JP2000296336A - Catalyst for production of methacrylic acid and production of methacrylic acid - Google Patents

Catalyst for production of methacrylic acid and production of methacrylic acid

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Publication number
JP2000296336A
JP2000296336A JP2000028009A JP2000028009A JP2000296336A JP 2000296336 A JP2000296336 A JP 2000296336A JP 2000028009 A JP2000028009 A JP 2000028009A JP 2000028009 A JP2000028009 A JP 2000028009A JP 2000296336 A JP2000296336 A JP 2000296336A
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Prior art keywords
solution
catalyst
methacrylic acid
liquid
amount
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JP2000296336A5 (en
JP3995381B2 (en
Inventor
Hiroyuki Naito
Motomu Okita
啓幸 内藤
求 大北
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Mitsubishi Rayon Co Ltd
三菱レイヨン株式会社
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Priority to JP11-30307 priority
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Priority to JP2000028009A priority patent/JP3995381B2/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

PROBLEM TO BE SOLVED: To oxidize methacrolein by vapor phase catalytic oxidation with molecular oxygen and to produce methacrylic acid in a high yield by using a catalyst produced while specifying the amount of ammonium radicals in one solution in a specified mixed solution and the amount of ammonium radicals in the mixed solution. SOLUTION: The catalyst used in the production of methacrylic acid by the vapor phase catalytic oxidation of methacrolein with molecular oxygen has a composition of the formula PaMobVcCudXeYfZgOh and is produced by mixing a solution (A) containing at least molybdenum, phosphorus and vanadium with a solution (B) containing an ammonia compound and further mixing the resulting mixed solution (AB) with a solution (C) containing the element Z. The amount of ammonium radicals in the solution A is <=1.5 mol based 12 mol molybdenum atoms in the solution A and the amount of ammonium radicals in the solution AB is 6-17 mols based 12 mol molybdenum atoms in the solution AB.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for producing methacrylic acid by gas 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. About.

[0002]

2. Description of the Related Art Among the conventionally known methods for producing a catalyst for producing methacrylic acid, a method for mixing two or more mixed solutions containing a catalyst component element is disclosed in, for example, Japanese Patent Application Laid-Open No.
No. 82450, JP-A-5-31368, 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 with the obtained mixed liquid. Is described.

[0003] Japanese Patent Application Laid-Open No. 9-290162 discloses that
A method is described in which the pH of a raw material solution containing all the raw materials for a catalyst is adjusted by adding nitric acid or aqueous ammonia.

[0004]

However, the methacrylic acid yield of a catalyst produced by using such a conventional method for mixing catalyst raw materials or a method for adjusting pH is not always sufficient as an industrial catalyst, and is further improved. It is the present situation that is desired.

Accordingly, an object of the present invention is to provide a catalyst capable of producing methacrylic acid in a high yield by gas phase catalytic oxidation of methacrolein with molecular oxygen and a method for producing methacrylic acid.

[0006]

The present invention SUMMARY OF] is represented by the following formula is used in producing methacrylic acid by vapor phase catalytic oxidation of methacrolein with molecular oxygen (1) P a Mo b V c Cu d X e Y f Z g O h (1) ( wherein, P, Mo, V, Cu and O, each represent phosphorus, molybdenum, vanadium, copper and oxygen, X
Represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron, and Y represents iron, zinc, chromium, magnesium, tantalum, cobalt , Manganese, barium, gallium, cerium, and lanthanum, and 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 to 3, f = 0 to 3, g = 0.01 to 3, and h is the atomic ratio of oxygen necessary to satisfy the valence of each component. And a solution or slurry containing at least molybdenum, phosphorus and vanadium (Solution A) and a solution or slurry containing ammonia compound (Solution B). In the catalyst manufactured by the manufacturing method including the step of mixing the solution containing the Z element or the slurry (C solution) with the mixed slurry (AB mixed solution), the amount of the ammonium root in the A solution is changed to the molybdenum atom in the A solution. 1.5 for 12 moles
It is a catalyst for producing methacrylic acid, characterized in that the catalyst is produced in an amount of 6 mol or less and the amount of ammonium root in the AB mixture is 6 to 17 mol with respect to 12 mol of molybdenum atoms in the AB mixture.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The catalyst of the present invention has a composition represented by the above formula (1). It is essential that the production of the catalyst of the present invention includes the following two steps. (I) A “solution or slurry containing at least molybdenum, phosphorus, and vanadium” called liquid A and a “solution or slurry containing ammonia compound” called liquid B are mixed,
A step of obtaining a mixed solution or slurry of the A liquid and the B liquid, called an AB mixed liquid. (II) a step of producing a solution or slurry containing a catalyst precursor by mixing a solution or slurry containing the Z element, referred to as Liquid C, with an AB mixture.

