WO1999054037A1 - Catalyseur de production de nitrile insature - Google Patents

Catalyseur de production de nitrile insature Download PDF

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Publication number
WO1999054037A1
WO1999054037A1 PCT/JP1999/002146 JP9902146W WO9954037A1 WO 1999054037 A1 WO1999054037 A1 WO 1999054037A1 JP 9902146 W JP9902146 W JP 9902146W WO 9954037 A1 WO9954037 A1 WO 9954037A1
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WO
WIPO (PCT)
Prior art keywords
raw material
group
element selected
iron
catalyst
Prior art date
Application number
PCT/JP1999/002146
Other languages
English (en)
Japanese (ja)
Inventor
Yutaka Sasaki
Kunio Mori
Yoshimi Nakamura
Takao Shimizu
Yuichi Tagawa
Kenichi Miyaki
Seiichi Kawatou
Original Assignee
Mitsubishi Rayon Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co., Ltd. filed Critical Mitsubishi Rayon Co., Ltd.
Priority to ROA200001018A priority Critical patent/RO119228B1/ro
Priority to EP99917105A priority patent/EP1075871B1/fr
Priority to US09/673,571 priority patent/US6479691B1/en
Priority to DE69920437T priority patent/DE69920437T2/de
Publication of WO1999054037A1 publication Critical patent/WO1999054037A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B01J27/192—Molybdenum with bismuth

