JP2004008834A - Method for producing catalyst for use in manufacturing methacrylic acid - Google Patents

Method for producing catalyst for use in manufacturing methacrylic acid Download PDF

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Publication number
JP2004008834A
JP2004008834A JP2002161724A JP2002161724A JP2004008834A JP 2004008834 A JP2004008834 A JP 2004008834A JP 2002161724 A JP2002161724 A JP 2002161724A JP 2002161724 A JP2002161724 A JP 2002161724A JP 2004008834 A JP2004008834 A JP 2004008834A
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Japan
Prior art keywords
catalyst
methacrylic acid
molybdenum
producing
methacrolein
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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.)
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JP2002161724A
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Japanese (ja)
Inventor
Takashi Karasuda
Toru Kuroda
Hiroyuki Naito
Ko Ninomiya
二宮 航
内藤 啓幸
烏田 隆志
黒田 徹
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Mitsubishi Rayon Co Ltd
三菱レイヨン株式会社
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Priority to JP2002161724A priority Critical patent/JP2004008834A/en
Publication of JP2004008834A publication Critical patent/JP2004008834A/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention provides a catalyst capable of producing methacrylic acid in high yield by gas phase catalytic oxidation of methacrolein with molecular oxygen, a method for producing the same, and a method for producing methacrylic acid using the catalyst.
A method for producing a molybdenum-containing catalyst having a specific composition containing molybdenum, phosphorus, vanadium, copper, and the like, which is used in producing methacrylic acid by gas phase catalytic oxidation of methacrolein with molecular oxygen,
As a raw material of the molybdenum-containing catalyst, 2θ = 12.7 ± 0.20 °, 2θ = 23.3 ± 0.20 °, 2θ = 25.7 ± 0 in an X-ray diffraction diagram using CuKα ray as the X-ray. .20 °, 2θ = 27.3 ± 0.20 °, and 2θ = 12.7 ± 0.2 when the intensity of the diffraction peak at 2θ = 27.3 ± 0.20 ° is 100. Use molybdenum oxides having relative intensity ratios of 20 °, 2θ = 23.3 ± 0.20 °, 2θ = 25.7 ± 0.20 ° of 20 to 80, 40 to 90, and 25 to 80, respectively. A method for producing a catalyst for producing methacrylic acid, comprising:
[Selection diagram] None

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a method for producing a catalyst used for producing methacrylic acid by gas phase catalytic oxidation of methacrolein with molecular oxygen (hereinafter referred to as a catalyst for producing methacrylic acid), a catalyst produced by this method, And a method for producing methacrylic acid using the catalyst.
[0002]
[Prior art]
As a catalyst for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein with molecular oxygen, a heteropolyacid catalyst containing phosphorus and molybdenum as main components has been conventionally known. Various molybdenum compounds such as ammonium molybdate, molybdenum trioxide, and phosphomolybdic acid are used.
[0003]
JP-A-57-177347, JP-A-58-74142, JP-A-8-47643 and JP-A-8-196908 describe examples in which molybdenum trioxide is used as a molybdenum raw material. I have.
[0004]
[Problems to be solved by the invention]
However, none of the catalysts proposed so far has sufficient reaction results, and further improvement has been desired as an industrial catalyst.
[0005]
An object of the present invention is to provide a catalyst capable of producing methacrylic acid in a high yield by subjecting methacrolein to gas-phase catalytic oxidation with molecular oxygen, a method for producing the same, and a method for producing methacrylic acid using the catalyst. I do.
[0006]
[Means for Solving the Problems]
The present invention provides a method for producing a molybdenum-containing catalyst having a composition represented by the following formula (1), which is used in producing methacrylic acid by subjecting methacrolein to gas-phase catalytic oxidation with molecular oxygen:
As a raw material of the molybdenum-containing catalyst, 2θ = 12.7 ± 0.20 °, 2θ = 23.3 ± 0.20 °, 2θ = 25.7 ± 0 in an X-ray diffraction diagram using CuKα ray as the X-ray. .20 °, 2θ = 27.3 ± 0.20 °, and 2θ = 12.7 ± 0.2 when the intensity of the diffraction peak at 2θ = 27.3 ± 0.20 ° is 100. Use molybdenum oxides having relative intensity ratios of 20 °, 2θ = 23.3 ± 0.20 °, 2θ = 25.7 ± 0.20 ° of 20 to 80, 40 to 90, and 25 to 80, respectively. A method for producing a catalyst for producing methacrylic acid, characterized in that:
P a Mo b V c Cu d X e Y f O g (1)
(Where P, Mo, V, Cu, and O represent phosphorus, molybdenum, vanadium, copper, and oxygen, respectively, and X represents antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, and tungsten. , Boron, iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium, and at least one element selected from the group consisting of lanthanum, Y is potassium, rubidium, cesium, thallium At least one element selected from the group consisting of: when b = 12, a = 0.5-3, c = 0.01-3, d = 0.01-2, e is 0-3, f = 0.01 to 3 and g is the atomic ratio of oxygen necessary to satisfy the valence of each element.)
