JP2009050770A - Method for manufacturing catalyst for producing methacrylic acid and catalyst and method for producing methacrylic acid - Google Patents

Method for manufacturing catalyst for producing methacrylic acid and catalyst and method for producing methacrylic acid Download PDF

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JP2009050770A
JP2009050770A JP2007218127A JP2007218127A JP2009050770A JP 2009050770 A JP2009050770 A JP 2009050770A JP 2007218127 A JP2007218127 A JP 2007218127A JP 2007218127 A JP2007218127 A JP 2007218127A JP 2009050770 A JP2009050770 A JP 2009050770A
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JP4895303B2 (en
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Masahide Kondo
Keiko Maehara
桂子 前原
正英 近藤
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Mitsubishi Rayon Co Ltd
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
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    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

Disclosed is a method for producing a catalyst for producing methacrylic acid having a high selectivity for methacrylic acid, which is used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen.
A method for producing a catalyst for producing methacrylic acid comprising the following steps (a) to (d):
(A) A solution or slurry obtained by dissolving or suspending a catalyst raw material containing at least a molybdenum raw material, a phosphorus raw material and a vanadium raw material in a solvent and heating to a temperature not lower than 30 ° C. and not higher than 80 ° C. Step (c) of obtaining a liquid A in which a dried product obtained by drying contains cubic and triclinic crystals of heteropolyacid (b) A step of preparing a liquid B by mixing the antimony raw material and the liquid A (c) ) A step of preparing liquid C which is a solution or slurry containing at least one selected from alkali metal elements and alkaline earth metal elements. (D) A step of mixing liquid B and liquid C. [Selection] None

Description

  The present invention relates to a method for producing a catalyst used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen (hereinafter referred to as “catalyst for methacrylic acid production”), and methacrylic acid obtained by this production method. The present invention relates to a production catalyst and a method for producing methacrylic acid.

Among the conventionally known methods for producing a catalyst for methacrylic acid production, there are many preparation examples of a catalyst containing antimony in the catalyst, which are described in Patent Literature 1, Patent Literature 2, Patent Literature 3, Patent Literature 4, and the like. . In any case, this is a catalyst preparation method in which antimony is mixed after adding a molybdenum raw material, a vanadium raw material, a phosphorus raw material or the like. Patent Document 1 is a preparation method in which an antimony solution is added after refluxing a homogeneous solution containing molybdenum, phosphorus and the like, and the preparation temperature is preferably 0 to 25 ° C. when the antimony is mixed. Patent Document 2 proposes a method for producing a catalyst for methacrylic acid production, in which a molybdenum raw material solution and a raw material solution excluding molybdenum are mixed at room temperature to 80 ° C. to deposit a Dawson type heteropolyacid salt and calcined in an inert gas. ing. In Patent Document 3, a molybdenum raw material, a vanadium raw material, and a phosphorus raw material are mixed and dissolved or suspended in water. After heat treatment at 120 ° C. for 17 hours in the presence of an ammonium root, an antimony raw material is added, and then 120 times again. A method for producing a catalyst for methacrylic acid production in which heat treatment is carried out at 17 ° C. for 17 hours has been proposed. Furthermore, in Reference Example 1 of Patent Document 4, a solution obtained by adding cesium nitrate, phosphoric acid or the like to water heated to 40 ° C. and a solution obtained by dissolving ammonium molybdate in water heated to 40 ° C. and then adding ammonium metavanadate. A method for producing a catalyst for methacrylic acid production is described, in which antimony trioxide is added to the latter solution, followed by hydrothermal synthesis by adding the former solution to the latter solution.
JP-A-5-31368 JP-A-7-185354 JP-A-9-75740 JP 2005-272313 A

  However, the methacrylic acid selectivity of the catalyst produced using the method described in these publications is not always sufficient, and further improvement in catalyst performance is desired as an industrial catalyst.

  An object of the present invention is to provide a method for producing a methacrylic acid production catalyst having a high selectivity for methacrylic acid, which is used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen, and methacrylic acid obtained by this production method. It is an object to provide a catalyst for producing acid and a method for producing methacrylic acid using the catalyst for producing methacrylic acid.

