JP3995381B2 - Catalyst for producing methacrylic acid and method for producing methacrylic acid - Google Patents

Catalyst for producing methacrylic acid and method for producing methacrylic acid Download PDF

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JP3995381B2
JP3995381B2 JP2000028009A JP2000028009A JP3995381B2 JP 3995381 B2 JP3995381 B2 JP 3995381B2 JP 2000028009 A JP2000028009 A JP 2000028009A JP 2000028009 A JP2000028009 A JP 2000028009A JP 3995381 B2 JP3995381 B2 JP 3995381B2
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liquid
catalyst
solution
methacrylic acid
mixed
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JP2000296336A5 (en
JP2000296336A (en
Inventor
啓幸 内藤
求 大北
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三菱レイヨン株式会社
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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

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen (hereinafter simply referred to as a catalyst for producing methacrylic acid) and a method for producing methacrylic acid.
[0002]
[Prior art]
Of the conventionally known methods for producing a catalyst for producing methacrylic acid, as a method of mixing two or more kinds of mixed solutions containing catalyst component elements, for example, JP-A-4-182450 and JP-A-5-31368 are disclosed. And JP-A-7-185354, JP-A-8-157414, JP-A-8-196908 and the like. In particular, JP-A-5-31368 discloses a catalyst for producing methacrylic acid, in which a liquid containing at least molybdenum, phosphorus and vanadium and a liquid containing an ammonia compound are mixed, and a liquid containing a cesium element is mixed into the obtained mixed liquid. The manufacturing method is described.
[0003]
Japanese Patent Application Laid-Open No. 9-290162 describes a method for adjusting the pH of a raw material solution containing all catalyst raw materials by adding nitric acid or aqueous ammonia.
[0004]
[Problems to be solved by the invention]
However, the methacrylic acid yield of a catalyst produced by using such a conventional catalyst raw material mixing method and pH adjusting method is not necessarily sufficient as an industrial catalyst, and further improvement is desired at present. is there.
[0005]
Therefore, an object of the present invention is to provide a catalyst and a method for producing methacrylic acid, which can produce methacrylic acid in high yield by vapor phase catalytic oxidation of methacrolein with molecular oxygen.
[0006]
[Means for Solving the Problems]
In the present invention, methacrolein is vapor-phase catalytically oxidized with molecular oxygen to produce methacrylic acid.
P a Mo b V c Cu d X e Y f Z g O h (1)
(Wherein P, Mo, V, Cu and O represent phosphorus, molybdenum, vanadium, copper and oxygen, respectively, X represents antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and Represents at least one element selected from the group consisting of boron, and Y represents at least one element selected from the group consisting of iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium and lanthanum Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, a, b, c, d, e, f, g and h represent the atomic ratio of each element. And when b = 12, a = 0.5-3, c = 0.01-3, d = 0.01-2, e = 0-3, f = 0-3 , G = 0.01 to 3 and h is an atomic ratio of oxygen necessary to satisfy the valence of each of the above components)), at least molybdenum, phosphorus And a solution or slurry (liquid A) containing vanadium and a solution or slurry (liquid B) containing an ammonia compound, and a solution or slurry (C) containing Z element in the obtained liquid mixture or mixed slurry (AB liquid mixture). In the catalyst manufactured by the manufacturing method including the step of mixing the liquid), the amount of ammonium root in the liquid A is 1.5 mol or less with respect to 12 mol of molybdenum atoms in the liquid A, and the AB mixed liquid A catalyst for producing methacrylic acid, characterized in that the amount of ammonium radicals in the mixture is 6 to 17 mol per 12 mol of molybdenum atoms in the AB mixture.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The catalyst of the present invention has a composition represented by the formula (1). In order to produce the catalyst of the present invention, it is essential to include the following two steps.
(I) “A solution or slurry containing at least molybdenum, phosphorus and vanadium” referred to as A solution and “solution or slurry containing an ammonia compound” referred to as B solution, and a mixed solution of A solution and B solution as AB mixture Obtaining a slurry;
(II) The process of manufacturing the solution or slurry containing a catalyst precursor by mixing the solution or slurry containing the said Z element called C liquid with AB mixed liquid.