Definitions

  • the present invention relates to a metal oxide catalyst used for producing unsaturated nitrile by ammoxidation.
  • 4,290,922 includes molybdenum, cobalt, nickel, bismuth, vanadium, calcium, and potassium as essential components.
  • Patent No. 2,640,356 discloses an oxide catalyst containing molybdenum, bismuth, iron, nickel, and metal alloys;
  • U.S. Patent No. 5,093,299 and US Pat. No. 5,175,334 describe oxides containing molybdenum, bismuth, iron, nickel, magnesium, potassium and cesium.
  • 7-47272 disclose at least one element selected from the group consisting of molybdenum, bismuth, iron, nickel, chromium and indium, and alkalis such as potassium.
  • No. 5,132,269 discloses iron, antimony, and molybdenum, bismuth, cerium, iron, nickel, and oxide catalysts containing magnesium or zinc, and alkali metals.
  • a catalyst containing molybdenum, bismuth, iron, antimony, or the like comprises chromium, zirconium, lanthanum, and cerium.
  • At least one element selected from the group consisting of chromium, zirconium, lanthanum and cerium has a clear effect when added in a relatively small amount, and excessive addition rather decreases the yield of the target product sharply .
  • the ratio of zirconium, lanthanum, cerium, and the like to chromium is small. If the ratio is large, ammonia flammability increases and the yield of the target product decreases.
  • Chromium is used in combination with at least one element selected from the group consisting of zirconium, lanthanum and cerium, and by finding a favorable quantitative relationship at the time of addition, the yield of the target product is improved, and The flammability was suppressed and the yield of by-products was also reduced.
  • the present invention provides a catalyst composition represented by the following empirical formula, which is used when producing unsaturated nitrile by ammoxidation:
  • Mo, Bi, Fe, Sb, Ni, Cr, and K represent molybdenum, bismuth, iron, antimony, nickel, chromium, and potassium, respectively, and F represents zirconium, lanthanum, and cerium.
  • X is at least one element selected from the group consisting of phosphorus, boron and tellurium
  • Y is at least one element selected from the group consisting of lithium, sodium, rubidium and cesium
  • O is oxygen
  • U.S. Pat. No. 3,350,323 discloses a method of adding an aqueous solution of bismuth citrate to an aqueous solution of molybdic acid, JP-A-53-10387, JP-A-53-10388, and U.S. Pat. No. 4,847,831 describes a method of adding a bismuth compound in a solid state to an aqueous molybdic acid solution, and US Pat. No. 4,418,007 discloses a method in which the pH is in the range of 6 to 8.
  • 4,803,190 describes a method of using bismuth oxide or bismuth subcarbonate as a bismuth source
  • US Pat. No. 4,803,190 describes a method of forming bismuth compounds in advance. Adjusting a slurry containing at least one selected from the group consisting of: bismuth and tellurium and a molybdenum compound to a pH range above pH 7, US Pat.
  • Japanese Patent No. 5,071,814 discloses a method in which a chelating agent is added to a slurry containing molybdenum compound containing silicide to adjust ⁇ 1 to 1 ⁇ 6 or more.
  • the specification discloses a method of mixing a bismuth compound after a slurry containing molybdenum is adjusted to pH 6 or more.
  • Molybdenum, bismuth, iron, nickel, chromium, potassium, and the metal elements represented by F are essential components, and the objects of the present invention cannot be achieved unless each of the above composition ranges.
  • the catalyst composition of the present invention contains iron antimonate, it necessarily contains antimony.
  • the selectivity of the target product is improved, and the physical properties of the catalyst are improved. Advantages are noted.
  • silica is preferably used as a carrier.
  • j is preferably in a range of 20 to 80.
  • the catalyst composition of the present invention may be prepared by appropriately selecting and applying the preparation method disclosed as the above-mentioned prior art.
  • the raw materials for the molybdenum component include dimethyl molybdenum acid and ammonium paramolybdate; the raw materials for the bismuth component include bismuth trioxide, bismuth nitrate, bismuth carbonate, and bismuth oxalate; and the raw material for the iron component include nitric acid. Iron, iron oxalate, and the like, chromium nitrate and chromic acid are used as raw materials for the chromium component, and potassium hydroxide and potassium nitrate are used as the raw material for the potassium component.
  • the raw materials of the zirconium component include zirconium oxide and zirconium oxynitrate; the raw materials of the lanthanum component include lanthanum oxide and lanthanum nitrate; and the raw materials of the cerium component include cerium oxide and cerium ammonium nitrate. Etc. are for Also, organic acid salts of these elements can be used.
  • the respective nitrates as the raw materials for the components such as nickel, cobalt, magnesium, manganese and zinc, but it is also possible to use the respective organic acid salts, hydroxides and oxides.
  • the tellurium component when added, as a raw material of the tellurium component, a material capable of using telluric acid or a salt thereof or tellurous acid or a salt thereof, or a solution obtained by dissolving metallic tellurium in a heated aqueous hydrogen peroxide solution. May be used.
  • oxides, hydroxides, nitrates, organic acid salts, etc. of the respective elements are used as raw materials for other components.