  In order to solve the above-mentioned problems, a method for producing a methacrylic acid production catalyst used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen, comprising the following (a) to (d) The method for producing a catalyst for methacrylic acid production comprising the step (1) is a first invention.

(A) A catalyst raw material containing at least a molybdenum raw material, a phosphorus raw material, and a vanadium raw material is dissolved or suspended in a solvent, and heated to a temperature not lower than 30 ° C. and not higher than 80 ° C. to form cubic and triclinic heteropolyacids (B) A step of preparing the B liquid by mixing the antimony raw material and the A liquid (c) A solution containing at least one selected from alkali metal elements and alkaline earth metal elements Or a step of preparing a liquid C as a slurry (d) a step of mixing the liquid B and the liquid C. The catalyst for producing methacrylic acid produced by the above method for producing a catalyst for producing methacrylic acid is the second invention. And

  Furthermore, a third aspect of the present invention is a method for producing methacrylic acid in which methacrolein is subjected to gas phase catalytic oxidation with molecular oxygen in the presence of the above catalyst for producing methacrylic acid.

  According to the present invention, a catalyst having a high selectivity for methacrylic acid for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen, a method for producing the same, and a method for producing methacrylic acid at a high selectivity. The manufacturing method of methacrylic acid which can be provided can be provided.

  In the method for producing a catalyst for methacrylic acid production of the present invention, (a) a step of preparing A liquid, (b) a step of preparing B liquid, (c) a step of preparing C liquid, and (d) B liquid And C liquid are mixed to prepare a mixed liquid (hereinafter referred to as “BC liquid”), and the catalyst precursor solution or slurry is dried to obtain a catalyst precursor. The catalyst can be obtained by calcination.

  In the present invention, the catalyst for producing methacrylic acid used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen preferably has a composition represented by the following formula (1). .

P a Mo b V c Sb d X e Y f Z g O h (1)
(P, Mo, V, Sb and O represent phosphorus, molybdenum, vanadium, antimony and oxygen, respectively. X is a group consisting of bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and 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, and Z represents And at least one element selected from the group consisting of potassium, rubidium, and cesium, wherein a, b, c, d, e, f, g, and h represent the atomic ratio of each element, and when b = 12, a = 0.5 to 3, c = 0.01 to 3, d = 0.01 to 2, e = 0 to 3, f = 0 to 3, g = 0.01 to 3 Ri, h is the atomic ratio of oxygen required to satisfy the valence of each component.)
(A) Preparation of solution A Solution A is prepared by dissolving or suspending at least a compound of molybdenum, phosphorus, and vanadium in a solvent to form a solution or slurry, which is heated. In addition to molybdenum, phosphorus, and vanadium, copper, X element, Y element, Z element, and ammonium root may be included. The “ammonium root” in the present invention is a general term for ammonium contained in ammonium-containing compounds such as ammonia (NH 3 ) and ammonium salts that can be ammonium (NH 4 + ).

  The amount of ammonium radical contained in the liquid A is preferably 0 to 1.5 mol, more preferably 0 to 1.0 mol, per 12 mol of molybdenum atoms. By setting the amount of ammonium root within this range, a catalyst having a high methacrylic acid selectivity can be obtained. The amount of ammonium root contained in the liquid A can be adjusted by the amount of the catalyst raw material containing these and the amount of ammonia used.

  As a catalyst raw material used for preparing the liquid A, oxides, oxygen acids, ammonium salts, and the like of each element of molybdenum, phosphorus, and vanadium can be appropriately selected and used. For example, the molybdenum element material is preferably an ammonium-free compound such as molybdenum trioxide or molybdic acid, but a small amount of various ammonium molybdates such as ammonium paramolybdate, ammonium dimolybdate, or ammonium tetramolybdate. Can be used. In addition, as a raw material for the phosphorus element, orthophosphoric acid, phosphorus pentoxide, ammonium phosphate, and the like can be used. Further, vanadium pentoxide, ammonium metavanadate, or the like can be used as a raw material for the vanadium element. Furthermore, heteropolyacids such as phosphomolybdic acid, molybdovanadolinic acid, and ammonium phosphomolybdate can also be used as raw materials for each element of phosphorus, molybdenum, and vanadium. In preparing the liquid A, it is preferable not to use antimony as a catalyst raw material.