In the present invention, the amount of ammonium root in the solution A is 1.5 mol or less, preferably 1 mol or less, based on 12 mol of molybdenum atoms in the solution A. Further, the amount of ammonium root in the AB mixture is 6 to 17 mol, preferably 7 to 15 mol, per 12 mol of molybdenum atoms in the AB mixture.

The state of the liquid A, the liquid B, the mixed liquid AB, and the liquid C is not particularly limited as long as the catalyst raw material is contained in the liquid. A slurry in which a part or the whole amount is suspended in a solvent may be used. Here, water is preferable as the solvent.

The solution or slurry containing the catalyst precursor thus obtained is dried and then calcined to obtain a catalyst for producing methacrylic acid.

Although the mechanism by which the catalyst performance is improved by adopting such a production method is not clear, it is necessary to control the mixing order of the catalyst raw materials and the specific amount of ammonium root in the mixed solution A and AB. Therefore, it is presumed that a crystal structure capable of obtaining methacrylic acid in a high yield is formed.

Hereinafter, the method for producing the catalyst of the present invention will be described in more detail. (Preparation of Solution A) Solution A is prepared by dissolving or suspending at least molybdenum, phosphorus and vanadium catalyst raw materials in a solvent, and then dissolving the same at 80 to 150 ° C, preferably 90 to 13 ° C.
It is prepared by heating and stirring at 0 ° C. for 0.5 to 24 hours, preferably 1 to 12 hours. By setting the heating temperature to 80 to 150 ° C., a catalyst having high activity in the methacrylic acid production reaction can be obtained. Further, by setting the heating time to 0.5 hours or more, the reaction between the catalyst raw materials can sufficiently proceed.

The solution A is a solution or slurry containing at least molybdenum, phosphorus and vanadium catalyst raw materials, and may also contain molybdenum, phosphorus and vanadium as well as elements other than Z element catalyst raw materials.

As a raw material for the catalyst used in the production of the solution A, oxides, nitrates, carbonates, ammonium salts and the like of each element can be appropriately selected and used. For example, as a raw material of molybdenum, a raw material containing no ammonium root such as molybdenum trioxide and molybdic acid is suitable, but ammonium paramolybdate, ammonium dimolybdate,
Various ammonium molybdates such as ammonium tetramolybdate can be used in a small amount, and as a phosphorus raw material, orthophosphoric acid, phosphorus pentoxide, ammonium phosphate, etc. can be used, and as a vanadium raw material, vanadium pentoxide, metavanadium Ammonium acid and the like can be used. Further, as a raw material of molybdenum, phosphorus and vanadium, a heteropolyacid such as phosphomolybdic acid, molybdovanadophosphoric acid, and ammonium phosphomolybdate can also be used.

It is important that the amount of ammonium radical in the solution A is 1.5 mol or less with respect to 12 mol of molybdenum atoms in the solution. In order to further increase the yield of methacrylic acid, it is 1 mol or less. It is preferable that The amount of the ammonium radical in the solution A can be adjusted by the amount of the catalyst material containing the ammonium radical.