  • silica sol As a raw material of silica, silica sol, fumed silica and the like are used, and silica sol is particularly preferable. As the silica sol, one having a low sodium content is preferably used.
  • the catalyst composition of the present invention is prepared by mixing these raw materials, drying and calcining.
  • the slurry prepared by mixing the raw materials preferably has a pH of 6 or more. This operation reduces the ammonia flammability during the reaction and improves the yield of the target product. In that case, the viscosity of the slurry can be reduced by mixing the chelating agent into the slurry, and the operability can be improved.
  • the present catalyst composition was prepared with a pH of 6 or more, it was found that the presence of the chromium component contributed to lowering the viscosity of the slurry. This is an advantage for improving operability, and it is noteworthy.
  • Further heat treatment of the prepared slurry may be advantageous in that the stability of the slurry is increased and the reproducibility is improved.
  • chelating agents examples include ethylenediaminetetraacetic acid, lactic acid, citric acid, tartaric acid, and dalconic acid.
  • the amount of the chelating agent is preferably in the range of 0.1 to 10%, preferably 0.5 to 8% by weight of the oxide catalyst to be produced. More preferably, it is used in the range of / 0 . If the amount of the chelating agent is less than 0.1% by weight with respect to the oxide catalyst, the effect is not sufficiently exhibited, and if the amount exceeds 10% by weight, a large number of cracks may be formed in the completed catalyst.
  • the chelating agent is iron 1 0.1 to 2 gram molecules are preferred for gram ions.
  • iron antimonate When iron antimonate is contained, it is preferable to prepare iron antimonate in advance and then mix it with a raw material of other components such as molybdenum to form a slurry. .
  • a molybdenum raw material and / or a raw material of at least one element selected from the group consisting of nickel, cobalt, magnesium, chromium, manganese and zinc and having a pH of 6 or more are contained.
  • a method is also preferable in which a certain aqueous slurry is mixed with a solution or slurry containing a tellurium raw material and a Z or iron raw material, and then the mixture is dried and fired.
  • a solution or slurry containing a raw material of iron and a solution containing a raw material of tellurium are mixed with the aqueous slurry having a pH of 6 or more, or Also preferred is a method of mixing a mixed solution or slurry containing a raw material and a tellurium raw material with the aqueous slurry having a pH of 6 or more, followed by drying and firing the mixture.
  • metallic iron may be used by dissolving it in heated nitric acid.
  • the solution containing the iron component may be used after adjusting the pH with ammonia water or the like.
  • coexistence of a chelating agent in a solution containing an iron component can prevent precipitation of the iron component, and a highly active catalyst can be obtained.
  • chelating agents that can be used here include ethylenediaminetetraacetic acid, lactic acid, citric acid, tartaric acid, and glyconic acid.
  • the drying of the slurry mixture is preferably carried out by a spray drying method in the case of producing a fluidized bed catalyst, and granulation is carried out simultaneously with drying. Thereby, fine spherical particles can be obtained.
  • the mixture is preferably calcined at 200 to 500 ° C, and more preferably calcined at 500 to 700 ° C.
  • the firing time may be 1 to 20 hours.
  • the atmosphere during firing is preferably an oxygen-containing gas.
  • the baking is conveniently performed in the air, but may be performed in an atmosphere in which oxygen and nitrogen, carbon dioxide, water vapor, organic compounds, and the like are appropriately mixed. Box furnaces, tunnel furnaces, rotary furnaces, fluidized furnaces, etc. are used for baking.
  • the final calcination is preferably performed in a fluidized furnace. This makes it easier to strictly control the final firing conditions, and makes it possible to produce fluidized bed catalysts with excellent performance with good reproducibility.
  • the particle size of the fluidized bed catalyst produced in this way is preferably from 10 to 200 ⁇ m.
  • the catalyst composition of the present invention or the catalyst composition produced by the production method of the present invention as described above is suitable for producing unsaturated nitrile by ammoxidation of olefin.
  • the apparent contact time is 0.1 to 20 seconds.
  • the reaction pressure was 20 ° kPa.
  • Atarilonitrile yield (%) number of moles of acrylonitrile produced Number of moles of propylene supplied / number of moles X 100
  • Acrylonitrile selectivity (%) number of moles of atarilonitrile produced, number of moles of propylene reacted x 100
  • Propylene conversion (%) number of moles of propylene reacted / propylene supplied Number of monoles of X 100
  • Ammonia combustion rate (%) 100- [(weight of nitrogen in product + weight of nitrogen in unreacted ammonia) Z weight of nitrogen in supplied ammonia X loo]
  • a catalyst having a K of 0.7 P 0.2 T e 0.25 ° 53.7 ⁇ i ° 2) 40 (atomic ratio) was prepared.
  • the above mixture was spray-dried with a rotating disk spray dryer at an inlet temperature of 330 ° C and an outlet temperature of 160 ° C.
  • the particles were heat-treated at 250 ° C. for 2 hours and 400 ° C. for 2 hours, and finally fluidized at 590 ° C. for 3 hours.