[0008]
In the present invention, the amount of ammonium radicals in the liquid A is 1.5 moles or less, preferably 1 mole or less, with respect to 12 moles of molybdenum atoms in the liquid A. Further, the amount of ammonium radicals in the AB mixed solution is 6 to 17 mol, preferably 7 to 15 mol, with respect to 12 mol of molybdenum atoms in the AB mixed solution.
[0009]
The state of liquid A, liquid B, AB mixed liquid and liquid C is not particularly limited as long as the catalyst raw material is contained in the liquid, and even if the catalyst raw material is completely dissolved in the solvent, part or all of the state May be a slurry suspended in a solvent. Here, water is preferable as the solvent.
[0010]
The solution or slurry containing the catalyst precursor thus obtained is dried and then calcined to obtain a catalyst for producing methacrylic acid.
[0011]
Although the mechanism for improving the catalyst performance by adopting such a production method is not clear, by controlling the mixing order of the catalyst raw materials and the ammonium root in the liquid A and the liquid AB to a specific amount, methacryl It is presumed that a crystal structure capable of obtaining an acid in a high yield is formed.
[0012]
Hereinafter, the method for producing the catalyst of the present invention will be described in more detail.
(Preparation of solution A)
In the liquid A, at least molybdenum, phosphorus and vanadium catalyst raw materials are dissolved or suspended in a solvent, and then this is 80 to 150 ° C., preferably 90 to 130 ° C., and 0.5 to 24 hours, preferably 1 to Prepare by heating and stirring for 12 hours. By setting the heating temperature to 80 to 150 ° C., a catalyst having a high activity in the methacrylic acid production reaction can be obtained. Moreover, reaction of catalyst raw materials can fully be advanced by making heating time 0.5 hours or more.
[0013]
The liquid A is a solution or slurry containing at least molybdenum, phosphorus and vanadium catalyst raw materials, and may contain a catalyst raw material for elements other than the element Z in addition to molybdenum, phosphorus and vanadium.
[0014]
As a catalyst raw material used for manufacturing the liquid A, oxides, nitrates, carbonates, ammonium salts, and the like of each element can be appropriately selected and used. For example, a raw material that does not contain ammonium roots such as molybdenum trioxide and molybdic acid is suitable as a raw material for molybdenum, but various ammonium molybdates such as ammonium paramolybdate, ammonium dimolybdate, and ammonium tetramolybdate are also small. If it can be used, normal phosphoric acid, phosphorus pentoxide, ammonium phosphate, etc. can be used as the phosphorus raw material, and vanadium pentoxide, ammonium metavanadate, etc. can be used as the raw material for vanadium. In addition, heteropolyacids such as phosphomolybdic acid, molybdovanadolinic acid, and ammonium phosphomolybdate can also be used as raw materials for molybdenum, phosphorus, and vanadium.
[0015]
It is important that the amount of the ammonium root in the liquid A is 1.5 mol or less with respect to 12 mol of molybdenum atoms in the liquid, and in order to further increase the yield of methacrylic acid, the amount is 1 mol or less. Is preferred. The amount of the ammonium root in the liquid A can be adjusted by the amount of the catalyst raw material containing the ammonium root.
[0016]
(Preparation of liquid B)
Liquid B is a solution or slurry containing an ammonia compound, and is prepared by dissolving or suspending the ammonia compound in a solvent. The B liquid may contain, in addition to the ammonia compound, a catalyst raw material of an element other than the Z element as long as it is not a total amount, but it is preferable that no component other than the ammonia compound is contained. Here, the ammonia compound is a compound containing ammonium group or ammonia, and examples thereof include aqueous ammonia, ammonium nitrate, ammonium carbonate, and ammonium hydrogen carbonate.
[0017]
The amount of the ammonia compound in the B liquid is such that the amount of ammonium radicals in the AB mixed liquid obtained by mixing the A liquid and the B liquid is 6 to 17 mol with respect to 12 mol of molybdenum atoms in the liquid, preferably The amount is 7-15.
