KR20100101533A - Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid - Google Patents

Method for regenerating catalyst for the production of methacrylic acid and process for preparing methacrylic acid Download PDF

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KR20100101533A
KR20100101533A KR1020100020328A KR20100020328A KR20100101533A KR 20100101533 A KR20100101533 A KR 20100101533A KR 1020100020328 A KR1020100020328 A KR 1020100020328A KR 20100020328 A KR20100020328 A KR 20100020328A KR 20100101533 A KR20100101533 A KR 20100101533A
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catalyst
aqueous slurry
molybdenum
methacrylic acid
compound
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KR101640255B1 (en
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준지 시바따
에이이찌 시라이시
도시아끼 미야따께
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스미또모 가가꾸 가부시키가이샤
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    • 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
    • B01J38/02Heat treatment
    • 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
    • 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
    • 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

The present invention is a regeneration method of a catalyst for producing methacrylic acid comprising a heteropolyacid compound containing phosphorus, molybdenum and an element X selected from potassium, rubidium, cesium and thallium, wherein (I) deterioration recovered from the method for producing methacrylic acid Mixing the catalyst, nitrate ions, ammonium ions and water to obtain an aqueous slurry A adjusted so that the atomic ratio (X: Mo) of the element X to molybdenum is from 2:12 to 4:12; (II) mixing the raw material compound of the heteropolyacid compound and water to obtain an aqueous slurry B adjusted so that the atomic ratio (X: Mo) of the element X to molybdenum is from 0:12 to 0.5: 12; (III) After mixing the aqueous slurry A obtained in the step (I) and the aqueous slurry B obtained in the step (II), the element X in the heteropolyacid compound constituting the regeneration catalyst, comprising the step of drying and firing the mixture. The atomic ratio of: molybdenum is 0.5: 12 to 2:12.

Description

Regeneration method of catalyst for methacrylic acid production and production method of methacrylic acid {METHOD FOR REGENERATING CATALYST FOR THE PRODUCTION OF METHACRYLIC ACID AND PROCESS FOR PREPARING METHACRYLIC ACID}

The present invention is subjected to regeneration treatment to a deterioration catalyst (catalyst used) comprising a heteropolyacid compound containing phosphorus, molybdenum, and at least one element X selected from the group consisting of potassium, rubidium, cesium and thallium, and methacrylic acid A method for regenerating a production catalyst and a method for producing methacrylic acid using a regeneration catalyst obtained by such a regeneration method.

The catalyst for producing methacrylic acid containing a heteropolyacid compound containing phosphorus, molybdenum and at least one element X selected from the group consisting of potassium, rubidium, cesium and thallium is, for example, a gas phase using methacrolein or the like as a raw material. When used for a long time in a catalytic oxidation reaction, it is known that catalyst activity falls by heat load etc.

As a method for regenerating such a deterioration catalyst, JP-A-2008-80232, JP-A-2008-86928 and JP-A-2008-93595 are mixed with a deterioration catalyst with nitrate ions and ammonium ions to obtain an aqueous slurry, and the slurry is Disclosed is a method for regenerating a deterioration catalyst comprising drying to obtain a dried catalyst and then calcining the dried catalyst.

However, the regenerated catalyst obtained by the conventional method was not necessarily satisfactory in terms of catalytic activity.

It is an object of the present invention to provide a method for regenerating a catalyst for producing methacrylic acid, which can favorably restore the catalytic activity of such a catalyst.

It is also an object of the present invention to provide a method for producing methacrylic acid at high conversion and selectivity using the regeneration catalyst obtained by the regeneration method of the present invention.

In order to achieve the above object, the present invention provides a method for regenerating a catalyst for producing methacrylic acid comprising a heteropolyacid compound containing at least one element X selected from the group consisting of phosphorus, molybdenum, potassium, rubidium, cesium and thallium. And an atomic ratio (X: Mo) of the element X to molybdenum in the heteropolyacid compound constituting the regenerated catalyst, comprising the following steps (I) to (III): 0.5: 12 to 2:12 A method for regenerating a catalyst for producing methacrylic acid is provided.