(Preparation of Solution B) Solution B is a solution or slurry containing an ammonia compound, and is prepared by dissolving or suspending the ammonia compound in a solvent. The solution B may contain a catalyst raw material of an element other than the Z element in addition to the ammonia compound if it is not in the entire amount, but preferably does not contain any components other than the ammonia compound. Here, the ammonia compound is a compound containing an ammonium group or ammonia, and examples thereof include ammonia water, ammonium nitrate, ammonium carbonate, and ammonium hydrogen carbonate.

The amount of the ammonia compound in the solution B is such that the amount of ammonium root in the AB mixture obtained by mixing the solution A and the solution B is 6 to 17 moles with respect to 12 moles of molybdenum atoms in the solution. , Preferably 7 to 15.

(Preparation of Solution C) Solution C is a solution or slurry containing the above-mentioned Z element, and is prepared by dissolving or suspending at least a catalyst raw material of the Z element in a solvent. The liquid C may contain a catalyst raw material of an element other than the element Z, but it is preferable that these are not contained as much as possible. Further, it is preferable that the liquid C contains as little ammonia compound as possible. As a catalyst raw material of the liquid C, a nitrate, a carbonate, a hydroxide or the like of each element can be appropriately selected and used.
For example, as a raw material of cesium, cesium nitrate, cesium carbonate, cesium hydroxide and the like can be used.

(Preparation of AB mixture) In the present invention,
The A liquid and the B liquid are mixed to obtain an AB mixed liquid. The method of mixing the liquid A and the liquid B is not particularly limited. For example, a method of adding the liquid B to the container containing the liquid A, a method of adding the liquid A to the container containing the liquid B, and the liquid A and the liquid B Any method such as a method of pouring at the same time can be used. For the obtained AB mixture,
Operations such as heat aging may be performed as appropriate. In order to obtain a catalyst having a high activity, the temperatures of the solution A and the solution B at the time of mixing are each preferably 70 ° C. or lower, and particularly preferably 60 ° C. or lower.

A catalyst raw material other than the Z component may be added to the mixture of the liquid A and the liquid B. As the catalyst raw material to be added in this manner, any catalyst raw material of an element other than the element Z contained in the catalyst composition represented by the formula (1) may be used. It may be added in the form of a solution or a suspension.

(Mixing of AB mixed liquid and C liquid) In the present invention, the AB mixed liquid and the C liquid are mixed. The method of mixing the AB mixed liquid and the C liquid is not particularly limited.
Examples of the method include adding the liquid C to the container containing the AB liquid, adding the liquid AB to the container containing the liquid C, and simultaneously pouring the liquid AB and the liquid C into the container.

In the present invention, when mixing the AB mixed solution and the C solution, it is more preferable to mix the AB mixed solution and copper or the Y element in advance, and then mix the obtained mixed solution and the C solution. Here, it is particularly preferable to add copper or the Y element by dissolving or suspending these catalyst raw materials in a solvent. When adding the copper or the Y element, a catalyst raw material of an element other than the Z element may be added together, but it is preferable not to add them at this time as much as possible. Also, it is preferable not to add an ammonia compound at this time as much as possible. As the catalyst raw material for the 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 of copper. The method of mixing the liquid mixture C and the liquid mixture obtained by mixing the AB liquid mixture with copper or the Y element is not particularly 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 an operation such as heat aging. The temperature of both solutions during mixing is not particularly limited, but is preferably 100 ° C. or lower.

(Drying and calcination) 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, evaporating to dryness, spray drying, drum drying,
Flash drying or the like can be used. The type of dryer used for drying, the temperature at the time of drying, and the like are not particularly limited, and a dried product of the catalyst precursor according to the purpose can be obtained by appropriately changing the drying conditions.

The dried catalyst precursor may be calcined without molding, but usually, the molded article is calcined.
The molding method is not particularly limited, and various known dry and wet molding methods can be applied, but a molding method without a carrier or the like is preferable. Specific molding methods include, for example, tablet molding, press molding, extrusion molding, granulation molding and the like. The shape of the molded article is not particularly limited, 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, a small amount of a known additive such as graphite or talc may be added.

