JP2010207694A - Method of regenerating catalyst for manufacturing methacrylic acid and method of manufacturing methacrylic acid - Google Patents

Method of regenerating catalyst for manufacturing methacrylic acid and method of manufacturing methacrylic acid Download PDF

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JP2010207694A
JP2010207694A JP2009055727A JP2009055727A JP2010207694A JP 2010207694 A JP2010207694 A JP 2010207694A JP 2009055727 A JP2009055727 A JP 2009055727A JP 2009055727 A JP2009055727 A JP 2009055727A JP 2010207694 A JP2010207694 A JP 2010207694A
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catalyst
aqueous slurry
methacrylic acid
molybdenum
compound
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JP5335490B2 (en
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Toshiaki Miyatake
Junji Shibata
Eiichi Shiraishi
俊明 宮武
順二 柴田
英市 白石
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Sumitomo Chemical Co Ltd
住友化学株式会社
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198Vanadium
    • B01J27/199Vanadium with chromium, molybdenum, tungsten or polonium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/28Regeneration or reactivation
    • B01J27/285Regeneration or reactivation of catalysts comprising compounds of phosphorus
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/06Fabrics or filaments
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0045Drying a slurry, e.g. spray drying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/48Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/48Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/485Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • 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
    • Y02P20/584Recycling of catalysts

Abstract

PROBLEM TO BE SOLVED: To provide a method for regenerating a catalyst for methacrylic acid production capable of satisfactorily recovering catalyst activity.
A method for regenerating a catalyst comprising a heteropolyacid compound containing phosphorus, molybdenum, and a specific element X, wherein a spent catalyst, a nitrate radical, an ammonium radical, and water are mixed, and the element X with respect to molybdenum is mixed. Step (I) for obtaining an aqueous slurry A adjusted so that the atomic ratio (X / Mo ratio) is 2/12 to 4/12, the heteropolyacid compound raw material compound and water are mixed, and the X / Mo ratio is Step (II) for obtaining an aqueous slurry B adjusted to 0/12 to 0.5 / 12, aqueous slurry A obtained in step (I), and aqueous slurry B obtained in step (II) After mixing, after the step of drying and firing (III), the X / Mo ratio in the heteropolyacid compound constituting the regenerated catalyst is set to 0.5 / 12 to 2/12.
[Selection figure] None

Description

  The present invention regenerates a used catalyst composed of a heteropolyacid compound containing phosphorus, molybdenum, and at least one element selected from the group consisting of potassium, rubidium, cesium, and thallium. The present invention relates to a method for regenerating a catalyst and a method for producing methacrylic acid using a regenerated catalyst obtained by this method.

  A catalyst for producing methacrylic acid comprising a heteropolyacid compound containing phosphorus, molybdenum, and at least one element selected from the group consisting of potassium, rubidium, cesium and thallium is, for example, vapor phase contact using methacrolein as a raw material. It is known that when used for an oxidation reaction for a long time, the catalytic activity is lowered due to heat load or the like.

  As a method for regenerating such a spent catalyst, there has been proposed a method in which an aqueous slurry obtained by mixing a nitrate radical and an ammonium root with a spent catalyst is dried and then calcined (Patent Documents 1 to 3). .

JP 2008-80232 A JP 2008-86928 A JP 2008-93595 A

  However, the regenerated catalyst regenerated by the conventional regeneration method is not always satisfactory in terms of catalyst activity.

  Then, the objective of this invention is providing the reproduction | regeneration method of the catalyst for methacrylic acid manufacture which can recover | restore catalyst activity favorably. Furthermore, an object of the present invention is to provide a method for producing methacrylic acid with a good conversion and selectivity using the regenerated catalyst obtained by this method.

  The present inventor has intensively studied to solve the above problems. As a result, a nitrate slurry and an ammonium root are mixed with the spent catalyst to obtain an aqueous slurry, and the aqueous slurry is dried and calcined. From the group consisting of phosphorus, molybdenum, potassium, rubidium, cesium and thallium. In regenerating a catalyst comprising a heteropolyacid compound containing at least one element X selected, the atomic ratio of element X to molybdenum in the aqueous slurry A obtained from the used catalyst is larger than the atomic ratio in the regenerated catalyst. In addition to the aqueous slurry A, an aqueous slurry B having a lower atomic ratio of element X to molybdenum than the atomic ratio of the regenerated catalyst is prepared by using a raw material compound of a heteropolyacid compound separately from the aqueous slurry A. The composition ratio of the heteropolyacid compound in the regenerated catalyst obtained ( By atomic ratio of the element X) are mixed so that a particular range for Ribuden found that can solve the above problems, and have completed the present invention.