  Examples of the solvent used for preparing the liquid A include water, ethyl alcohol, ethylene glycol, acetone, and a mixed solution thereof, but it is preferable to use water. The amount of the solvent is not particularly limited, but the mass ratio of the molybdenum compound and the solvent contained in the solution or slurry containing molybdenum, phosphorus and vanadium is preferably 1: 0.1 to 1: 100, and 1: 0.5 to 1 : 50 is more preferable.

  The heating temperature of the solution or slurry in preparation of A liquid is 30-80 degreeC, and 35-60 degreeC is preferable. Moreover, regarding a heating time, the range of 0 to 5 hours is preferable normally, and 0 to 0.5 hours are more preferable.

  By preparing the liquid A at this heating temperature, as shown in FIG. 1, in the X-ray diffraction (counter cathode Cu-Kα) of the dried liquid A, about 2θ = 26.5 derived from the heteropolyacid cubic system. Between the peak at ° and the peak at about 2θ = 30.7 °, three peaks of about 2θ = 27.8, 28.5, and 29.1 appearing from the triclinic system of heteropolyacid appear. Further, peaks of about 2θ = 25.7 ° and about 2θ = 27.4 ° appearing from molybdenum trioxide appear, and in order to improve the selectivity, when the intensity of about 2θ = 26.5 ° is 100, The relative intensity at about 2θ = 27.4 ° is preferably 40% or less.

  Moreover, it exists in the tendency which can obtain a catalyst with high methacrylic acid selectivity by controlling the temperature of A liquid in this range.

  When performing X-ray diffraction measurement of the dried product of liquid A, liquid A is dispensed into a sample bottle and dried under reduced pressure at room temperature to 80 ° C. to completely remove moisture contained in liquid A.

(B) Preparation of liquid B When the antimony raw material and the liquid A are mixed to form liquid B, the antimony raw material can be used by dissolving or suspending it in a solvent, but it is preferable to use the antimony raw material as it is. .

  When mixing the antimony material and the liquid A, in addition to antimony, phosphorus, molybdenum, vanadium, copper, X element, Y element, Z element, alkali metal element and alkaline earth metal element may be mixed. These elements are preferably not mixed.

  As the antimony raw material, for example, antimony trioxide, antimony pentoxide, antimony sulfate, antimony sol and the like can be used. These raw materials may be used alone or in combination of two or more. In particular, a catalyst having a high selectivity tends to be obtained by using antimony trioxide.

  As a mixing method of the A liquid and the antimony raw material, there are a method of mixing the antimony raw material with the A liquid, a method of mixing the A liquid with the antimony raw material, and a method of simultaneously mixing the A liquid and the antimony raw material. It is preferable to mix by the method of mixing an antimony raw material with A liquid. Moreover, mixing of A liquid and an antimony raw material may be performed once, or may be mixed in 2 times or more.

  Mixing of A liquid and an antimony raw material has temperature of A liquid of 30-80 degreeC, and 35-60 degreeC is more preferable. By preparing a liquid mixture of the liquid A and the antimony raw material at the temperature of the liquid A, a catalyst having a high methacrylic acid selectivity tends to be obtained. Further, the temperature of the antimony raw material is not particularly limited.

  In the present invention, in order to maintain the temperature at the time of mixing the liquid A and the antimony raw material, a method of adjusting the mixing speed of the liquid A and the antimony raw material, a method of adjusting the concentration of the liquid A and the antimony raw material, the liquid A and the antimony Various methods such as a method by cooling or passing a heating medium through a jacket portion of a tank for preparing raw materials, a method of adjusting the rotation speed of a stirring blade during mixing, and the like can be used. These methods can be used alone or in combination. Here, the mixing speed of the liquid A and the antimony raw material may be the same speed from the start to the end of the mixing, or may be changed in the middle. The heating time is not particularly limited and may be determined as appropriate.