The dried 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, the catalyst composition and the preparation method used, but the usual calcination conditions are 200 to 5 under the flow of an oxygen-containing gas such as air and / or the flow of an inert gas.
The temperature is 00 ° C, preferably 300 to 450 ° C, for 0.5 hours or more, preferably 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, helium, and argon.

When methacrylic acid is produced 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 changed in a wide range.
-20% by volume is appropriate, and particularly preferably 3-10% by volume. The source gas may contain a small amount of impurities such as water and lower saturated aldehyde, but it is preferable that the amount is as small as possible. Although it is economical to use air as the molecular oxygen source, air enriched with pure oxygen can be used if necessary. The molecular oxygen concentration in the raw material gas is 0.4 to 4 mol, particularly 0.5 to 4 mol per 1 mol of methacrolein.
3 moles are preferred. The source gas may be diluted by adding an inert gas such as nitrogen or carbon dioxide, and steam may be added to the source gas. The reaction pressure for the methacrylic acid production reaction is preferably from normal pressure to several atmospheres. The reaction temperature is 230-4
It can be selected in the range of 50 ° C., but in particular 250 to 40
0 ° C. is preferred.

[0027]

The present invention will be described in more detail with reference to examples and comparative examples, 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 amount of raw materials charged for the catalyst components. The analysis of the reaction raw materials and products was performed using gas chromatography. The conversion of methacrolein, the selectivity of generated methacrylic acid, and the single-stream yield of methacrylic acid are defined as follows. Conversion of methacrolein (%) = (B / A) × 100 Selectivity of methacrylic acid (%) = (C / B) × 100 Single flow 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.

Example 1 In 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 of iron oxide
The mixture was stirred under reflux for 5 hours to obtain a liquid A. The amount of ammonium root in Solution A was 0 mol per 12 mol of molybdenum atoms. After the solution A was cooled to 50 ° C., 37.4 parts of 29% by weight aqueous ammonia as the solution B was added dropwise.
After stirring for minutes, an AB mixture was obtained. The amount of ammonium root in the AB mixture was 11 mol per 12 mol of molybdenum atoms. Next, a solution obtained by dissolving 9.03 parts of cesium nitrate as the C liquid in 30 parts of pure water was added dropwise 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., evaporated to dryness with stirring, and the resulting solid was dried at 130 ° C. for 16 hours. This dried product is molded under pressure, and is then circulated at 375 ° C. for 10
And baking time, P 1.1 Mo 12 V 0.9 Cu 0.2 Fe 0 .05 Cs
A catalyst having a composition of 0.8 was obtained. This catalyst was filled in a reaction tube, and methacrolein 5%, oxygen 10%, steam 30%,
A mixed gas of 55% (volume%) of nitrogen is reacted at 285 ° C.
The contact time was 3.6 seconds. The results are shown in Table 1.

Example 2 In Example 1, AB was prepared by using 24 parts of 29% by weight ammonia water as the liquid B.
Table 1 shows the same results as in Example 1 except that the amount of ammonium root in the mixture was changed to 6 mol per 12 mol of molybdenum atoms.

Example 3 In Example 1, AB solution was prepared by using 51 parts of 29% by weight ammonia water as the B solution.
Table 1 shows the same results as in Example 1 except that the amount of ammonium root in the mixture was changed to 15 mol per 12 mol of molybdenum atoms.

Example 4 The procedure of Example 1 was repeated except that 13.6 parts of 29% by weight aqueous ammonia was used as the liquid B to obtain the liquid A.
The amount of ammonium root in the B mixture was adjusted to 12 molybdenum atoms.
Table 1 shows the same results as in Example 1 except that the amount was changed to 4 moles per mole.

Example 5 In Example 1, the amount of ammonium root in the AB mixture was changed to 20 mol per 12 mol of molybdenum atom by using 68 parts of 29% by weight ammonia water as the liquid B. Table 1 shows the results obtained in the same manner as in Example 1 except for the point described above.

