℃に、そして、出口
温度を１３０℃に保持してスラリーの噴霧乾燥を行なっ
た。得られた乾燥粉体をキルンに移し、先ず４００℃で
１時間脱硝し、次いで５６０℃で２時間焼成して触媒を
得た。[Chemical 3] 30% silica sol 1667 g, ammonium heptamolybdate in water 1200g [(NH 4) 6 Mo 7 O 24 · 4
H 2 O] A solution in which 406.1 g was dissolved was added with stirring, and finally, 55.7 g of bismuth nitrate [Bi (NO 3 ) 3 .5H 2 O], 139.8 g was added to 600 g of 13% nitric acid in advance.
Of ferric nitrate [Fe (NO 3) 3 · 9H 2 O ], 41
9.3g of nickel nitrate [Ni (NO 3) 2 · 6H
2 O], 46.2 g of chromium nitrate [Cr (NO 3 ) 3 ·
9H 2 O] and 3.87 g of potassium nitrate [KN
A mixed solution in which O 3 ] was dissolved was added. The raw material mixed solution obtained here was in the form of a slurry and had a pH of 0.3. Atomization of the slurry was performed using a centrifugal atomizer equipped with a dish rotor installed in the center of the upper part of the dryer. The slurry was spray dried by keeping the inlet air temperature of the dryer at 250 ° C and the outlet temperature at 130 ° C. The obtained dry powder was transferred to a kiln, first denitrated at 400 ° C. for 1 hour, and then calcined at 560 ° C. for 2 hours to obtain a catalyst.
【００２１】上記と同様の方法により表１記載の組成を
有する触媒２〜１１と比較触媒１と２を製造した。これ
らの触媒の製造に当って、Ｍｏ、Ｂｉ、Ｆｅ、Ｎｉ、Ｃ
ｒ、ＫおよびＳｉＯ2 源として触媒１と同じ原料を用い
た。触媒成分にインジウム、ルビジウム、セシウム、マ
ンガン、マグネシウム、亜鉛、セリウム、ナトリウム、
リンが含まれる場合は、それぞれインジウム〔Ｉｎ（Ｎ
Ｏ3 ）3 ・３Ｈ2 Ｏ〕、硝酸ルビジウム〔ＲｂＮ
Ｏ3 〕、硝酸セシウム〔ＣｓＮＯ3 〕、硝酸マンガン
〔Ｍｎ（ＮＯ3 ）2 ・６Ｈ2 Ｏ〕、硝酸マグネシウム
〔Ｍｇ（ＮＯ3 ）2 ・６Ｈ2 Ｏ〕、硝酸亜鉛〔Ｚｎ（Ｎ
Ｏ3 ）2 ・６Ｈ2 Ｏ〕、硝酸セリウム〔Ｃｅ（ＮＯ3 ）
3 ・６Ｈ2 Ｏ〕、硝酸ナトリウム〔ＮａＮＯ3 〕、リン
酸〔Ｈ3 ＰＯ4 〕を用いた。これらの触媒の焼成は、そ
れぞれ表１記載の温度で行なった。Catalysts 2 to 11 having the composition shown in Table 1 and comparative catalysts 1 and 2 were produced by the same method as described above. In the production of these catalysts, Mo, Bi, Fe, Ni, C
The same raw materials as in Catalyst 1 were used as the r, K and SiO 2 sources. The catalyst component is indium, rubidium, cesium, manganese, magnesium, zinc, cerium, sodium,
When phosphorus is contained, indium [In (N
O 3) 3 · 3H 2 O], rubidium nitrate [RbN
O 3], cesium nitrate [CsNO 3], manganese nitrate [Mn (NO 3) 2 · 6H 2 O ], magnesium nitrate [Mg (NO 3) 2 · 6H 2 O ], zinc nitrate [Zn (N
O 3) 2 · 6H 2 O], cerium nitrate [Ce (NO 3)
3 · 6H 2 O], sodium nitrate [NaNO 3], using phosphoric acid [H 3 PO 4]. The calcination of these catalysts was performed at the temperatures shown in Table 1, respectively.