[0007]
Further, the present invention is a catalyst for producing methacrylic acid produced by the above-mentioned method, and a method for producing methacrylic acid in which gas phase catalytic oxidation of methacrolein with molecular oxygen in the presence of the catalyst for producing methacrylic acid.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
In the method for producing a catalyst for producing methacrylic acid of the present invention, the produced catalyst is a molybdenum-containing catalyst having a composition represented by the above formula (1). A feature of the present invention resides in that a specific molybdenum oxide is used as a raw material of the catalyst. That is, the specific molybdenum oxide means 2θ = 12.7 ± 0.20 °, 2θ = 23.3 ± 0.20 °, 2θ = 25.7 in the X-ray diffraction diagram using CuKα ray as the X-ray. It has a diffraction peak at ± 0.20 °, 2θ = 27.3 ± 0.20 °, and 2θ = 12.7 ± when the intensity of the diffraction peak at 2θ = 27.3 ± 0.20 ° is 100. Molybdenum oxides whose relative intensity ratios of 0.20 °, 2θ = 23.3 ± 0.20 °, 2θ = 25.7 ± 0.20 ° are 20-80, 40-90, 25-80, respectively ( Hereinafter, it is referred to as a specific molybdenum oxide.)
[0009]
Although the atomic ratio of molybdenum to oxygen of such a specific molybdenum oxide is not particularly limited, the molybdenum trioxide having an atomic ratio of molybdenum: oxygen of about 1: 3, which shows the X-ray diffraction pattern described above, may be used. preferable. Strictly, molybdenum trioxide refers to one having an atomic ratio of molybdenum: oxygen of 1: 3, but in the present specification, the oxidation state is slightly different from the oxidation side or the reduction side to 1: 2.85 to 1: 3. The molybdenum oxide of 15 is also called molybdenum trioxide.
[0010]
In addition, the specific molybdenum oxide, for example, sodium, potassium, iron, lead, sulfate, nitrate, ammonium traces may contain a small amount of impurities, but these impurities are preferably as small as possible, It is particularly preferred that they are not included.
[0011]
The method for measuring the X-ray diffraction angle (2θ) of a specific molybdenum oxide is as follows. That is, using a rotor flex RU-200 manufactured by Rigaku Corporation under the conditions of X-ray CuKα ray (λ = 0.154 nm), output 40 kV, 100 mA, measurement range 5 to 70 °, and measurement speed 4 ° per minute. The line diffraction angle (2θ) is measured.
[0012]
Such a specific molybdenum oxide includes, for example, ammonium molybdate having a ratio of molybdenum atom to ammonium of 1: 0.6 to 1: 1.5, preferably 1: 0.7 to 1: 1.2. It can be produced by a method of decomposing by heating at a high temperature or oxidizing metal molybdenum in a solution, followed by drying and firing at a high temperature. The molybdenum oxide produced by this method is molybdenum trioxide.
[0013]
The average particle diameter of the primary particles of the specific molybdenum oxide according to the median diameter is not particularly limited, but is preferably in the range of 0.1 to 10 μm, and more preferably in the range of 0.2 to 8 μm. The particle size distribution of the primary particles of the specific molybdenum oxide according to the median diameter is preferably in the range of 0.01 to 500 μm, and more preferably in the range of 0.05 to 100 μm. The method of adjusting the particle size distribution is not particularly limited.For example, when producing molybdenum trioxide by a method of decomposing ammonium molybdate by heating at a high temperature, adjusting the particle size distribution by adjusting the heating temperature of ammonium molybdate. Can be. When molybdenum trioxide is produced by oxidizing metal molybdenum in a solution, followed by drying and firing at a high temperature, the conditions of the oxidizing treatment and the drying and firing conditions of the molybdenum oxide precursor produced by oxidation are adjusted. By doing so, the particle size distribution can be adjusted.