That is, this invention consists of the following structures.
(1) A method for regenerating a catalyst for methacrylic acid production comprising a heteropolyacid compound comprising phosphorus, molybdenum, and at least one element X selected from the group consisting of potassium, rubidium, cesium and thallium, wherein The atomic ratio (X / Mo) of element X to molybdenum in the heteropolyacid compound comprising (I) to (III) and constituting the regenerated catalyst is 0.5 / 12 to 2/12 A method for regenerating a catalyst for producing methacrylic acid.
Step (I): A spent catalyst obtained by using methacrylic acid, a nitrate radical, an ammonium radical and water are mixed, and the atomic ratio of element X to molybdenum (X / Mo) is 2/12 to 4 / A step of obtaining an aqueous slurry A adjusted to be 12.
Step (II): An aqueous slurry B prepared by mixing the heteropolyacid compound raw material compound and water so that the atomic ratio of element X to molybdenum (X / Mo) is 0/12 to 0.5 / 12. Obtaining.
Step (III): A step of mixing the aqueous slurry A obtained in step (I) and the aqueous slurry B obtained in step (II), followed by drying and firing.
(2) The method for regenerating a catalyst for methacrylic acid production according to (1) above, wherein the aqueous slurry A obtained in the step (I) contains 0.1 to 3.0 moles of ammonium roots per 1 mole of nitrate radicals.
(3) The method for regenerating a catalyst for methacrylic acid production according to (1) or (2), wherein the pH of the liquid phase of the aqueous slurry A obtained in step (I) is 8 or less.
(4) The heteropolyacid compound further includes vanadium and at least one element selected from the group consisting of copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum, and cerium (1 )-(3) The regeneration method of the catalyst for methacrylic acid manufacture in any one.
(5) A catalyst for producing methacrylic acid is regenerated by the method according to any one of (1) to (4) above, and in the presence of the regenerated catalyst, methacrolein, isobutyraldehyde, isobutane and isobutyric acid are used. A method for producing methacrylic acid, which comprises subjecting a compound selected from the group to a gas phase catalytic oxidation reaction.

  According to the present invention, the catalyst activity can be recovered satisfactorily when the catalyst for producing methacrylic acid is regenerated. Moreover, if the regenerated catalyst regenerated by this method is used, methacrylic acid can be produced with good conversion and selectivity.

Hereinafter, the present invention will be described in detail.
The method for regenerating a catalyst for producing methacrylic acid of the present invention is a method for obtaining a regenerated catalyst by subjecting a used catalyst for producing methacrylic acid obtained by the production of methacrylic acid to a regeneration treatment.
The catalyst for methacrylic acid production (hereinafter sometimes referred to as “target catalyst”) applicable to the regeneration method of the present invention is at least one selected from the group consisting of phosphorus, molybdenum, potassium, rubidium, cesium and thallium. It consists of a heteropolyacid compound containing the element X, may consist of a free heteropolyacid, or may consist of a salt of a heteropolyacid. Especially, what consists of an acidic salt (partially neutralized salt) of heteropolyacid is preferable, More preferably, it consists of an acidic salt of Keggin type heteropolyacid. The heteropolyacid compound further includes at least one element selected from the group consisting of vanadium and copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium (hereinafter referred to as “element Y”). It may be desirable to contain.

The composition of the heteropolyacid compound constituting the methacrylic acid production catalyst (target catalyst) is preferably as shown in the following formula (1) in the state of a new catalyst before use.
PaMobVcXdYeOx (1)
(In the formula (1), P, Mo and V represent phosphorus, molybdenum and vanadium, respectively, X represents at least one element X selected from the group consisting of potassium, rubidium, cesium and thallium, Y represents copper, Represents at least one element (element Y) selected from the group consisting of arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium, O represents oxygen, and when b = 12, 0 < a ≦ 3, 0 ≦ c ≦ 3, 0 <d ≦ 3, 0 ≦ e ≦ 3, and x is a value determined by the oxidation state of each element)
In particular, in the composition of the heteropolyacid compound constituting the methacrylic acid production catalyst (target catalyst), the atomic ratio of element X to molybdenum (X / Mo) is 0.5 / 12 to 2/12. preferable.

  The catalyst for producing methacrylic acid (target catalyst) includes, for example, a compound containing each of the above-described elements constituting a heteropolyacid compound (for example, oxo acid, oxo acid salt, oxide, nitrate, carbonate, bicarbonate of each element) Salts, hydroxides, halides, etc.) may be mixed, formed into a desired shape, then fired, etc. For example, phosphoric acid, phosphate and the like are used as the compound containing phosphorus, and molybdate such as molybdic acid and ammonium molybdate, molybdenum oxide, molybdenum chloride and the like are used as the compound containing molybdenum, and vanadium. As the compound containing Vanadate, vanadate (metavanadate) such as ammonium vanadate (ammonium metavanadate), vanadium oxide, vanadium chloride, etc. are used. As the compound containing element X, potassium oxide, oxidation Oxides such as rubidium, cesium oxide, potassium nitrate, rubidium nitrate, cesium nitrate, nitrates such as thallium nitrate, carbonates such as potassium carbonate, rubidium carbonate, cesium carbonate, bicarbonates such as potassium bicarbonate, cesium bicarbonate, water Potassium oxide, ruby hydroxide Um, such as hydroxides of cesium hydroxide, potassium chloride, rubidium chloride, cesium fluoride, cesium chloride, cesium bromide, such halides such as cesium iodide is used. Examples of the compound containing the element Y include oxo acids, oxo acid salts, oxides, nitrates, carbonates, hydroxides, halides, and the like.

  In general, when a target catalyst that has been set to the preferred catalyst composition described above in the state of a new catalyst before use is used for the production of methacrylic acid, the catalytic activity may be reduced due to heat load or the like. In the regeneration method of the present invention, the spent catalyst having reduced catalytic activity is subjected to regeneration treatment, and two kinds of aqueous slurry are mixed, dried and fired, whereby the atomic ratio of element X to molybdenum (X / Mo) is within the above-described range.