【００２２】[0022]
【表１】
（プロピレンのアンモ酸化反応実施例）１０メッシュの
金網を１ｃｍ間隔で１２枚内蔵した内径２５ｍｍのバイ
コールガラス流動層反応管に５０ｃｃの触媒１をとり、
反応温度４３５℃、反応圧力常圧下に、プロピレン９容
積％の混合ガス（プロピレン：アンモニア：酸素：ヘリ
ウムの容積比が１：１．２：１．８５：７．０６）を毎
秒３．５０ｃｃ（ＮＴＰ換算）の流速で通過させた。こ
の反応の結果を下記式で定義されるプロピレン転化率、
アクリロニトリル選択率およびアクリロニトリル収率の
３つの指標によって評価し、それらの値を表２に記載し
た。[Table 1] (Example of ammoxidation reaction of propylene) 50 cc of catalyst 1 was placed in a Vycor glass fluidized bed reaction tube having an inner diameter of 25 mm and containing 12 pieces of 10-mesh wire mesh at 1 cm intervals.
At a reaction temperature of 435 ° C. and a reaction pressure of normal pressure, a mixed gas of propylene 9% by volume (volume ratio of propylene: ammonia: oxygen: helium 1: 1.2: 1.85: 7.06) was applied at 3.50 cc / s. It was passed at a flow rate of NTP conversion). The result of this reaction is the propylene conversion rate defined by the following formula,
Acrylonitrile selectivity and acrylonitrile yield were evaluated by three indexes, and those values are shown in Table 2.
【００２３】[0023]
【数２】
触媒２、３、４、６、７、８、９および１０、そして、
比較触媒１と２について上と同様の反応を行なった。こ
れらの反応は、原料混合ガスのプロピレンを９容積％、
プロピレンに対するアンモニアの容積比を１：１．２に
固定し、プロピレンに対する酸素の容積比を１．８〜
１．９の範囲から適宜選択して行なった。また、各触媒
のプロピレン反応活性に応じて、反応温度および次式で
定義される接触時間を適宜変更した。各触媒の反応条件
および反応成績を表２に示す。[Equation 2] Catalysts 2, 3, 4, 6, 7, 8, 9 and 10, and
Comparative catalysts 1 and 2 were subjected to the same reaction as above. In these reactions, 9% by volume of propylene, which is a raw material mixed gas,
The volume ratio of ammonia to propylene is fixed at 1: 1.2, and the volume ratio of oxygen to propylene is 1.8 to
It was performed by appropriately selecting from the range of 1.9. Further, the reaction temperature and the contact time defined by the following formula were appropriately changed according to the propylene reaction activity of each catalyst. Table 2 shows the reaction conditions and reaction results of each catalyst.
【００２４】[0024]
【数３】 但し、Ｖ：触媒量（ｃｃ） Ｆ：原料混合ガス流量（ｃｃ−ＮＴＰ／ｓｅｃ） Ｔ：反応温度（℃）[Equation 3] However, V: catalyst amount (cc) F: raw material mixed gas flow rate (cc-NTP / sec) T: reaction temperature (° C)
【００２５】[0025]
【表２】
（イソブチレンのアンモ酸化反応実施例）５０ｃｃの触
媒５を上記のプロピレンのアンモ酸化反応に用いた反応
管にとり、反応温度４３０℃、反応圧力常圧下に、イソ
ブチレン７．５容積％の混合ガス（イソブチレン：アン
モニア：酸素：水：ヘリウム＝１：１．２：１．９５：
１．８：７．３８）を毎秒３．８８ｃｃ（ＮＴＰ換算）
の流速で通過させた。この反応の結果をプロピレンの場
合と同様に定義されるイソブチレン転化率、メタクリロ
ニトリル選択率およびメタクリロニトリル収率の３つの
指標によって評価し、それらの値を表３に示した。[Table 2] (Example of ammoxidation reaction of isobutylene) A 50 cc catalyst 5 was placed in a reaction tube used for the ammoxidation reaction of propylene, and a mixed gas of 7.5% by volume of isobutylene (isobutylene was added at a reaction temperature of 430 ° C. and a normal reaction pressure). : Ammonia: Oxygen: Water: Helium = 1: 1.2: 1.95:
1.8: 7.38) 3.88cc per second (NTP conversion)
At a flow rate of The results of this reaction were evaluated by the three indices of isobutylene conversion, methacrylonitrile selectivity and methacrylonitrile yield, which were defined as in the case of propylene, and those values are shown in Table 3.