[0014]
As a catalyst raw material to be used other than the specific molybdenum oxide, nitrate, carbonate, acetate, ammonium salt, oxide salt, halide and the like of each element can be used in combination. For example, vanadium raw materials include ammonium metavanadate, vanadium pentoxide, vanadium chloride, vanadyl oxalate, etc., and phosphorus raw materials include orthophosphoric acid, metaphosphoric acid, diphosphorus pentoxide, pyrophosphoric acid, ammonium phosphate, and the like. The copper raw materials include copper nitrate, copper sulfate, cuprous chloride, cupric chloride and the like. Further, a molybdenum material other than the above-mentioned specific molybdenum oxide may be used in combination as a catalyst material, but the smaller the amount, the more preferable.
[0015]
In the method for producing a catalyst for producing methacrylic acid of the present invention, the production procedure and production conditions are not particularly limited, and the catalyst can be produced by various methods such as a conventionally well-known precipitation method and an oxide mixing method. it can.
[0016]
As a preferable procedure for the production of the catalyst, for example, a method in which a specific molybdenum oxide is suspended in water, mixed with other catalyst raw materials, the obtained mixed solution or aqueous slurry is dried, and a heat treatment is performed. The other catalyst raw materials can be used as they are or appropriately dissolved or suspended in a liquid medium such as water. Ammonia water may be added during or after the mixing of the catalyst raw materials.
[0017]
Next, the solution or slurry containing all the catalyst raw materials thus obtained is dried to obtain a dried catalyst precursor. Various methods can be used as the drying method, and for example, an evaporation to dryness method, a spray drying method, a drum drying method, a flash drying method and the like can be used. There is no particular limitation on the type of dryer used for drying, the temperature and time for drying, and the like, and a dried catalyst precursor suitable for the purpose can be obtained by appropriately changing the drying conditions.
[0018]
The dried product of the catalyst precursor thus obtained may be pulverized as necessary, and then subjected to the subsequent calcination without molding, but the molded product is usually baked. The molding method is not particularly limited, and various known dry and wet molding methods can be applied, but it is preferable that the molding is performed without including a carrier such as silica. Specific molding methods include, for example, tablet molding, press molding, extrusion molding, and granulation molding. The shape of the molded product is not particularly limited, either. For example, a desired shape such as a columnar shape, a ring shape, and a spherical shape can be selected. At the time of molding, known additives such as graphite and talc may be added in small amounts.
[0019]
Then, the dried product of the catalyst precursor thus obtained or the molded product thereof is calcined to obtain a catalyst for producing methacrylic acid. The firing method and firing conditions are not particularly limited, and known processing methods and conditions can be applied. The optimum conditions for the calcination vary depending on the catalyst raw material used, the catalyst composition, the preparation method and the like, but are usually 200 to 500 ° C., preferably 300 to 450 ° C. under a flow of an oxygen-containing gas such as air or a flow of an inert gas. , 0.5 hours or more, preferably 1 to 40 hours. Here, the inert gas refers to a gas that does not decrease the reaction activity of the catalyst, and specific examples include nitrogen, carbon dioxide, helium, and argon.
[0020]
The mechanism by which the catalyst performance is improved by using a specific molybdenum oxide as a raw material is not clear, but there are certain molybdenum oxides formed in the catalyst due to a certain crystal structure of the specific molybdenum oxide. It is presumed that the seed crystal structure contributes to producing methacrylic acid in high yield.
[0021]
Next, the method for producing methacrylic acid of the present invention will be described. In the method for producing methacrylic acid of the present invention, methacrylic acid is produced by gas phase catalytic oxidation of methacrolein with molecular oxygen in the presence of the catalyst of the present invention obtained as described above.
[0022]
The reaction is usually performed in a fixed bed. The catalyst layer may be a single layer or two or more layers, and may be one supported on a carrier or a mixture of other additive components.