The regeneration method of the present invention is to obtain a regenerated catalyst through the above steps (I) to (III).
In step (I), the spent catalyst, nitrate radical, ammonium radical and water are mixed, and the atomic ratio of element X to molybdenum (X / Mo) in the resulting slurry is 2/12 to 4/12, Preferably, it adjusts so that it may become 2.5 / 12-3.5 / 12, and the aqueous slurry A is obtained. Here, the conversion rate and selectivity in the obtained regenerated catalyst are improved by mixing the nitrate group and the ammonium group.

  In order to mix the nitrate radicals, for example, nitrates including the elements constituting the target catalyst, nitrates such as nitric acid and ammonium nitrate, etc. may be used as the nitrate root supply source. As the ammonium root supply source, for example, ammonium salts containing elements constituting the target catalyst, ammonium salts such as ammonia, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, and ammonium acetate may be used. Preferably, a nitrate or ammonium salt containing an element constituting the target catalyst is used as a nitrate radical source or an ammonium radical source, and the ratio of nitrate radical to ammonium radical is within the range described below. In order to adjust, it is preferable to use nitric acid, ammonia, or ammonium nitrate.

  In the aqueous slurry A obtained in the step (I), the ratio of the nitrate root to the ammonium root is preferably 0.1 to 3.0 moles of ammonium roots per 1 mole of nitrate roots. More preferably, the ammonium radicals are 0.5 to 2.5 moles per mole of nitrate radicals. If the amount of ammonium radical is outside the above range, the catalytic activity may not be sufficiently recovered.

  When preparing the aqueous slurry A, it is necessary to adjust the atomic ratio (X / Mo) of the element X to the molybdenum present in the aqueous slurry A to be in the above-described range (X / Mo ratio in the aqueous slurry A). It is. Specifically, the adjustment of the atomic ratio may be performed by adding at least one of a compound containing element X (element X-containing compound) and a molybdenum compound, and the mixing amount of the spent catalyst before being subjected to regeneration is adjusted. After analyzing the catalyst composition (type and amount of component) by fluorescent X-ray analysis, ICP emission analysis, etc., based on the catalyst composition of this used catalyst, after adding element X-containing compound and / or molybdenum compound What is necessary is just to determine so that the atomic ratio (X / Mo) of the element X with respect to molybdenum in the composition of may become the range mentioned above. Normally, the element X-containing compound is added in consideration of the amount of molybdenum in the spent catalyst. However, when molybdenum is scattered and disappears due to heat load due to long-term use in the production of methacrylic acid. Depending on the amount of reduction, the composition of the spent catalyst may be the X / Mo ratio in the aqueous slurry A described above. In such a case, do not add both the element X-containing compound and the molybdenum compound. There can be.

  As the molybdenum compound and the element X-containing compound to be mixed in the preparation of the aqueous slurry A, one or more kinds of the molybdenum-containing compound and the element X-containing compound that can be used for the production of the target catalyst described above are appropriately selected. Just choose.

  In preparing the aqueous slurry A, a compound containing a catalyst constituent element other than molybdenum and element X can be added as needed based on the catalyst composition of the used catalyst. As the compound containing catalyst constituent elements other than molybdenum and element X, one or more kinds may be appropriately selected from the compounds containing each element that can be used for the production of the target catalyst described above.

As water to be mixed in the preparation of the aqueous slurry A, ion exchange water is usually used. The amount of water mixed is usually 1 to 20 parts by weight with respect to 1 part by weight of molybdenum in the aqueous slurry A obtained (total of molybdenum contained in the used catalyst and molybdenum compound added). .
When preparing the aqueous slurry A, the mixing order of the components described above is not particularly limited, and may be set as appropriate.

  When preparing the aqueous slurry A, the spent catalyst may be used for mixing as it is, or may be subjected to heat treatment as a pretreatment in advance.

  The treatment temperature of the heat treatment performed as a pretreatment of the spent catalyst is not particularly limited, but is preferably 350 to 600 ° C. The treatment time for heat treatment is not particularly limited, but is usually 0.1 to 24 hours, preferably 0.5 to 10 hours. Further, the heat treatment performed as a pretreatment of the used catalyst may be performed in an atmosphere of an oxidizing gas such as an oxygen-containing gas, or may be performed in an atmosphere of a non-oxidizing gas such as nitrogen.

Moreover, when the used catalyst used for preparation of the aqueous slurry A is a molded body, it may be used as it is, but if necessary, it can be pulverized by a conventionally known method in advance. However, if the molded body (used catalyst) contains fibers or the like that develop the strength of the catalyst, if these fibers are cut, there is a concern that the strength may be lowered, so that the fibers or the like are not cut. It is preferable to adjust the degree of grinding.
In addition, when performing both the pulverization treatment and the heat treatment performed as a pretreatment to the spent catalyst used for the preparation of the aqueous slurry A, the order of both treatments is not particularly limited, but usually the heat treatment is performed after the pulverization treatment. Applied.

  In the aqueous slurry A obtained in the step (I), the pH of the liquid phase is preferably 8 or less. If the pH of the liquid phase of the aqueous slurry A exceeds 8, the catalytic activity may not be sufficiently recovered.

  In the step (II), the atomic ratio (X / Mo) of the element X to molybdenum in the obtained slurry of the raw compound of the heteropolyacid compound constituting the target catalyst and water is 0/12 to 0.5 / 12. The aqueous slurry B is preferably obtained by adjusting the mixture so that it is 0/12 to 0.3 / 12.