【００２６】触媒１１および比較触媒１について、上と
同様の反応を行なった。各触媒の反応条件および反応成
績を表３に示す。With respect to the catalyst 11 and the comparative catalyst 1, the same reaction as above was performed. Table 3 shows the reaction conditions and reaction results of each catalyst.
【００２７】[0027]
【表３】 [Table 3]
【００２８】[0028]
【発明の効果】本発明によれば、プロピレンまたはイソ
ブチレンのアンモ酸化反応に用いるモリブデン、ビスマ
ス、鉄を含有する触媒成分に、さらに特定の金属成分を
複合した酸化物を触媒として用いることにより、アクリ
ロニトリルまたはメタクリロニトリルの収率を一層向上
することができる。INDUSTRIAL APPLICABILITY According to the present invention, the catalyst component containing molybdenum, bismuth and iron used for the ammoxidation reaction of propylene or isobutylene is further mixed with a specific metal component to form an acrylonitrile. Alternatively, the yield of methacrylonitrile can be further improved.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−59046（ＪＰ，Ａ) 特開 平２−251250（ＪＰ，Ａ) 特開 昭51−40391（ＪＰ，Ａ) 特開 昭61−18435（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 C07B 61/00 ─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-2-59046 (JP, A) JP-A-2-251250 (JP, A) JP-A-51-40391 (JP, A) JP-A-61- 18435 (JP, A) (58) Fields surveyed (Int.Cl. 7 , DB name) B01J 21/00-38/74 C07B 61/00
Claims (3)
存在下アンモニアおよび酸素と高温で気相接触させてア
クリロニトリルまたはメタクリロニトリルを製造するに
当り、次の一般組成式 【化１】 （式中、Ｍｏはモリブデン、Ｂｉはビスマス、Ｆｅは
鉄、Ｎｉはニッケル、Ｑはクロムおよびインジウムの中
から選ばれる少なくとも一種の元素、Ａはカリウム、ル
ビジウムおよびセシウムの中から選ばれる少なくとも一
種の元素、Ｅはマンガン、マグネシウム、亜鉛、セリウ
ム、ナトリウムおよびリンの中から選ばれる少なくとも
一種の元素、Ｏは酸素であり、ｍ、ｂ、ｆ、ｎ、ｑ、
ａ、ｅおよびｘは原子比を表わし、ｍ＝１０〜１４、ｂ
＝０．１〜３、ｆ＝０．１〜３、ｎ＝４〜１０、ｑ＝
０．１〜２、ａ＝０．０１〜０．５、ｅ＝０〜３、そし
て、ｘは組成式中の金属成分の酸化物に対応する酸素の
原子比である。）で示される組成物を４０〜６０重量％
のシリカに担持された触媒を使用し、原料混合スラリー
のｐＨを２以下とすることを特徴とするアクリロニトリ
ルまたはメタクリロニトリルの製造法。1. In producing acrylonitrile or methacrylonitrile by vapor-contacting propylene or isobutylene with ammonia and oxygen in the presence of a catalyst at a high temperature, the following general composition formula: (In the formula, Mo is molybdenum, Bi is bismuth, Fe is iron, Ni is nickel, Q is at least one element selected from chromium and indium, and A is at least one element selected from potassium, rubidium and cesium. An element, E is at least one element selected from manganese, magnesium, zinc, cerium, sodium and phosphorus, O is oxygen, and m, b, f, n, q,
a, e and x represent atomic ratios, m = 10 to 14, b
= 0.1-3, f = 0.1-3, n = 4-10, q =
0.1 to 2, a = 0.01 to 0.5, e = 0 to 3, and x is the atomic ratio of oxygen corresponding to the oxide of the metal component in the composition formula. 40% to 60% by weight of the composition
Raw material mixed slurry using the catalyst supported on silica
The method for producing acrylonitrile or methacrylonitrile is characterized in that the pH of the solution is 2 or less .
る少なくとも一種の元素である請求項１記載の方法。2. The method according to claim 1, wherein the component E is at least one element selected from zinc and cerium.