[0023]
When producing methacrylic acid using the catalyst of the present invention as described above, a raw material gas containing methacrolein and molecular oxygen is brought into contact with the catalyst. The methacrolein concentration in the raw material gas can be changed in a wide range, but usually 1 to 20% by volume is appropriate, and 3 to 10% by volume is more preferable. Although it is economical to use air as the molecular oxygen source, air or the like enriched with pure oxygen can be used if necessary. Usually, the molecular oxygen concentration in the raw material gas is suitably from 0.4 to 4 mol, more preferably from 0.5 to 3 mol, per mol of methacrolein. The source gas may be one obtained by diluting methacrolein and a molecular oxygen source with an inert gas such as nitrogen or carbon dioxide. Further, steam may be added to the source gas. When the reaction is carried out in the presence of water, methacrylic acid can be obtained in higher yield. The concentration of water vapor in the source gas is preferably from 0.1 to 50% by volume, more preferably from 1 to 40% by volume.
[0024]
The source gas may contain a small amount of impurities such as a lower saturated aldehyde, but the amount is preferably as small as possible.
[0025]
The reaction pressure for the methacrylic acid production reaction is used up to 100 to 200 kPa (absolute pressure). The reaction temperature can be usually selected in the range of 230 to 450 ° C, but more preferably 250 to 400 ° C.
[0026]
The flow rate of the source gas is not particularly limited, but usually, the contact time is preferably 1.5 to 15 seconds, more preferably 2 to 5 seconds.
[0027]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the examples and comparative examples, "parts" is parts by mass.
[0028]
X-ray diffraction measurement was performed with the following apparatus and conditions.
Equipment used: Rotorflex RU-200 (Rigaku Corporation)
X-ray: CuKα ray (λ = 0.154 nm)
Output: 40kV, 100mA
Measuring range: 5-70 °
Measuring speed: 4 ° per minute
[0029]
The particle size distribution was measured using a laser diffraction particle size distribution analyzer SALD-2000 (manufactured by Shimadzu) by a wet method using pure water as a dispersion medium. Here, the average particle diameter to be determined is a particle diameter when the relative particle amount is 50%, that is, a median diameter.
The analysis of the raw material gas and the product was performed using gas chromatography. The conversion of methacrolein, the selectivity of methacrylic acid to be produced, and the single-stream yield are defined as follows.
Conversion of methacrolein (%) = (B / A) × 100
Methacrylic acid selectivity (%) = (C / B) × 100
Single-stream yield of methacrylic acid (%) = (C / A) × 100
Here, A is the number of moles of supplied methacrolein, B is the number of moles of reacted methacrolein, and C is the number of moles of methacrylic acid generated.
[0030]
[Example 1]
In 400 parts of pure water, 100 parts of molybdenum trioxide having the X-ray diffraction pattern and the average particle size shown in Table 1 were suspended, and while stirring, 4.34 parts of vanadium pentoxide and 85% by mass of phosphoric acid were added. 0 parts, 2.80 parts of copper nitrate and 7.02 parts of ferric nitrate were added, and the mixture was stirred under reflux for 1.5 hours to obtain a liquid A. After the solution A was cooled to 50 ° C., 37.3 parts of 29% by weight aqueous ammonia as the solution B was added dropwise and stirred for 15 minutes to obtain an AB mixed solution. Next, a solution obtained by dissolving 9.03 parts of cesium nitrate, which is the C liquid, in 30 parts of pure water was dropped into the AB mixture and stirred for 15 minutes to obtain a slurry. The slurry thus obtained was heated to 101 ° C. and evaporated to dryness with stirring, and the obtained solid was dried at 130 ° C. for 16 hours. The dried product was pressurized with a press molding machine, crushed, sized to 10 to 20 mesh, and calcined at 375 ° C. for 10 hours under air flow to obtain a catalyst. The element composition of this catalyst other than oxygen was P 1.5 Mo 12 V 0.5 Cu 0.2 Fe 0.3 Cs 0.8 .
[0031]
This catalyst was charged into a stainless steel reaction tube, and a reaction gas consisting of 5% methacrolein, 10% oxygen, 30% steam, and 55% (volume%) nitrogen was reacted at a reaction temperature of 285 ° C., a reaction pressure of 101 kPa (absolute pressure), A methacrolein gas phase catalytic oxidation reaction was carried out for a contact time of 3.6 seconds. The results are shown in Table 2.
[0032]
[Examples 2 to 5]
A catalyst was produced in the same manner as in Example 1 except that the molybdenum oxide (molybdenum trioxide) used as a catalyst raw material in Example 1 was changed to that shown in Table 1, and a methacrolein gas phase was prepared using the catalyst. Table 2 shows the results of the catalytic oxidation reaction.