  In the preparation of the aqueous slurry B, a compound containing at least molybdenum is used as a raw material compound of the heteropolyacid compound, and the atomic ratio (X / Mo) of element X to molybdenum with respect to the compound containing molybdenum is within the above-described range ( A compound containing the element X is used so that the X / Mo ratio in the aqueous slurry B). Therefore, when the atomic ratio of element X to molybdenum (X / Mo) is set to 0/12, the compound containing element X does not necessarily have to be mixed.

  As the molybdenum compound and the element X-containing compound to be mixed in the preparation of the aqueous slurry B, one or more of the molybdenum-containing compound and the element X-containing compound that can be used for the production of the target catalyst described above are appropriately used. Just choose.

  In preparing the aqueous slurry B, a compound containing a catalyst constituent element other than molybdenum and the element X can be added as necessary. As the compound containing catalyst constituent elements other than molybdenum and element X, one or more kinds may be appropriately selected from the compounds containing each element that can be used for the production of the target catalyst described above.

As water to be mixed in the preparation of the aqueous slurry B, ion-exchanged water is usually used. The mixing amount of water is usually 1 to 20 parts by weight with respect to 1 part by weight of molybdenum in the obtained aqueous slurry B.
When preparing the aqueous slurry B, the mixing order of the components described above is not particularly limited, and may be set as appropriate.

  In step (III), first, the aqueous slurry A obtained in step (I) and the aqueous slurry B obtained in step (II) are mixed. The mixing ratio of the aqueous slurry A and the aqueous slurry B is determined by considering the amounts of molybdenum and element X contained in both slurries, and the atoms of element X with respect to molybdenum in the heteropolyacid compound constituting the finally obtained regenerated catalyst. The ratio (X / Mo) may be 0.5 / 12 to 2/12.

The mixing order, temperature, stirring conditions and the like when mixing the aqueous slurry A and the aqueous slurry B are not particularly limited, and may be set as appropriate.
When the aqueous slurry A and the aqueous slurry B are mixed, during the aging treatment described later or after the aging treatment, a compound containing the catalyst constituent element of the target catalyst, if necessary, a compound containing the element Y among them Can also be mixed. In that case, it is usually preferable to add a compound containing a catalyst constituent element (such as a compound containing the element Y) suspended in water. What is necessary is just to set those mixing amounts suitably so that the composition of the heteropolyacid compound which comprises the regenerated catalyst finally obtained may become a preferable composition of the object catalyst in the state of the new catalyst before use mentioned above.

  In step (III), the mixed slurry obtained by mixing aqueous slurry A and aqueous slurry B is then subjected to drying. The drying method at the time of drying is not particularly limited, and for example, a method usually used in this field such as an evaporation to dryness method, a spray drying method, a drum drying method, and an airflow drying method can be employed. The drying conditions may be appropriately set so that the water content in the mixed slurry is sufficiently reduced, and is not particularly limited, but the temperature is usually less than 300 ° C.

  The mixed slurry obtained by mixing the aqueous slurry A and the aqueous slurry B is preferably subjected to an aging treatment for aging by heating at 100 ° C. or higher in a closed container before being subjected to the drying described above. By subjecting the mixed slurry to such aging treatment, the catalyst activity can be effectively recovered. The upper limit of the heating temperature in the aging treatment is preferably 200 ° C. or less, and more preferably 150 ° C. or less. In order to obtain a sufficient activity recovery effect, the heating time in the aging treatment is usually 0.1 hour or longer, preferably 2 hours or longer, and 20 hours or shorter from the viewpoint of productivity.

  In step (III), the dried product obtained after the drying is then subjected to calcination. Firing can be performed by a method usually used in this field, and is not particularly limited. For example, it may be performed in an atmosphere of an oxidizing gas such as oxygen, or may be performed in an atmosphere of a non-oxidizing gas such as nitrogen, and the firing temperature is usually 300 ° C. or higher. Among them, in order to recover the catalyst life satisfactorily, it is preferable to perform multi-stage calcination in an atmosphere of oxidizing gas or non-oxidizing gas. First-stage calcination is performed in the atmosphere of oxidizing gas, and then non-oxidizing gas. It is more preferable to employ a two-stage firing method in which the second-stage firing is performed in an atmosphere of

  The oxidizing gas used for firing is a gas containing an oxidizing substance, and examples thereof include an oxygen-containing gas. In the case of using an oxygen-containing gas, the oxygen concentration is usually about 1 to 30% by volume. As the oxygen source, air or pure oxygen is usually used, and diluted with an inert gas as necessary. . The oxidizing gas may contain moisture as required, but the concentration is usually 10% by volume or less. Of these, air is preferable as the oxidizing gas. Firing performed in an oxidizing gas atmosphere is usually performed under such an oxidizing gas stream. Moreover, the temperature of baking performed in oxidizing gas atmosphere is 360-410 degreeC normally, Preferably it is 380-400 degreeC.

  The non-oxidizing gas used for the firing is a gas that does not substantially contain an oxidizing substance such as oxygen, and examples thereof include inert gases such as nitrogen, carbon dioxide, helium, and argon. The non-oxidizing gas may contain moisture as required, but the concentration is usually 10% by volume or less. Of these, nitrogen is preferable as the non-oxidizing gas. Firing performed in a non-oxidizing gas atmosphere is usually performed under such a non-oxidizing gas stream. Moreover, the temperature of baking performed in non-oxidizing gas atmosphere is 420-500 degreeC normally, Preferably it is 420-450 degreeC.