[0018]
(Preparation of liquid C)
The liquid C is a solution or slurry containing the Z element, and is prepared by dissolving or suspending at least a Z element catalyst raw material in a solvent. The liquid C may contain a catalyst raw material of an element other than the Z element, but it is preferable that these are not contained as much as possible. Further, it is preferable that the C liquid contains as little ammonia compound as possible. As the catalyst raw material for the liquid C, nitrates, carbonates, hydroxides, and the like of each element can be appropriately selected and used. For example, cesium nitrate, cesium carbonate, cesium hydroxide, or the like can be used as a cesium raw material.
[0019]
(Preparation of AB mixture)
In the present invention, the A liquid and the B liquid are mixed to obtain an AB mixed liquid. The mixing method of A liquid and B liquid is not specifically limited, For example, the method of adding B liquid to the container containing A liquid, the method of adding A liquid to the container containing B liquid, and the A liquid and B liquid in the container Any method such as a method of pouring at the same time can be used. The obtained AB mixed solution may be appropriately subjected to an operation such as heat aging. In order to obtain a highly active catalyst, the temperatures of the liquid A and the liquid B during mixing are each preferably 70 ° C. or less, and particularly preferably 60 ° C. or less.
[0020]
You may add the catalyst raw material except a Z component to what mixed A liquid and B liquid. As the catalyst raw material to be added in this manner, any catalyst raw material of an element other than the Z element contained in the catalyst composition represented by the formula (1) may be used, and the additional method may be performed by adding the catalyst raw material as it is. It may be added in the form of a solution or suspension.
[0021]
(A mixture of AB mixture and C solution)
In the present invention, the AB mixed solution and the C solution are mixed. The method of mixing the AB liquid mixture and the C liquid is not particularly limited. For example, the method of adding the C liquid to the container containing the AB liquid mixture, the method of adding the AB liquid mixture to the container containing the C liquid, and the AB mixing to the container. Examples thereof include a method of pouring the liquid and the liquid C at the same time.
[0022]
In the present invention, when the AB mixed solution and the C solution are mixed, it is more preferable that the AB mixed solution and copper or the Y element are mixed in advance, and the obtained mixed solution and the C solution are mixed. Here, copper or the Y element is particularly preferably added by dissolving or suspending these catalyst raw materials in a solvent. When adding this copper or said Y element, you may add together the catalyst raw material of elements other than Z element, but it is preferable not to add these at this time as much as possible. Also, it is preferable not to add ammonia compounds as much as possible at this point. As catalyst raw materials for copper and Y elements, nitrates, carbonates, hydroxides, and the like of each element can be appropriately selected and used. For example, copper nitrate, copper oxide, or the like can be used as a raw material for copper. The method of mixing the liquid mixture C obtained by mixing AB liquid mixture and copper or the said Y element, and C liquid is not specifically limited.
The solution or slurry obtained by mixing at least the AB mixed solution and the C solution thus obtained may be appropriately subjected to operations such as heat aging. Although the temperature of both liquids at the time of mixing is not specifically limited, 100 degrees C or less is preferable.
[0023]
(Drying and firing)
When a solution or slurry containing all the catalyst raw materials is obtained in this way, the solution or slurry is dried to obtain a dried catalyst precursor. At this time, various drying methods can be used. For example, an evaporating and drying method, a spray drying method, a drum drying method, an air flow drying method, and the like can be used. The model of the dryer used for drying, the temperature during drying, and the like are not particularly limited, and a dried catalyst precursor according to the purpose can be obtained by appropriately changing the drying conditions.
[0024]
The dried catalyst precursor may be calcined without molding, but usually the molded product is calcined. The molding method is not particularly limited, and various known dry and wet molding methods can be applied, but a method of molding without including a carrier or the like is preferable. Specific examples of the molding method include tableting molding, press molding, extrusion molding, and granulation molding. The shape of the molded product is not particularly limited, and for example, a desired shape such as a columnar shape, a ring shape, or a spherical shape can be selected. In molding, a small amount of known additives such as graphite and talc may be added.
[0025]
The catalyst precursor for methacrylic acid production is obtained by calcining the dried catalyst precursor or the molded product thus obtained. The firing method and firing conditions are not particularly limited, and known treatment methods and conditions can be applied. Optimum conditions for calcination vary depending on the catalyst raw material, catalyst composition, and preparation method to be used, but normal calcination conditions are 200 to 500 ° C., preferably 300 to 300 ° C. under an oxygen-containing gas flow such as air and / or an inert gas flow. It is -450 degreeC and it is 0.5 hour or more, Preferably it is 1 to 40 hours. Here, the inert gas means a gas that does not decrease the reaction activity of the catalyst. Examples of such a gas include nitrogen, carbon dioxide gas, helium, and argon.