Example 6 The results are shown in Table 1 in the same manner as in Example 1 except that the dropping temperature of the solution B was changed to 80 ° C.

[Comparative Example 1]
13.6 parts by weight of aqueous ammonia was added, and the amount of ammonium root in Solution A was 4% with respect to 12 mol of molybdenum atoms.
Example 1 except that the amount of ammonium root in the AB mixture was changed to 11 mol with respect to 12 mol of molybdenum atoms by using 23.8 parts of 29 wt% ammonia water in the AB mixture. Table 1 shows the results obtained in the same manner as described above.

[Comparative Example 2] In Example 1, except that the mixing order of the liquid B and the liquid C was reversed, the liquid C was dropped on the liquid A, and the liquid B was dropped on the mixed liquid. Example 1
Table 1 shows the results obtained in the same manner as described above.

Comparative Example 3 Table 1 shows the same results as in Example 1 except that the mixture of Liquid B and Liquid C was added dropwise to Liquid A.

[Example 7] 100 parts of molybdenum trioxide, 8.88 parts of 85% by weight phosphoric acid, 4.74 parts of ammonium metavanadate, and 1.40 parts of cupric nitrate were added to 400 parts of pure water in 10 parts of pure water. 2.33 parts of ferric nitrate dissolved in 10 parts of pure water, 60% by weight arsenic acid aqueous solution 4.1
One part and 1.00 part of cerium oxide were added, and the mixture was stirred in an autoclave under saturated steam at 120 ° C. for 3 hours to obtain a liquid A. The amount of ammonium root in solution A is 12 molybdenum atoms.
0.7 mole per mole. After cooling the solution A to 60 ° C., a solution obtained by dissolving 37.0 parts of ammonium carbonate as the solution B in 80 parts of pure water was added dropwise and stirred for 15 minutes.
A mixture was obtained. The amount of ammonium root in the AB mixture was 14 mol per 12 mol of molybdenum atoms. Next, a solution obtained by dissolving 18.0 parts of cesium bicarbonate as liquid C in 30 parts of pure water was added dropwise to the AB mixture, and the mixture was stirred for 15 minutes to obtain a slurry. The slurry thus obtained is heated at 101 ° C.
And dried with stirring at 130 ° C. for 16 hours. This dried product was molded under pressure, 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
A catalyst having a composition of V 0.7 Cu 0.1 Fe 0.1 As 0.3 Ce 0.1 Cs 1.6 was obtained. Using this catalyst, the reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was changed to 290 ° C., and the results are shown in Table 1.

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, and 4.11 parts of a 60% by weight aqueous arsenic acid solution were added. Medium, under saturated steam 1
It stirred at 20 degreeC for 3 hours, and obtained the liquid A. The amount of ammonium root in Solution A was 0.7 mol with respect to 12 mol of molybdenum atoms. After the solution A was cooled to 60 ° C., a solution in which 37.0 parts of ammonium carbonate as the solution B was dissolved in 80 parts of pure water was added dropwise and stirred for 15 minutes to obtain an AB mixed solution. The amount of ammonium root in the AB mixture was 14 mol per 12 mol of molybdenum atoms. Next, a solution of 1.40 parts of cupric nitrate in 10 parts of pure water, a solution of 2.34 parts of ferric nitrate in 10 parts of pure water, and 1.00 part of cerium oxide were successively added to the AB mixture. After the addition, a solution obtained by dissolving 18.0 parts of cesium bicarbonate as a C solution in 30 parts of pure water was added dropwise to the solution.
After stirring for minutes, a slurry was obtained. The slurry thus obtained was heated to 101 ° C., evaporated to dryness with stirring, and the resulting solid was dried at 130 ° C. for 16 hours. The dried product is molded under pressure, baked at 400 ° C. for 5 hours under nitrogen flow, and further baked 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. Using this catalyst, the reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was changed to 290 ° C., and the results are shown in Table 1.