  The dried product obtained after the drying is subjected to a heat treatment that is maintained at a temperature of about 180 to 300 ° C. in an oxidizing gas or non-oxidizing gas atmosphere as pre-baking prior to the above-described baking. Is preferred.

  The dried product obtained after the drying is subjected to a forming process for forming into a desired shape (ring shape, pellet shape, spherical shape, cylindrical shape, etc.) as necessary before being subjected to the above-described firing or pre-firing. be able to. The molding process may be performed by a method usually used in this field, such as tableting molding or extrusion molding. In the molding treatment, water, a molding aid, a pore agent and the like can be added to the dried product as necessary. Examples of the molding aid include ammonium nitrate as well as ceramic fiber and glass fiber. In particular, ammonium nitrate has not only a function as a molding aid but also a function as a pore agent.

  It is preferable that the molded body obtained by the molding process is subsequently subjected to a temperature and humidity control process. A more stable catalyst can be obtained by subjecting the temperature and humidity control treatment to calcination or pre-calcination. Specifically, the temperature control and humidity control treatment is performed by exposing the molded body for about 0.5 to 10 hours in an atmosphere of 40 to 100 ° C. and a relative humidity of 10 to 60%. The treatment may be performed, for example, in a temperature-controlled and humidity-controlled tank or by spraying a temperature-controlled and humidity-controlled gas on the molded body. In addition, air is usually used as the atmospheric gas for the treatment, but an inert gas such as nitrogen may be used.

Thus, it is possible to obtain a regenerated catalyst whose catalytic activity has been successfully recovered. Similar to the target catalyst, this regenerated catalyst is made of a heteropolyacid compound, may be made of a free heteropolyacid, or may be made of a salt of a heteropolyacid. Especially, what consists of an acidic salt of heteropolyacid is preferable, and what consists of acidic salt of a Keggin type heteropolyacid is more preferable. Further, the atomic ratio (X / Mo) of element X to molybdenum in the heteropolyacid compound constituting the regenerated catalyst is 0.5 / 12 to 2/12, and preferably the same preferred composition as that of the target catalyst described above. Have
The method for regenerating a catalyst for producing methacrylic acid according to the present invention is intended for regeneration of a used catalyst obtained by producing methacrylic acid. The regeneration method of the present invention can also be carried out on a catalyst that is not used in the production of methacrylic acid, such as a catalyst that does not have the desired performance. In such a case, the spent catalyst is regenerated. As in the case, good effects can be obtained.

  The method for producing methacrylic acid of the present invention comprises a compound selected from the group consisting of methacrolein, isobutyraldehyde, isobutane and isobutyric acid in the presence of the catalyst for producing methacrylic acid regenerated by the regeneration method of the present invention (hereinafter referred to as “ (Sometimes referred to as “methacrylic acid raw material”) is subjected to a gas phase catalytic oxidation reaction. Thus, by using the regenerated catalyst of the present invention, methacrylic acid can be produced with good conversion and selectivity.

  The production of methacrylic acid is usually performed by filling a fixed bed multitubular reactor with a catalyst and supplying the raw material gas containing the methacrylic acid raw material and oxygen to the reactor, but the present invention is not limited to this. Alternatively, a reaction mode such as a fluidized bed or a moving bed can be adopted. Air is usually used as the oxygen source. Further, the raw material gas may contain nitrogen, carbon dioxide, carbon monoxide, water vapor and the like as components other than the methacrylic acid raw material and oxygen.

  The methacrylic acid raw material contained in the raw material gas is not necessarily a high-purity purified product. For example, methacrolein includes methacrolein obtained by a gas phase catalytic oxidation reaction of isobutylene or t-butyl alcohol. A reaction product gas can also be used. In addition, the methacrylic acid raw material contained in the said raw material gas may be only 1 type, and 2 or more types may be sufficient as it.

What is necessary is just to set suitably the reaction conditions in manufacture of methacrylic acid according to the kind etc. of the methacrylic acid raw material contained in raw material gas. For example, when using methacrolein as the methacrylic acid raw material, the concentration of methacrolein in the raw material gas is usually 1 to 10% by volume, the water vapor concentration is 1 to 30% by volume, and the molar ratio of oxygen to methacrolein is 1 to 5, The reaction is carried out under conditions where the space velocity is 500 to 5000 h −1 (standard condition standard), the reaction temperature is 250 to 350 ° C., and the reaction pressure is 0.1 to 0.3 MPa. On the other hand, when isobutane is used as the methacrylic acid raw material, the isobutane concentration in the raw material gas is usually 1 to 85% by volume, the water vapor concentration is 3 to 30% by volume, the molar ratio of oxygen to isobutane is 0.05 to 4, and the space The reaction is carried out under conditions where the speed is 400 to 5000 h −1 (standard condition standard), the reaction temperature is 250 to 400 ° C., and the reaction pressure is 0.1 to 1 MPa. In addition, when isobutyraldehyde or isobutyric acid is used as the methacrylic acid raw material, generally the same reaction conditions as when methacrolein is used as the raw material are employed.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these.
The air used below contains 3.5% by volume of water (corresponding to the atmosphere), and nitrogen used below contains substantially no water.