[0033]
[Comparative Example 1]
A catalyst was produced in the same manner as in Example 1 except that the molybdenum oxide (molybdenum trioxide) used as a catalyst raw material in Example 1 was changed to that shown in Table 1, and a methacrolein gas phase was prepared using the catalyst. Table 2 shows the results of the catalytic oxidation reaction.
[0034]
[Example 6]
In 400 parts of pure water, 100 parts of molybdenum trioxide having the X-ray diffraction pattern and the average particle size shown in Table 1 were suspended, and while stirring, 3.39 parts of ammonium metavanadate and 85% by mass of phosphoric acid 6. 67 parts, 6.85 parts of a 60% arsenic acid aqueous solution, 2.80 parts of copper nitrate, and 5.03 parts of cerium nitrate were added, and the mixture was stirred under reflux for 1.5 hours to obtain a liquid A. After the solution A was cooled to 50 ° C., a solution obtained by dissolving 11.3 parts of cesium nitrate as the solution B in 30 parts of pure water was added dropwise and stirred for 15 minutes to obtain an AB mixed solution. Next, a solution obtained by dissolving 13.9 parts of ammonium nitrate, which is the C liquid, in 50 parts of pure water was added to the AB mixture, and the mixture was stirred for 15 minutes to obtain a slurry. The slurry thus obtained was heated to 101 ° C. and evaporated to dryness with stirring, and the obtained solid was dried at 130 ° C. for 16 hours. The dried product was pressurized with a press molding machine, crushed, sized to 10 to 20 mesh, and calcined at 375 ° C. for 10 hours under air flow to obtain a catalyst. The elemental composition of this catalyst other than oxygen was P 1.0 Mo 12 V 0.5 Cu 0.2 As 0.5 Ce 0.2 Cs 1.0 .
[0035]
This catalyst was charged into a stainless steel reaction tube, and a reaction gas consisting of 5% methacrolein, 10% oxygen, 30% steam, and 55% (volume%) nitrogen was reacted at a reaction temperature of 285 ° C., a reaction pressure of 101 kPa (absolute pressure), A methacrolein gas phase catalytic oxidation reaction was carried out for a contact time of 3.6 seconds. The results are shown in Table 2.
[0036]
[Example 7]
A catalyst was produced in the same manner as in Example 6 except that the molybdenum oxide (molybdenum trioxide) used in Example 2 was used, and methacrolein gas-phase catalytic oxidation reaction was performed using the catalyst. It was shown to.
[0037]
[Comparative Example 2]
A catalyst was produced in the same manner as in Example 6 except that the molybdenum oxide (molybdenum trioxide) used in Comparative Example 1 was used, and a methacrolein gas-phase catalytic oxidation reaction was performed using the catalyst. It was shown to.
[0038]
[Table 1]
[0039]
[Table 2]
[0040]
【The invention's effect】
By using the catalyst of the present invention, methacrylic acid can be produced in high yield.

Claims (3)

  1. A method for producing a molybdenum-containing catalyst having a composition represented by the following formula (1), which is used when producing methacrylic acid by gas phase catalytic oxidation of methacrolein with molecular oxygen,
    As a raw material of the molybdenum-containing catalyst, 2θ = 12.7 ± 0.20 °, 2θ = 23.3 ± 0.20 °, 2θ = 25.7 ± 0 in an X-ray diffraction diagram using CuKα ray as the X-ray. .20 °, 2θ = 27.3 ± 0.20 °, and 2θ = 12.7 ± 0.2 when the intensity of the diffraction peak at 2θ = 27.3 ± 0.20 ° is 100. Use molybdenum oxides having relative intensity ratios of 20 °, 2θ = 23.3 ± 0.20 °, 2θ = 25.7 ± 0.20 ° of 20 to 80, 40 to 90, and 25 to 80, respectively. A method for producing a catalyst for producing methacrylic acid, comprising:
    P a Mo b V c Cu d X e Y f O g (1)
    (Where P, Mo, V, Cu, and O represent phosphorus, molybdenum, vanadium, copper, and oxygen, respectively, and X represents antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, and tungsten. , Boron, iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium, and at least one element selected from the group consisting of lanthanum, Y is potassium, rubidium, cesium, thallium At least one element selected from the group consisting of: when b = 12, a = 0.5-3, c = 0.01-3, d = 0.01-2, e is 0-3, f = 0.01 to 3 and g is the atomic ratio of oxygen necessary to satisfy the valence of each element.)