[0026]
When producing methacrylic acid using the catalyst thus produced, a raw material gas containing methacrolein and molecular oxygen is brought into contact with the catalyst. The concentration of methacrolein in the raw material gas can be varied within a wide range, but 1 to 20% by volume is appropriate, and 3 to 10% by volume is particularly preferable. The source gas may contain a small amount of impurities such as water and lower saturated aldehyde, but is preferably as small as possible. Although it is economical to use air as the molecular oxygen source, air enriched with pure oxygen can also be used if necessary. The molecular oxygen concentration in the raw material gas is preferably 0.4 to 4 mol, more preferably 0.5 to 3 mol, per 1 mol of methacrolein. The source gas may be diluted by adding an inert gas such as nitrogen or carbon dioxide, and water vapor may be added to the source gas. The reaction pressure of the methacrylic acid production reaction is preferably from normal pressure to several atmospheres. The reaction temperature can be selected in the range of 230 to 450 ° C, and 250 to 400 ° C is particularly preferable.
[0027]
【Example】
EXAMPLES The present invention will be described in further detail with reference to examples and comparative examples below, but the present invention is not limited to these examples. “Parts” in Examples and Comparative Examples means parts by weight. The composition of the catalyst was determined from the raw material charge of the catalyst component. Reaction raw materials and products were analyzed using gas chromatography.
In addition, the reaction rate of methacrolein, the selectivity of the produced methacrylic acid, and the single flow yield of methacrylic acid are defined as follows.
Reaction rate 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 methacrolein supplied, B is the number of moles of reacted methacrolein, and C is the number of moles of methacrylic acid produced.
[0028]
[Example 1]
To 400 parts of pure water, 100 parts of molybdenum trioxide, 7.34 parts of 85% by weight phosphoric acid, 4.74 parts of vanadium pentoxide, 0.92 parts of copper oxide and 0.23 parts of iron oxide are added and refluxed for 5 hours. A liquid A was obtained by stirring. The amount of ammonium root in the liquid A was 0 mol with respect to 12 mol of molybdenum atoms.
After the liquid A was cooled to 50 ° C., 37.4 parts of 29 wt% ammonia water as the liquid B was added dropwise and stirred for 15 minutes to obtain an AB mixed liquid. The amount of ammonium radicals in the AB mixture was 11 moles per 12 moles of molybdenum atoms.
Next, a solution prepared by dissolving 9.03 parts of cesium nitrate as a C liquid in 30 parts of pure water was added dropwise to the AB mixed liquid and stirred for 15 minutes to obtain a slurry.
The slurry thus obtained was heated to 101 ° C., evaporated to dryness with stirring, and the obtained solid was dried at 130 ° C. for 16 hours. This dried product was pressure-molded and calcined at 375 ° C. for 10 hours under air flow to obtain a catalyst having a composition of P 1.1 Mo 12 V 0.9 Cu 0.2 Fe 0.05 Cs 0.8 .
This catalyst was filled in a reaction tube, and a mixed gas of 5% methacrolein, 10% oxygen, 30% water vapor, and 55% (volume%) nitrogen was passed at a reaction temperature of 285 ° C. and a contact time of 3.6 seconds. The results are shown in Table 1.
[0029]
[Example 2]
In Example 1, except that 24 parts of 29% by weight aqueous ammonia was used as the B liquid, and the amount of ammonium radicals in the AB mixed liquid was changed to 6 mol per 12 mol of molybdenum atoms. The results obtained in the same manner as in Table 1 are shown in Table 1.
[0030]
[Example 3]
In Example 1, except that 51 parts of 29% by weight aqueous ammonia was used as the B liquid, and the amount of ammonium radicals in the AB mixed liquid was changed to 15 moles with respect to 12 moles of molybdenum atoms. The results obtained in the same manner as in Table 1 are shown in Table 1.