The analysis and evaluation of the catalyst obtained in each of the following examples were performed as follows.
<Catalyst composition (ratio of constituent elements)>
Using a fluorescent X-ray analyzer (“ZSX Primus II” manufactured by Rigaku Corporation), the catalyst was determined by fluorescent X-ray analysis.

<Catalyst activity test>
9 g of catalyst was filled in a glass microreactor having an inner diameter of 16 mm, and a raw material gas prepared by mixing methacrolein, air, steam and nitrogen (composition: methacrolein 4 vol%, molecular oxygen 12 vol%, Steam 17 volume%, nitrogen 67 volume%) was supplied at a space velocity of 670 h −1 , and once the reaction was performed at 355 ° C. for 1 hour at the furnace temperature (furnace temperature for heating the microreactor), A raw material gas having the same composition was supplied at the same space velocity as described above, and the reaction was performed at a furnace temperature of 280 ° C. From this reaction start (after setting the furnace temperature to 280 ° C.), the outlet gas (gas after reaction) after 1 hour was sampled, analyzed by gas chromatography, and methacrolein conversion rate (%) based on the following formula The methacrylic acid selectivity (%) and yield (%) were determined.

Conversion rate of methacrolein (%) = [number of moles of reacted methacrolein ÷ number of moles of methacrolein supplied] × 100
Methacrylic acid selectivity (%) = [number of moles of methacrylic acid produced / number of moles of reacted methacrolein] × 100
Yield (%) = [conversion (%) × selectivity (%)] ÷ 100

(Reference Example 1-Preparation of a new catalyst)
In 224 kg of ion-exchanged water heated to 40 ° C., 38.2 kg of cesium nitrate [CsNO 3 ], 27.4 kg of 75% by weight orthophosphoric acid, and 25.2 kg of 70% by weight nitric acid were dissolved to obtain α liquid. On the other hand, after 297 kg of ammonium molybdate tetrahydrate [(NH 4 ) 6 Mo 7 O 24 · 4H 2 O] was dissolved in 330 kg of ion-exchanged water heated to 40 ° C., ammonium metavanadate [NH 4 VO 3 ] 8.19 kg was suspended and this was made into beta solution.

While maintaining the temperature of the α liquid and the β liquid at 40 ° C., the α liquid was added dropwise to the β liquid with stirring, and then stirred at 120 ° C. for 5.8 hours in a sealed container. Next, 10.2 kg of antimony trioxide [Sb 2 O 3 ] and 10.2 kg of copper nitrate trihydrate [Cu (NO 3 ) 2 .3H 2 O] were suspended in 23 kg of ion-exchanged water. After that, the mixture was stirred in a sealed container at 120 ° C. for 5 hours. The slurry thus obtained was dried with a spray dryer, and 4 parts by weight of ceramic fiber, 13 parts by weight of ammonium nitrate, and 9.7 parts by weight of ion-exchanged water were added to and kneaded with 100 parts by weight of the obtained dry powder. Thereafter, it was extruded into a cylindrical shape having a diameter of 5 mm and a height of 6 mm. The obtained molded body was dried at a temperature of 90 ° C. and a relative humidity of 30% for 3 hours, and then held in a nitrogen stream at 435 ° C. for 3 hours, and then kept in an air stream at 390 ° C. for 3 hours. After that, the molded body was taken out and used as a new catalyst.

  The new catalyst obtained is from a heteropolyacid compound containing phosphorus, molybdenum, vanadium, antimony, copper and cesium in atomic ratios of 1.5, 12, 0.50, 0.5, 0.3 and 1.4, respectively. It was. The results of the activity test of this new catalyst are shown in Table 1.

(Reference Example 2-Preparation of spent catalyst)
The new catalyst obtained in Reference Example 1 was subjected to methacrolein catalytic gas phase oxidation reaction for a predetermined time to obtain a used catalyst.
The atomic ratio of the metal elements excluding oxygen in the heteropolyacid compound constituting the obtained spent catalyst was 1.3, 9.6, 0.48, 0.8 for phosphorus, molybdenum, vanadium, antimony, copper, and cesium, respectively. 5, 0.3 and 1.4. The results of the activity test of this spent catalyst are shown in Table 1.

Example 1
[Step (I): Preparation of aqueous slurry A]
100 g of the used catalyst obtained in Reference Example 2 was added to 200 g of ion-exchanged water and stirred. Next, 15.8 g of molybdenum trioxide [MoO 3 ] as a molybdenum source, 1.3 g of 75 wt% orthophosphoric acid as a phosphorus source, and ammonium metavanadate as a vanadium source to make up for the insufficient components of the used catalyst relative to the new catalyst. 0.1 g was added, and further 17.9 g of cesium nitrate and 27.0 g of ammonium nitrate [NH 4 NO 3 ] were added, and then the temperature was raised to 70 ° C. and kept at the same temperature for 1 hour. Next, 6.23 g of 25 wt% aqueous ammonia was added and held at 70 ° C. for 1 hour, and then stirred at 120 ° C. for 5 hours in an airtight container to obtain an aqueous slurry A1. The molar ratio of ammonium radicals to nitrate radicals in the obtained aqueous slurry A1 was 1.0, and the pH of the liquid phase of the aqueous slurry A1 was 2.8. The atomic ratio of the metal elements contained in the aqueous slurry A1 is 1.5, 12, 0.50, 0.5, 0.3, and 3.2 for phosphorus, molybdenum, vanadium, antimony, copper, and cesium, respectively. Yes, the atomic ratio of cesium to molybdenum was 3.2 / 12.