  • Example 11 A catalyst having the same composition as in Example 1 was prepared by the following method.
  • This slurry was adjusted to pH 7.7 by adding 15% aqueous ammonia with stirring, and then heat-treated at 100 ° C. for 1.5 hours under reflux.
  • To 208 g of water were added 4.65 g of metal tellurium, 3.9 g of ammonium paramolybdate, and 16 g of hydrogen peroxide solution, and the mixture was stirred at 95 to 100 ° C. and dissolved.
  • the solution was cooled to room temperature, and 20 g of citric acid and 35.33 g of iron nitrate were dissolved. While stirring this, 15% aqueous ammonia was added to adjust the pH to 9.2, and 99.1 g of ammonium paramolybdate was added little by little to dissolve.
  • ammonia water was added to adjust the pH to 7. This solution was mixed with the slurry previously heated, and 138.3 g of iron antimonate powder was mixed.
  • the mixture was spray-dried and heat-treated in the same manner as in Example 11-11, and finally fluidized at 580 ° C for 3 hours.
  • Example 1-11 The above mixture was spray-dried and heat-treated in the same manner as in Example 1-11, and finally fluidized-fired at 590 ° C for 3 hours.
  • a catalyst having the same composition as in Example 2-1 was prepared by the following method.
  • Example 1-11 The above mixture was spray-dried and heat-treated in the same manner as in Example 1-11, and finally fluidized-fired at 590 ° C for 3 hours.
  • Example 11-11 The above mixture was spray-dried and heat-treated in the same manner as in Example 11-11, and finally fluidized-fired at 600 ° C for 3 hours.
  • Example 4 1 The composition is Mo! 0 B i 0. 4 F e o . EN i 5. 75 C r 0. 5 Z r 0. 2 K o. 7
  • the catalyst was prepared a 2 T e 0. 25O39. 8 ( S i 0 2) 40 ( atomic ratio). 309.5 g of ammonium paramolybdate was dissolved in 1800 g of pure water, and then 4.04 g of 85% phosphoric acid was added. To this solution was added 293.2 g of nickel nitrate to 250 g of 3.3% nitric acid, 35.08 g of chromium nitrate, 9.37 g of zirconium oxynitrate, 12.41 g of potassium nitrate, and 34.02 of bismuth nitrate g was dissolved and then 2107 g of 20% silica sol was mixed to obtain a slurry.
  • the slurry was adjusted to pH 8 by adding 15% aqueous ammonia while stirring.
  • a solution of 10.1 g of telluric acid and 35.33 g of iron nitrate dissolved in 200 g of pure water was added to the slurry and mixed.
  • the mixture was spray-dried and heat-treated in the same manner as in Example 11-11, and finally fluidized at 580 ° C for 3 hours.
  • Example 4 A catalyst having the same composition as in Example 11 was prepared by the following method.
  • the mixture was spray-dried and heat-treated in the same manner as in Examples 13 to 13, and finally fluidized at 580 ° C for 3 hours.
  • Example 5 Composition Mo 10 B i 0. 4 F e o_ 6 N i 5. 75 C r x. 5 L a 0 _ 2 Mn 0. 2
  • the composition is Mo! 0 B i 1 F e 4. 5 S b 4 N i 6 C r 0. 5 zr o. I zn o. 2 b o. O 5 K 0. 6 P 0. 5 B 0. 3 T e 0. 25
  • a catalyst having a temperature of 56.0 (Si 2 ) 40 (atomic ratio) was prepared according to the method of Example 6.
  • composition is Mo! 0 B i! F e 4. 5 S b 4 N i 5. 5 C r 0. 5 L a 0. l ⁇ g 0. 5
  • Example 1 - were prepared in accordance with the second method. However, no zirconium component was added.
  • a catalyst having a ratio of 0 (S 10 2 ) 40 (atomic ratio) was prepared according to the method of Example 12-12. However, no kumumu component was added.
  • a catalyst having a ratio of P 0.2 T e 0.25 455.4 (S i ⁇ 2 ) 40 (atomic ratio) was prepared according to the method of Example 1-2.
  • the catalyst of the present invention can provide a high acrylonitrile yield in the production of atarilonitrile by ammoxidation of olefin, in particular, ammoxidation of propylene, and can suppress the flammability of ammonia.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne une composition de catalyseur représenté par la formule expérimentale suivante: Mo10BiaFebSbcNidCreFfGgHhKkXxYyOi(SiO2)j, laquelle est destinée à être utilisée dans la production d'un nitrile insaturé par ammoxydation, formule dans laquelle F représente au moins un élément choisi dans le groupe comprenant le zirconium, le lanthane et le cérium; G représente au moins un élément choisi dans le groupe comprenant le magnésium, le cobalt, le manganèse et le zinc; H représente au moins un élément sélectionné dans le groupe comprenant le vanadium, le niobium, le tantale et le tungstène; X représente au moins un élément choisi dans le groupe comprenant le phosphore, le bore et le tellure; Y représente au moins un élément choisi dans le groupe comprenant le lithium, le sodium, le rubidium et le césium; et les indices a à k, x, et y, lesquels représentent des proportions des atomes et le groupe d'atomes, représentent des nombres tels que a=0,1 à 3, b=0,3 à 15, c=0 à 20, d=3 à 8, e=0,2 à 2, f=0,05 à 1, e/f⊃1, g=0 à 5, h=0 à 3, k=0,1 à 1, x=0 à 3, y=0 à 1, i est le nombre d'atomes d'oxygène résultant de la liaison des ingrédients précités, et j=0 à 100.
PCT/JP1999/002146 1998-04-23 1999-04-22 Catalyseur de production de nitrile insature WO1999054037A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
ROA200001018A RO119228B1 (ro) 1998-04-23 1999-04-22 Catalizator şi procedeu pentru obţinerea nitrililor nesaturaţi
EP99917105A EP1075871B1 (fr) 1998-04-23 1999-04-22 Catalyseur de production de nitrile insature
US09/673,571 US6479691B1 (en) 1998-04-23 1999-04-22 Catalyst for producing unsaturated nitrile
DE69920437T DE69920437T2 (de) 1998-04-23 1999-04-22 Katalysator zur herstellung von ungesättigten nitrilen