  In this invention, 0.1 to 15 minutes are preferable from a viewpoint of methacrylic acid selectivity, and, as for the time which mixes A liquid and an antimony raw material, 0.5 to 10 minutes are more preferable.

(C) Preparation of liquid C When liquid C is prepared, it may contain at least one compound selected from an alkali metal element and an alkaline earth metal element as well as a compound of another element serving as a catalyst raw material unless the total amount. However, it is preferable that these elements are not basically contained.

  As the alkali metal element or alkaline earth metal element to be used, nitrates, carbonates, hydroxides and the like of each element can be appropriately selected and used. For example, as a raw material for cesium, cesium nitrate, cesium carbonate, and cesium hydroxide can be used. The raw materials for these catalyst components may be used alone or in combination of two or more for each element.

  Further, at least one selected from alkali metal elements and alkaline earth metal elements is used by dissolving or suspending in a solvent. Examples of the solvent include water, ethyl alcohol, and acetone. Water is preferably used. The amount of the solvent is not particularly limited, but usually the mass ratio of the raw material to the solvent is preferably 1: 0.1 to 1: 100, more preferably 1: 0.5 to 1:50.

  When at least one selected from alkali metal and alkaline earth metal elements is dissolved in a solvent to form a solution, or suspended in a solvent to form a slurry, the system may be prepared by stirring the system at room temperature. From the viewpoint of methacrylic acid selectivity, it is preferable to prepare by heating and stirring. The heating temperature may be adjusted by heating to about 100 ° C. as necessary, but 80 ° C. or less is more preferable.

(D) Preparation of BC liquid In this invention, the said B liquid and the said C liquid are mixed and BC liquid is prepared. The mixing method of B liquid and C liquid is not specifically limited, For example, the method of adding C liquid to B liquid and mixing, the method of adding B liquid to C liquid and mixing, and mixing B liquid and C liquid simultaneously Applicable methods are applicable. From the viewpoint of methacrylic acid selectivity, the method of adding the C liquid to the B liquid and mixing them is preferable. Although mixing of B liquid and C liquid may be performed at normal temperature, you may heat and prepare. From the viewpoint of methacrylic acid selectivity, the temperature during mixing is preferably 80 ° C. or less, and more preferably 70 ° C. or less.

<Mixing of BC liquid and catalyst raw material>
Next, if necessary, the BC solution prepared above and the remaining raw material used for the production of the catalyst (hereinafter referred to as “remaining raw material”) are mixed to prepare a solution or slurry containing the catalyst precursor. In the present invention, as the remaining raw material to be mixed, it is possible to add a small amount of X element, Y element, Z element and other compounds. The residual raw material to mix may use 1 type, or may use 2 or more types together.

  These remaining raw materials may be added as they are, or may be added in a solution state or in a suspended state. Examples of the solvent to be used include water, ethyl alcohol, acetone and the like, and a mixed solution thereof, but it is preferable to use water. The amount of this solvent is not particularly limited. Moreover, the method for mixing the remaining raw materials with the BC liquid is not particularly limited.

<Drying and firing>
Next, the solution or slurry containing all catalyst raw materials can be dried by a known treatment method and conditions to obtain a dried catalyst precursor.

  As a drying method, various methods can be used, and for example, an evaporation to dryness method, a spray drying method, a drum drying method, an airflow drying method, and the like can be used. There are no particular limitations on the model of the dryer used for drying, the temperature and time during drying, and a dried catalyst precursor according to the purpose can be obtained by appropriately changing the drying conditions.

  The dried product of the catalyst precursor thus obtained may be pulverized if necessary, and then subjected to subsequent firing without molding, but it is preferable to fire the molded product of the catalyst precursor. .

  The method for molding the catalyst precursor is not particularly limited, and various known dry and wet molding methods can be applied, but it is preferable to mold without including a carrier such as silica. Specific examples of the molding method include a tableting molding method, a press molding method, an extrusion molding method, and a granulation molding method. The shape of the molded product is not particularly limited, and for example, a desired shape such as a columnar shape, a ring shape, and a spherical shape can be selected.