[Step (II): Preparation of aqueous slurry B]
In 105 g of ion-exchanged water heated to 40 ° C., 12.9 g of 75 wt% orthophosphoric acid and 12.3 g of 67.5 wt% nitric acid were dissolved, and this was designated as solution a. On the other hand, after 139 g of ammonium molybdate tetrahydrate was dissolved in 165 g of ion-exchanged water heated to 40 ° C., 3.85 g of ammonium metavanadate was suspended, and this was designated as solution b. While maintaining the temperature of the liquid a and liquid b at 40 ° C., the liquid a was dropped into the liquid b with stirring to obtain an aqueous slurry B1. The atomic ratio of the metal elements contained in this aqueous slurry B1 is 1.5, 12, and 0.50 for phosphorus, molybdenum, and vanadium, respectively (antimony, copper, and cesium are all 0). The atomic ratio was 0/12.

[Step (III): Mixing of aqueous slurry A and aqueous slurry B]
After the total amount of the aqueous slurry B1 was mixed with the total amount of the aqueous slurry A1, the mixture was stirred for 5 hours at 120 ° C. in a sealed container, and then 4.80 g of antimony trioxide and 4.76 g of copper nitrate trihydrate were added. And added in a state of being suspended in 11.0 g of ion-exchanged water, and then stirred at 120 ° C. for 5 hours in a sealed container. The mixed slurry thus obtained was dried at 135 ° C., and 2 parts by weight of ceramic fiber, 14 parts by weight of ammonium nitrate, and 7.4 parts by weight of ion-exchanged water were added to 100 parts by weight of the obtained dried product and kneaded. Then, it was extruded into a cylindrical shape having a diameter of 5 mm and a height of 6 mm. The obtained molded body was dried at a temperature of 90 ° C. and a relative humidity of 30% for 3 hours, and then held in an air stream at 390 ° C. for 4 hours, and then held in a nitrogen stream at 435 ° C. for 4 hours. After that, the molded body was taken out and used as a regenerated catalyst (1).

  The obtained regenerated catalyst (1) is composed of a heteropolyacid compound, and the atomic ratio of metal elements excluding oxygen of the heteropolyacid compound is 1.5 for phosphorus, molybdenum, vanadium, antimony, copper and cesium, respectively. 12, 0.50, 0.5, 0.3, and 1.4, and the atomic ratio of cesium to molybdenum was 1.4 / 12. The results of the activity test of this regenerated catalyst (1) are shown in Table 1.

(Example 2)
Except that the amount of 25 wt% aqueous ammonia used in the preparation of the aqueous slurry A in Step (I) of Example 1 was changed from 6.23 g to 2.74 g, the same as Step (I) in Example 1 Operation was performed to obtain an aqueous slurry A2. The molar ratio of ammonium radicals to nitrate radicals in the obtained aqueous slurry A2 was 0.9, and the pH of the liquid phase of the aqueous slurry A2 was 1.6. Note that the atomic ratio of metal elements contained in the aqueous slurry A2 (the atomic ratio of cesium to molybdenum) is the same as that of the aqueous slurry A1 obtained in Example 1.
Next, using this aqueous slurry A2 and the aqueous chiller B1 obtained in the same manner as in Step (II) of Example 1, the same operation as in Step (III) of Example 1 was carried out to produce a regenerated catalyst ( 2) was obtained.

  The obtained regenerated catalyst (2) is composed of a heteropolyacid compound, and the atomic ratio of metal elements excluding oxygen of the heteropolyacid compound is 1.5 for phosphorus, molybdenum, vanadium, antimony, copper and cesium, respectively. 12, 0.50, 0.5, 0.3, and 1.4, and the atomic ratio of cesium to molybdenum was 1.4 / 12. The results of the activity test of this regenerated catalyst (2) are shown in Table 1.

Example 3
100 g of the used catalyst obtained in Reference Example 2 was added to 200 g of ion-exchanged water and stirred. Next, in order to make up for the insufficient components of the spent catalyst relative to the new catalyst, 15.8 g of molybdenum trioxide as the molybdenum source, 1.3 g of 75 wt% orthophosphoric acid as the phosphorus source, and 0.1 g of ammonium metavanadate as the vanadium source, Then, the temperature was raised to 40 ° C. Subsequently, 37.6 g of 25 wt% aqueous ammonia was added and held at 40 ° C. for 1 hour, then 19.1 g of 67.5 wt% nitric acid was added and held at 40 ° C. for 1 hour, and further 40 ° C. An aqueous solution in which 17.9 g of cesium nitrate was dissolved was added to 54 g of ion-exchanged water heated to 1, and kept at 40 ° C. for 15 minutes to obtain an aqueous slurry A3. The molar ratio of ammonium root to nitrate radical in the obtained aqueous slurry A3 was 1.9, and the pH of the liquid phase of the aqueous slurry A3 was 6.3. The atomic ratio of the metal elements contained in the aqueous slurry A3 is 1.5, 12, 0.50, 0.5, 0.3, and 3.2 for phosphorus, molybdenum, vanadium, antimony, copper, and cesium, respectively. Yes, the atomic ratio of cesium to molybdenum was 3.2 / 12.
Next, using this aqueous slurry A3 and the aqueous chiller B1 obtained in the same manner as in Step (II) of Example 1, the same operation as in Step (III) of Example 1 was carried out to produce a regenerated catalyst ( 3) was obtained.