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP10128098 1998-04-23
JP10/128098 1998-04-23
JP15538898 1998-05-21
JP10/155388 1998-05-21
JP10/159987 1998-05-26
JP15998798 1998-05-26

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WO1999054037A1 true WO1999054037A1 (fr) 1999-10-28

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001028984A1 (fr) * 1999-10-18 2001-04-26 Mitsubishi Rayon Co., Ltd. Procede de production d'acrylonitrile, catalyseur utilise et procede de preparation de celui-ci
WO2001028986A1 (fr) * 1999-10-18 2001-04-26 Mitsubishi Rayon Co., Ltd. Methode de production d'acrylonitrile, catalyseur employe et methode de preparation dudit produit
WO2002013963A3 (fr) * 2000-08-17 2002-05-02 Standard Oil Co Catalyseur ameliore destine a la fabrication d'acrylonitrile
EP1254713A1 (fr) * 1999-07-21 2002-11-06 Mitsubishi Rayon Co., Ltd. Catalyseur d'oxydes metalliques au molybdene-bismuth-fer pour couches fluidisees, son procede de preparation et ses utilisations
WO2004091776A1 (fr) 2003-04-18 2004-10-28 Dia-Nitrix Co., Ltd. Catalyseur pour la synthese d'acrylonitrile
EP1223163A4 (fr) * 1999-10-18 2005-02-23 Mitsubishi Rayon Co Proc d de production d'acrylonitrile, catalyseur utilis et proc d de pr paration de celui-ci
CN1299824C (zh) * 2001-04-13 2007-02-14 大野绿水株式会社 含有钼－铋－铁的复合氧化物流化床催化剂的制造方法

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JPS55139839A (en) * 1979-04-18 1980-11-01 Ube Ind Ltd Catalyst for production of acrylonitrile
JPS5835160A (ja) * 1981-08-25 1983-03-01 Asahi Chem Ind Co Ltd メタクリロニトリルを製造する方法
JPH02214543A (ja) * 1989-02-16 1990-08-27 Nitto Chem Ind Co Ltd 酸化反応に適するモリブデン含有金属酸化物流動層触媒の製法
JPH02251250A (ja) * 1989-03-23 1990-10-09 Nitto Chem Ind Co Ltd モリブデン―ビスマス含有複合酸化物触媒の製法
JPH04118051A (ja) * 1990-09-10 1992-04-20 Nitto Chem Ind Co Ltd 鉄・アンチモン・モリブデン含有酸化物触媒組成物およびその製法
JPH0747272A (ja) * 1993-08-06 1995-02-21 Asahi Chem Ind Co Ltd 不飽和ニトリルの製法