Comparative Example 4 The procedure of Example 7 was repeated, except that the mixing of the solution A, the solution B and the solution C was changed to a method in which the solution A, the solution B and the solution C were simultaneously poured into the container and mixed. Example 7
Table 1 shows the results obtained in the same manner as described above.

[0040]

[Table 1]

[0041]

According to the present invention, methacrylic acid can be produced in high yield by using the catalyst of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300

Claims (3)

[Claims]
1. A formula used in producing methacrylic acid by vapor phase catalytic oxidation by the methacrolein molecular oxygen (1) 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;
Represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron, and Y represents iron, zinc, chromium, magnesium, tantalum, cobalt , Manganese, barium, gallium, cerium, and lanthanum, and 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 to 3, f = 0 to 3, g = 0.01 to 3, and h is the atomic ratio of oxygen necessary to satisfy the valence of each component. And a solution or slurry containing at least molybdenum, phosphorus and vanadium (Solution A) and a solution or slurry containing ammonia compound (Solution B). In the catalyst manufactured by the manufacturing method including the step of mixing the solution containing the Z element or the slurry (C solution) with the mixed slurry (AB mixed solution), the amount of the ammonium root in the A solution is changed to the molybdenum atom in the A solution. 1.5 for 12 moles
A methacrylic acid production catalyst, characterized in that the catalyst is produced in an amount of not more than 1 mol and the amount of ammonium root in the AB mixture is 6 to 17 mol per 12 mol of molybdenum atoms in the AB mixture.
2. The catalyst for producing methacrylic acid according to claim 1, wherein copper or Y element is previously mixed into the AB mixture before mixing the AB mixture and the C solution.
3. A method for producing methacrylic acid using the catalyst for producing methacrylic acid according to claim 1 or 2.
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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Cited By (7)

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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
WO2004073857A1 (en) * 2003-02-20 2004-09-02 Nippon Kayaku Kabushiki Kaisha Catalyst for methacrylic acid production and process for producing the same
JP2006181463A (en) * 2004-12-27 2006-07-13 Mitsubishi Rayon Co Ltd Manufacturing method of catalyst for producing methacrylic acid
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
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
KR20100101533A (en) * 2009-03-09 2010-09-17 스미또모 가가꾸 가부시키가이샤 Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid
US8114805B2 (en) * 2007-06-13 2012-02-14 Lg Chem, Ltd. Method of preparing heteropoly acid catalyst

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004004900A1 (en) * 2002-07-05 2004-01-15 Mitsubishi Rayon Co., Ltd. Process for producing catalysts for the production of methacrylic acid
JPWO2004004900A1 (en) * 2002-07-05 2005-11-04 三菱レイヨン株式会社 Method for producing a catalyst for methacrylic acid production
JP4691359B2 (en) * 2002-07-05 2011-06-01 三菱レイヨン株式会社 Method for producing a catalyst for methacrylic acid production
US7625834B2 (en) 2002-07-05 2009-12-01 Mitsubishi Rayon Co., Ltd. Process for producing catalysts for the production of methacrylic acid
WO2004073857A1 (en) * 2003-02-20 2004-09-02 Nippon Kayaku Kabushiki Kaisha Catalyst for methacrylic acid production and process for producing the same
CN100457264C (en) * 2003-02-20 2009-02-04 日本化药株式会社 Catalyst for methacrylic acid production and process for producing the same
US7825061B2 (en) 2003-02-20 2010-11-02 Nippon Kayaku Kabushiki Kaisha Catalyst for producing methacrylic acid and preparation method thereof
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
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
JP2006181463A (en) * 2004-12-27 2006-07-13 Mitsubishi Rayon Co Ltd Manufacturing method of catalyst for producing methacrylic acid
US8114805B2 (en) * 2007-06-13 2012-02-14 Lg Chem, Ltd. Method of preparing heteropoly acid catalyst
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
KR20100101533A (en) * 2009-03-09 2010-09-17 스미또모 가가꾸 가부시키가이샤 Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid
KR101640255B1 (en) 2009-03-09 2016-07-15 스미또모 가가꾸 가부시키가이샤 Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid

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