[0031]
[Comparative Example 5]
In Example 1, except that 13.6 parts of 29% by weight ammonia water was used as the B liquid, and the amount of ammonium radicals in the AB mixed liquid was changed to 4 mol with respect to 12 mol of molybdenum atoms. The results obtained in the same manner as in Example 1 are shown in Table 1.
[0032]
[Comparative Example 6]
In Example 1, except that the amount of ammonium root in the AB mixed solution was changed to 20 mol per 12 mol of molybdenum atoms by using 68 parts of 29% by weight aqueous ammonia as the B solution. The results are shown in Table 1.
[0033]
[Example 6]
Table 1 shows the results obtained in the same manner as in Example 1 except that the dropping temperature of the B liquid was changed to 80 ° C. in Example 1.
[0034]
[Comparative Example 1]
In Example 1, 13.6 parts of 29 wt% ammonia water was added to A liquid, the amount of ammonium root in A liquid was 4 mol with respect to 12 mol of molybdenum atoms, and B liquid was 29 wt% ammonia water. Table 1 shows the results obtained in the same manner as in Example 1 except that the amount of ammonium radicals in the AB mixed solution was changed to 11 mol with respect to 12 mol of molybdenum atoms by using 23.8 parts. .
[0035]
[Comparative Example 2]
In Example 1, the order of mixing the B liquid and the C liquid was reversed, the C liquid was dropped into the A liquid, and the B liquid was dropped into the mixed liquid. The results are shown in Table 1.
[0036]
[Comparative Example 3]
Table 1 shows the results obtained in the same manner as in Example 1 except that the mixture of Liquid B and Liquid C was dropped into Liquid A in Example 1.
[0037]
[Example 7]
100 parts of pure water, 100 parts of molybdenum trioxide, 8.88 parts of 85 wt% phosphoric acid, 4.74 parts of ammonium metavanadate, 1.40 parts of cupric nitrate dissolved in 10 parts of pure water, A solution obtained by dissolving 2.34 parts of iron in 10 parts of pure water, 4.11 parts of 60 wt% arsenic acid aqueous solution and 1.00 parts of cerium oxide, and stirring in an autoclave at 120 ° C. for 3 hours under saturated steam, solution A Got. The amount of the ammonium root in the liquid A was 0.7 mol with respect to 12 mol of molybdenum atoms.
After the liquid A was cooled to 60 ° C., a solution prepared by dissolving 37.0 parts of ammonium carbonate as the liquid B in 80 parts of pure water was added dropwise and stirred for 15 minutes to obtain an AB mixed liquid. The amount of ammonium radicals in the AB mixture was 14 moles per 12 moles of molybdenum atoms. Next, a solution obtained by dissolving 18.0 parts of cesium bicarbonate as C liquid in 30 parts of pure water was added dropwise to the AB mixed liquid and stirred for 15 minutes to obtain a slurry.
The slurry thus obtained was heated to 101 ° C., evaporated to dryness with stirring, and the obtained solid was dried at 130 ° C. for 16 hours. This dried product was pressure-molded, fired at 400 ° C. for 5 hours under nitrogen flow, and further fired at 340 ° C. for 10 hours under air flow to obtain P 1.3 Mo 12 V 0.7 Cu 0.1 Fe 0.1 As 0.3 Ce 0.1 A catalyst having a composition of Cs 1.6 was obtained.
Table 1 shows the results of reaction using this catalyst under the same conditions as in Example 1 except that the reaction temperature was changed to 290 ° C.
[0038]
[Example 8]
To 400 parts of pure water, 100 parts of molybdenum trioxide, 8.88 parts of 85% by weight phosphoric acid, 4.74 parts of ammonium metavanadate, 4.11 parts of 60% by weight aqueous arsenic acid solution are added in an autoclave at 120 ° C. under saturated steam. A liquid A was obtained by stirring for 3 hours. The amount of the ammonium root in the liquid A was 0.7 mol with respect to 12 mol of molybdenum atoms.
After the liquid A was cooled to 60 ° C., a solution prepared by dissolving 37.0 parts of ammonium carbonate as the liquid B in 80 parts of pure water was added dropwise and stirred for 15 minutes to obtain an AB mixed liquid. The amount of ammonium radicals in the AB mixture was 14 moles per 12 moles of molybdenum atoms.