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
JPS55139839A (en) * 1979-04-18 1980-11-01 Ube Ind Ltd Catalyst for production of acrylonitrile
JPS5835160A (ja) * 1981-08-25 1983-03-01 Asahi Chem Ind Co Ltd メタクリロニトリルを製造する方法
JPH02214543A (ja) * 1989-02-16 1990-08-27 Nitto Chem Ind Co Ltd 酸化反応に適するモリブデン含有金属酸化物流動層触媒の製法
JPH02251250A (ja) * 1989-03-23 1990-10-09 Nitto Chem Ind Co Ltd モリブデン―ビスマス含有複合酸化物触媒の製法
JPH04118051A (ja) * 1990-09-10 1992-04-20 Nitto Chem Ind Co Ltd 鉄・アンチモン・モリブデン含有酸化物触媒組成物およびその製法
JPH0747272A (ja) * 1993-08-06 1995-02-21 Asahi Chem Ind Co Ltd 不飽和ニトリルの製法

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1254713A1 (fr) * 1999-07-21 2002-11-06 Mitsubishi Rayon Co., Ltd. Catalyseur d'oxydes metalliques au molybdene-bismuth-fer pour couches fluidisees, son procede de preparation et ses utilisations
US6740769B1 (en) 1999-07-21 2004-05-25 Mitsubishi Rayon Co., Ltd. Molybdenum-bismuth-iron-containing metal oxide catalysts for fluidized layer, method for preparation thereof, and use thereof
EP1254713A4 (fr) * 1999-07-21 2003-08-20 Mitsubishi Rayon Co Catalyseur d'oxydes metalliques au molybdene-bismuth-fer pour couches fluidisees, son procede de preparation et ses utilisations
US6653496B1 (en) 1999-10-18 2003-11-25 Mitsubishi Rayon Co., Ltd. Method for producing acrylonitrile, catalyst for use therein and method for preparing the same
US6642405B1 (en) 1999-10-18 2003-11-04 Mitsubishi Rayon Co., Ltd. Method for producing acrylonitrile, catalyst for use therein and method for preparing the same
WO2001028984A1 (fr) * 1999-10-18 2001-04-26 Mitsubishi Rayon Co., Ltd. Procede de production d'acrylonitrile, catalyseur utilise et procede de preparation de celui-ci
WO2001028986A1 (fr) * 1999-10-18 2001-04-26 Mitsubishi Rayon Co., Ltd. Methode de production d'acrylonitrile, catalyseur employe et methode de preparation dudit produit
EP1223164A4 (fr) * 1999-10-18 2005-02-23 Mitsubishi Rayon Co Methode de production d'acrylonitrile, catalyseur employe et methode de preparation dudit produit
EP1223162A4 (fr) * 1999-10-18 2005-02-23 Mitsubishi Rayon Co Procede de production d'acrylonitrile, catalyseur utilise et procede de preparation de celui-ci
EP1223163A4 (fr) * 1999-10-18 2005-02-23 Mitsubishi Rayon Co Proc d de production d'acrylonitrile, catalyseur utilis et proc d de pr paration de celui-ci
WO2002013963A3 (fr) * 2000-08-17 2002-05-02 Standard Oil Co Catalyseur ameliore destine a la fabrication d'acrylonitrile
CN1299824C (zh) * 2001-04-13 2007-02-14 大野绿水株式会社 含有钼－铋－铁的复合氧化物流化床催化剂的制造方法
WO2004091776A1 (fr) 2003-04-18 2004-10-28 Dia-Nitrix Co., Ltd. Catalyseur pour la synthese d'acrylonitrile

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