  2. A catalyst for producing methacrylic acid produced by the method according to claim 1.
  3. A method for producing methacrylic acid, comprising subjecting methacrolein to gas-phase catalytic oxidation with molecular oxygen in the presence of the catalyst for producing methacrylic acid according to claim 2.
JP2002161724A 2002-06-03 2002-06-03 Method for producing catalyst for use in manufacturing methacrylic acid Pending JP2004008834A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005039760A1 (en) * 2003-10-27 2005-05-06 Mitsubishi Rayon Co., Ltd. Process for producing catalyst for methacrylic acid production, catalyst for methacrylic acid production, and process for producing methacrylic acid
JP2007229561A (en) * 2006-02-28 2007-09-13 Mitsubishi Rayon Co Ltd Molybdenum oxide, catalyst, method for manufacturing the catalyst and method for producing (meth)acrylic acid or the like
JP2008528452A (en) * 2005-01-20 2008-07-31 ポリメーリ エウローパ ソシエタ ペル アチオニPolimeri Europa S.P.A. Method for producing phenol
JP2009050770A (en) * 2007-08-24 2009-03-12 Mitsubishi Rayon Co Ltd Method for manufacturing catalyst for producing methacrylic acid and catalyst and method for producing methacrylic acid
JP2009101251A (en) * 2007-10-19 2009-05-14 Mitsubishi Rayon Co Ltd Catalyst for producing methacrylic acid, method of manufacturing the same, and method of manufacturing methacrylic acid
WO2010013749A1 (en) * 2008-07-29 2010-02-04 三菱レイヨン株式会社 Catalyst for methacrylic acid production, process for producing same, and process for producing methacrylic acid
KR20200069340A (en) 2017-10-20 2020-06-16 미쯔비시 케미컬 주식회사 Method for preparing catalyst for production of α,β-unsaturated carboxylic acid, method for producing α,β-unsaturated carboxylic acid, and method for producing α,β-unsaturated carboxylic acid ester

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005039760A1 (en) * 2003-10-27 2005-05-06 Mitsubishi Rayon Co., Ltd. Process for producing catalyst for methacrylic acid production, catalyst for methacrylic acid production, and process for producing methacrylic acid
JP4922614B2 (en) * 2003-10-27 2012-04-25 三菱レイヨン株式会社 Method for producing a catalyst for methacrylic acid production
US7662742B2 (en) 2003-10-27 2010-02-16 Mitsubishi Rayon Co., Ltd. Process for producing catalyst for methacrylic acid production, catalyst for methacrylic acid production, and process for producing methacrylic acid
JP2008528452A (en) * 2005-01-20 2008-07-31 ポリメーリ エウローパ ソシエタ ペル アチオニPolimeri Europa S.P.A. Method for producing phenol
JP2007229561A (en) * 2006-02-28 2007-09-13 Mitsubishi Rayon Co Ltd Molybdenum oxide, catalyst, method for manufacturing the catalyst and method for producing (meth)acrylic acid or the like
JP2009050770A (en) * 2007-08-24 2009-03-12 Mitsubishi Rayon Co Ltd Method for manufacturing catalyst for producing methacrylic acid and catalyst and method for producing methacrylic acid
JP2009101251A (en) * 2007-10-19 2009-05-14 Mitsubishi Rayon Co Ltd Catalyst for producing methacrylic acid, method of manufacturing the same, and method of manufacturing methacrylic acid
WO2010013749A1 (en) * 2008-07-29 2010-02-04 三菱レイヨン株式会社 Catalyst for methacrylic acid production, process for producing same, and process for producing methacrylic acid
JP5659490B2 (en) * 2008-07-29 2015-01-28 三菱レイヨン株式会社 Method for producing catalyst for producing methacrylic acid, and method for producing methacrylic acid
KR20200069340A (en) 2017-10-20 2020-06-16 미쯔비시 케미컬 주식회사 Method for preparing catalyst for production of α,β-unsaturated carboxylic acid, method for producing α,β-unsaturated carboxylic acid, and method for producing α,β-unsaturated carboxylic acid ester

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