Next, 1.40 parts of cupric nitrate dissolved in 10 parts of pure water, AB solution of 2.34 parts of ferric nitrate dissolved in 10 parts of pure water, and 1.00 parts of cerium oxide were sequentially added to the AB mixed solution. After the addition, a solution obtained by dissolving 18.0 parts of cesium bicarbonate as C liquid in 30 parts of pure water was added dropwise and stirred for 15 minutes to obtain a slurry.
The slurry thus obtained was heated to 101 ° C., evaporated to dryness with stirring, and the obtained solid was dried at 130 ° C. for 16 hours. This dried product was pressure-molded, fired at 400 ° C. for 5 hours under nitrogen flow, and further fired at 340 ° C. for 10 hours under air flow to obtain P 1.3 Mo 12 V 0.7 Cu 0.1 Fe 0.1 As 0.3 Ce 0.1 A catalyst having a composition of Cs 1.6 was obtained.
Table 1 shows the results of reaction using this catalyst under the same conditions as in Example 1 except that the reaction temperature was changed to 290 ° C.
[0039]
[Comparative Example 4]
In Example 7, the results obtained in the same manner as in Example 7 except that the mixing of liquid A, liquid B and liquid C was changed to a method in which liquid A, liquid B and liquid C were simultaneously poured into the container and mixed. It is shown in Table 1.
[0040]
[Table 1]
[0041]
【The invention's effect】
By using the catalyst of the present invention, methacrylic acid can be produced in high yield.

Claims (3)

  1. The following formula (1) used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen
    P a Mo b V c Cu d X e Y f Z g O h (1)
    (Wherein P, Mo, V, Cu and O represent phosphorus, molybdenum, vanadium, copper and oxygen, respectively, X represents antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and Represents at least one element selected from the group consisting of boron, and Y represents at least one element selected from the group consisting of iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium and lanthanum Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, a, b, c, d, e, f, g and h represent the atomic ratio of each element. And when b = 12, a = 0.5-3, c = 0.01-3, d = 0.01-2, e = 0-3, f = 0-3 , G = 0.01 to 3 and h is an atomic ratio of oxygen necessary to satisfy the valence of each of the above components)), at least molybdenum, phosphorus And a solution or slurry (liquid A) containing vanadium and a solution or slurry (liquid B) containing an ammonia compound, and a solution or slurry (C) containing Z element in the obtained liquid mixture or mixed slurry (AB liquid mixture). In the catalyst manufactured by the manufacturing method including the step of mixing the liquid), the amount of ammonium root in the liquid A is 1.5 mol or less with respect to 12 mol of molybdenum atoms in the liquid A, and the AB mixed liquid A catalyst for producing methacrylic acid, characterized in that the amount of ammonium root in the mixture is 6 to 17 mol per 12 mol of molybdenum atoms in the AB mixture.
  2. The catalyst for methacrylic acid production according to claim 1, wherein copper or Y element is mixed in advance with the AB mixed solution before mixing the AB mixed solution and the C solution.
  3. A method for producing methacrylic acid using the catalyst for producing methacrylic acid according to claim 1.
JP2000028009A 1999-02-08 2000-02-04 Catalyst for producing methacrylic acid and method for producing methacrylic acid Expired - Fee Related JP3995381B2 (en)

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WO2004004900A1 (en) * 2002-07-05 2004-01-15 Mitsubishi Rayon Co., Ltd. Process for producing catalysts for the production of methacrylic acid
MY144325A (en) * 2003-02-20 2011-08-29 Nippon Kayaku Kk Catalyst for producing methacrylic acid and preparation method thereof
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
JP4601420B2 (en) * 2004-12-27 2010-12-22 三菱レイヨン株式会社 Method for producing a catalyst for methacrylic acid production
KR100954049B1 (en) * 2007-06-13 2010-04-20 주식회사 엘지화학 Method for preparing heteropoly acid catalyst
JP4895303B2 (en) * 2007-08-24 2012-03-14 三菱レイヨン株式会社 Method for producing catalyst for producing methacrylic acid, catalyst for producing methacrylic acid, and method for producing methacrylic acid
JP5335490B2 (en) * 2009-03-09 2013-11-06 住友化学株式会社 Method for regenerating catalyst for methacrylic acid production and method for producing methacrylic acid

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