  In molding, a small amount of known additives such as graphite and talc may be added.

  The dried catalyst precursor or molded product thereof thus obtained is fired to obtain a catalyst for producing methacrylic acid.

  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, preparation method, and the like, but are usually 200 to 500 ° C., preferably 300 to 450 ° C. under an oxygen-containing gas flow or an inert gas flow such as air. 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.

<Method for producing methacrylic acid>
Next, the manufacturing method of methacrylic acid of this invention is demonstrated. The method for producing methacrylic acid of the present invention is a process for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen in the presence of the catalyst of the present invention obtained as described above.

  The reaction is carried out in a normal fixed bed. The catalyst layer may be one layer or two or more layers. The catalyst may be supported on a carrier or may be a mixture of other additive components.

  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 concentration of methacrolein in the raw material gas can be varied within a wide range, but usually 1 to 20% by volume is appropriate, and 3 to 10% by volume is more preferable.

  It is economical to use air as the molecular oxygen, but if necessary, air enriched with pure oxygen can also be used. The concentration of molecular oxygen in the raw material gas is usually suitably 0.4-4 mol and more preferably 0.5-3 mol with respect to 1 mol of methacrolein.

  The source gas may be obtained by diluting methacrolein and molecular oxygen with an inert gas such as nitrogen or carbon dioxide.

  Further, water vapor may be added to the raw material gas. When the reaction is carried out in the presence of water, methacrylic acid is obtained in a higher yield. The concentration of water vapor in the raw material gas is preferably 0.1 to 50% by volume, more preferably 1 to 40% by volume.

  The source gas may contain a small amount of impurities such as lower saturated aldehyde, but the amount is preferably as small as possible.

  The reaction pressure for the methacrylic acid production reaction is from atmospheric pressure to several atmospheres. The reaction temperature is usually preferably 230 to 450 ° C, more preferably 250 to 400 ° C.

  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.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

  “Parts” in Examples and Comparative Examples means “parts by mass”. The composition of the catalyst was determined from the raw material charge of the catalyst component. The reaction raw material gas and the product were analyzed using gas chromatography. The amounts of ammonia and ammonium contained in the solution were measured by the Kjeldahl method.

  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 (%) = (β / α) × 100
Methacrylic acid selectivity (%) = (γ / β) × 100
Single flow yield of methacrylic acid (%) = (γ / α) × 100
Here, α is the number of moles of methacrolein supplied, β is the number of moles of reacted methacrolein, and γ is the number of moles of methacrylic acid produced.

[Example 1]
To 200 parts of pure water, 100 parts of molybdenum trioxide, 6.66 parts of 85% by mass phosphoric acid and 2.63 parts of vanadium pentoxide were added to form a slurry while stirring, and the resulting slurry was heated at 60 ° C. for 0.2 hours. Thus, liquid A was obtained. X-ray diffraction (counter cathode Cu-Kα) of the dried powder obtained by drying a part (2 ml) of this A liquid under reduced pressure at about 7 kPa at 50 ° C. for 8 hours was measured. From the diffraction pattern, as shown in FIG. 1, peaks of 2θ = 26.5 ° and 30.7 ° derived from the cubic system of heteropolyacid and 2θ = 27.8 ° derived from the triclinic system of heteropolyacid, 28 Peaks of .5 ° and 29.1 ° appeared. In a state where the liquid A was kept at 60 ° C., 2.53 parts of antimony trioxide was added all at once to the slurry to prepare a liquid B, which was stirred for 3 hours under reflux. After refluxing and stirring, the slurry was cooled to 50 ° C., and C solution in which 13.54 parts of cesium nitrate was dissolved in 28.43 parts of pure water was added and stirred for 5 minutes to prepare BC solution. 39.44 parts of water was added dropwise. The obtained solution was stirred at 50 ° C. for 2 hours to obtain a slurry containing a catalyst precursor.

The slurry containing the catalyst precursor was heated to 101 ° C. and evaporated to dryness with stirring. The obtained solid was dried at 130 ° C. for 16 hours. The obtained dried product was pressure-molded and then calcined at 375 ° C. for 10 hours under air flow to obtain a catalyst. The composition of the obtained catalyst was P 1.0 Mo 12 V 0.5 Sb 0.3 Cs 1.2 .