ある請求項１記載の方法。3. The method according to claim 1, wherein the component Q is a mixture of chromium and indium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21354293A JP3534431B2 (en) | 1993-08-06 | 1993-08-06 | Production of unsaturated nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21354293A JP3534431B2 (en) | 1993-08-06 | 1993-08-06 | Production of unsaturated nitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0747272A JPH0747272A (en) | 1995-02-21 |
| JP3534431B2 true JP3534431B2 (en) | 2004-06-07 |
Family
ID=16640923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21354293A Expired - Lifetime JP3534431B2 (en) | 1993-08-06 | 1993-08-06 | Production of unsaturated nitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3534431B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008050767A1 (en) | 2006-10-26 | 2008-05-02 | Dia-Nitrix Co., Ltd. | Fluidized-bed catalyst for the production of acrylonitrile and process for the production of acrylonitrile |
| EP2098288A1 (en) | 2008-03-03 | 2009-09-09 | Dia-Nitrix Co., Ltd. | Catalyst for producing acrylonitrile and process for producing acrlyonitrile |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063679C (en) * | 1997-01-10 | 2001-03-28 | 中国石油化工总公司 | Fluidized bed catalyst containing halogen for producing acrylonitrile |
| ES2226375T3 (en) | 1998-04-23 | 2005-03-16 | Mitsubishi Rayon Co., Ltd. | CATALYST TO PRODUCE INSURED NITRILE. |
| WO1999054037A1 (en) * | 1998-04-23 | 1999-10-28 | Mitsubishi Rayon Co., Ltd. | Catalyst for producing unsaturated nitrile |
| DE60030747T2 (en) * | 1999-10-18 | 2007-09-20 | Mitsubishi Rayon Co., Ltd. | A PROCESS FOR THE PRODUCTION OF ACRYLNITRILE, A CATALYST FOR THIS USE AND A METHOD FOR THE PRODUCTION THEREOF |
| US6458742B1 (en) | 2000-08-17 | 2002-10-01 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile |
| JP4030740B2 (en) | 2001-10-11 | 2008-01-09 | ダイヤニトリックス株式会社 | Method for producing ammoxidation catalyst |
| US7071140B2 (en) | 2002-12-02 | 2006-07-04 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile |
| CA2507182A1 (en) | 2002-12-02 | 2004-06-17 | The Standard Oil Company | Mixed oxide catalyst of k, cs, ce, cr, co, ni, fe, bi and mo for the manufacture of acrylonitrile |
| JP4425743B2 (en) * | 2004-08-19 | 2010-03-03 | ダイヤニトリックス株式会社 | Method for producing fluidized bed catalyst for acrylonitrile synthesis |
| JP5011176B2 (en) | 2008-03-14 | 2012-08-29 | ダイヤニトリックス株式会社 | Catalyst for synthesizing acrylonitrile and method for producing acrylonitrile |
| US8455388B2 (en) | 2010-03-23 | 2013-06-04 | Ineos Usa Llc | Attrition resistant mixed metal oxide ammoxidation catalysts |
| US8153546B2 (en) | 2010-03-23 | 2012-04-10 | Ineos Usa Llc | Mixed metal oxide ammoxidation catalysts |
| US8258073B2 (en) | 2010-03-23 | 2012-09-04 | Ineos Usa Llc | Process for preparing improved mixed metal oxide ammoxidation catalysts |
| US8420566B2 (en) | 2010-03-23 | 2013-04-16 | Ineos Usa Llc | High efficiency ammoxidation process and mixed metal oxide catalysts |
-
1993
- 1993-08-06 JP JP21354293A patent/JP3534431B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008050767A1 (en) | 2006-10-26 | 2008-05-02 | Dia-Nitrix Co., Ltd. | Fluidized-bed catalyst for the production of acrylonitrile and process for the production of acrylonitrile |
| US7902112B2 (en) | 2006-10-26 | 2011-03-08 | Dia-Nitrix Co., Ltd. | Fluidized bed catalyst for producing acrylonitrile and process for producing acrylonitrile |
| EP2098288A1 (en) | 2008-03-03 | 2009-09-09 | Dia-Nitrix Co., Ltd. | Catalyst for producing acrylonitrile and process for producing acrlyonitrile |
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| JPH0747272A (en) | 1995-02-21 |
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