  The obtained regenerated catalyst (3) is composed of a heteropolyacid compound, and the atomic ratio of metal elements excluding oxygen of the heteropolyacid compound is 1.5 for phosphorus, molybdenum, vanadium, antimony, copper and cesium, respectively. 12, 0.50, 0.5, 0.3, and 1.4, and the atomic ratio of cesium to molybdenum was 1.4 / 12. The results of the activity test of this regenerated catalyst (3) are shown in Table 1.

(Comparative Example 1)
200 g of the spent catalyst obtained in Reference Example 2 was added to 400 g of ion-exchanged water and stirred. Next, 31.5 g of molybdenum trioxide as a molybdenum source, 2.7 g of 75 wt% orthophosphoric acid as a phosphorus source, and 0.2 g of ammonium metavanadate as a vanadium source to compensate for the deficient components of the spent catalyst relative to the new catalyst After adding 69.2 g of ammonium nitrate, the temperature was raised to 70 ° C. and kept at that temperature for 1 hour. Thereafter, 41.2 g of 25 wt% aqueous ammonia was added and held at 70 ° C. for 1 hour, and then stirred at 120 ° C. for 5 hours in an airtight container to obtain an aqueous slurry C1. The molar ratio of ammonium radical to nitrate radical in the obtained aqueous slurry C1 was 1.7, and the pH of the liquid phase of the aqueous slurry C1 was 4.2. The atomic ratio of the metal elements contained in the aqueous slurry C1 is 1.5, 12, 0.5, 0.5, 0.3, and 1.4 for phosphorus, molybdenum, vanadium, antimony, copper, and cesium, respectively. Yes, the atomic ratio of cesium to molybdenum was 1.4 / 12.

  The aqueous slurry C1 thus obtained was dried at 135 ° C., and 2 parts by weight of ceramic fiber, 14 parts by weight of ammonium nitrate, and 7.4 parts by weight of ion-exchanged water were added to 100 parts by weight of the obtained dried product. After kneading, it was extruded into a cylindrical shape having a diameter of 5 mm and a height of 6 mm. The obtained molded body is dried at a temperature of 90 ° C. and a relative humidity of 30% for 3 hours, and then kept in an air stream at 390 ° C. for 4 hours, and then in a nitrogen stream at 435 ° C. for 4 hours. After that, the molded body was taken out and used as a comparative regenerated catalyst (C1).

  The obtained regenerated catalyst (C1) is composed of a heteropolyacid compound, and the atomic ratio of metal elements excluding oxygen in the heteropolyacid compound is 1.5 for phosphorus, molybdenum, vanadium, antimony, copper, and cesium, respectively. 12, 0.5, 0.5, 0.3, and 1.4, and the atomic ratio of cesium to molybdenum was 1.4 / 12. The results of the activity test of this regenerated catalyst (C1) are shown in Table 1.

Claims (5)

  1. A method for regenerating a catalyst for methacrylic acid production comprising a heteropolyacid compound comprising phosphorus, molybdenum, and at least one element X selected from the group consisting of potassium, rubidium, cesium and thallium,
    Including the following steps (I) to (III), the atomic ratio (X / Mo) of element X to molybdenum in the heteropolyacid compound constituting the regenerated catalyst is 0.5 / 12 to 2/12 A method for regenerating a catalyst for producing methacrylic acid.
    Step (I): A spent catalyst obtained by using methacrylic acid, a nitrate radical, an ammonium radical and water are mixed, and the atomic ratio of element X to molybdenum (X / Mo) is 2/12 to 4 / A step of obtaining an aqueous slurry A adjusted to be 12.
    Step (II): Aqueous slurry B prepared by mixing the heteropolyacid compound raw material compound with water and adjusting the atomic ratio of element X to molybdenum (X / Mo) to be 0/12 to 0.5 / 12. Obtaining.
    Step (III): A step of mixing the aqueous slurry A obtained in step (I) and the aqueous slurry B obtained in step (II), followed by drying and firing.
  2.   2. The method for regenerating a catalyst for methacrylic acid production according to claim 1, wherein the aqueous slurry A obtained in the step (I) contains 0.1 to 3.0 moles of ammonium roots per 1 mole of nitrate radicals.
  3.   The method for regenerating a catalyst for methacrylic acid production according to claim 1 or 2, wherein the pH of the liquid phase of the aqueous slurry A obtained in step (I) is 8 or less.
  4.   The heteropolyacid compound further comprises vanadium and at least one element selected from the group consisting of copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum, and cerium. The regeneration method of the catalyst for methacrylic acid manufacture in any one.
  5.   A catalyst selected from the group consisting of methacrolein, isobutyraldehyde, isobutane and isobutyric acid is regenerated in the presence of the regenerated catalyst by regenerating the catalyst for producing methacrylic acid by the method according to any one of claims 1 to 4. A method for producing methacrylic acid, which is subjected to a gas phase catalytic oxidation reaction.
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US8586499B2 (en) 2009-10-30 2013-11-19 Sumitomo Chemical Company, Limited Method for producing catalyst for preparation of methacrylic acid and method for preparing methacrylic acid
JP2014226614A (en) * 2013-05-23 2014-12-08 住友化学株式会社 Method for producing catalyst for producing methacrylic acid, and method for producing methacrylic acid

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