  The obtained catalyst was filled into a reaction tube, and a mixed gas of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of steam, and 55% by volume of nitrogen was used under normal pressure at a reaction temperature of 290 ° C. and a contact time of 3.6 seconds. As a result of the reaction, the methacrylic acid selectivity was 92.4% and the methacrolein reaction rate was 65.3%.

[Example 2]
In Example 1, the heating temperature at the time of preparing the liquid A was 40 ° C., and except that 2.53 parts of antimony trioxide was collectively added while maintaining the temperature of the liquid A at 40 ° C. A catalyst was prepared in a similar manner. In the X-ray diffraction of the dried product of the liquid A obtained in the same manner as in Example 1, peaks of 2θ = 26.5 ° and 30.7 ° derived from the cubic system of heteropolyacid and the triclinic system of heteropolyacid Peaks at 2θ = 27.8 °, 28.5 ° and 29.1 ° appearing. Table 1 shows the results of producing methacrylic acid by the same method as in Example 1 using the prepared catalyst.

[Comparative Example 1]
In Example 1, the heating temperature at the time of preparing the liquid A was 20 ° C., and the same procedure as in the example 1 except that 2.53 parts of antimony trioxide was collectively added while the temperature of the liquid A was kept at 20 ° C. The catalyst was prepared by the method described above. In the X-ray diffraction of the dried product of the liquid A obtained in the same manner as in Example 1, peaks of 2θ = 26.5 ° and 30.7 ° derived from the cubic system of heteropolyacid and the triclinic system of heteropolyacid 2θ = 27.8 °, 28.5 ° and 29.1 ° peaks did not appear. Table 1 shows the results of producing methacrylic acid by the same method as in Example 1 using the prepared catalyst.

[Comparative Example 2]
In Example 1, liquid C in which 13.54 parts of cesium nitrate was dissolved in 28.43 parts of pure water was added while maintaining the temperature of liquid A at 60 ° C., and then 2.53 parts of antimony trioxide was added all at once. After stirring for 3 hours under reflux, a catalyst was prepared in the same manner as in Example 1 except that the slurry was cooled to 50 ° C. Table 1 shows the results of producing methacrylic acid by the same method as in Example 1 using the prepared catalyst.

[Comparative Example 3]
In Example 1, the same procedure as in Example 1 was performed except that the mixture was refluxed (about 100 ° C.) for 1 hour in the heating for preparing the solution A, and 2.53 parts of antimony trioxide was added all at once to prepare the solution B. The catalyst was prepared by the method. In the X-ray diffraction of the dried product of the liquid A obtained in the same manner as in Example 1, peaks of 2θ = 25.7 ° and 2θ = 27.4 ° derived from molybdenum trioxide appeared remarkably. Table 1 shows the results of producing methacrylic acid by the same method as in Example 1 using the prepared catalyst.

It is an X-ray-diffraction chart of the dried product of molybdenum trioxide and A liquid.

Claims (3)

  1. A method for producing a catalyst for producing methacrylic acid used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen, comprising the following steps (a) to (d) A method for producing a catalyst.
    (A) A solution or slurry obtained by dissolving or suspending a catalyst raw material containing at least a molybdenum raw material, a phosphorus raw material and a vanadium raw material in a solvent and heating to a temperature not lower than 30 ° C. and not higher than 80 ° C. Step (c) of obtaining a liquid A in which a dried product obtained by drying contains cubic and triclinic crystals of heteropolyacid (b) A step of preparing a liquid B by mixing the antimony raw material and the liquid A (c) ) A step of preparing a liquid C which is a solution or slurry containing at least one selected from an alkali metal element and an alkaline earth metal element. (D) A step of mixing the liquid B and the liquid C.
  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.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011152519A (en) * 2010-01-28 2011-08-11 Mitsubishi Rayon Co Ltd Catalyst for producing methacrylic acid and method for producing the same, and method for producing methacrylic acid

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