Step (I): The deterioration catalyst, nitrate ions, ammonium ions and water recovered from the process for producing methacrylic acid are mixed so that the atomic ratio (X: Mo) of element X to molybdenum is 2:12 to 4:12. Process of obtaining the aqueous slurry A adjusted so as to be.

Process (II): The process of mixing the raw material compound of a heteropolyacid compound, and water, and obtaining the aqueous slurry B adjusted so that the atomic ratio (X: Mo) of the element X with respect to molybdenum may be 0:12 to 0.5: 12.

Process (III): The process of drying and baking, after mixing the aqueous slurry A obtained by process (I) and the aqueous slurry B obtained by process (II).

In a preferred embodiment, the aqueous slurry A obtained in step (I) contains 0.1 to 3.0 moles of ammonium ions per mole of nitrate ions.

In another preferred embodiment, the pH of the liquid phase of the aqueous slurry A obtained in step (I) is 8 or less.

In another preferred embodiment, 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.

Moreover, this invention is the process of regenerating the catalyst for methacrylic acid production by the regeneration method which concerns on this invention, and

Provided is a method for producing methacrylic acid comprising a step of subjecting at least one compound selected from the group consisting of methacrolein, isobutylaldehyde, isobutane and isobutyric acid to gas phase catalytic oxidation in the presence of the regenerated catalyst.

According to the present invention, in regenerating the catalyst for methacrylic acid production, the catalytic activity can be recovered well. In addition, by using the regeneration catalyst obtained by the regeneration method of the present invention, methacrylic acid can be produced at high conversion and selectivity.

Hereinafter, the present invention will be described in detail.

The regeneration method of the catalyst for producing methacrylic acid of the present invention includes regenerating the deteriorated catalyst recovered from the catalyst used, that is, the methacrylic acid production step to obtain a regeneration catalyst.

At least one element selected from the group consisting of phosphorus, molybdenum, potassium, rubidium, cesium and thallium may be a catalyst for producing methacrylic acid which may be regenerated by the regeneration method of the present invention (hereinafter sometimes referred to as "target catalyst"). It is a catalyst containing the heteropolyacid compound containing X. The catalyst may comprise free heteropolyacids or salts of heteropolyacids. Especially, the catalyst containing the acid salt (partially neutralized salt) of heteropoly acid is preferable, and the catalyst containing the acid salt of Keggin type heteropoly acid is more preferable. Preferably, the heteropolyacid compound further comprises 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"). Sometimes).

It is preferable that the composition of the heteropolyacid compound which comprises the said catalyst for methacrylic acid production (target catalyst) is the same as that of following General formula (1) in the state of the new catalyst before use.

Figure pat00001

Wherein P, Mo and V represent phosphorus, molybdenum and vanadium, respectively; X represents at least one element (element X) selected from the group consisting of potassium, rubidium, cesium and thallium; Y represents at least one element (element Y) selected from the group consisting of copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium; O represents oxygen; a, b, c, d and e are numbers satisfying 0 <a ≦ 3, 0 ≦ c ≦ 3, 0 <d ≦ 3, 0 ≦ e ≦ 3 when b is 12; x is a value determined by the oxidation state of each element.

In particular, in the composition of the heteropolyacid compound constituting the catalyst for producing methacrylic acid (target catalyst), the atomic ratio (X: Mo) of the element X to molybdenum is preferably 0.5: 12 to 2:12.

The catalyst for producing methacrylic acid (target catalyst) is a conventionally known method, for example, a compound containing each of the above-mentioned elements constituting a heteropolyacid compound (for example, oxo acid, oxoacid salt, oxide, nitrate, Carbonates, bicarbonates, hydroxides, halides, etc.) may be mixed and molded into a desired shape, and then the molded mixture may be produced by baking. Examples of the phosphorus-containing compound include phosphoric acid, phosphate, and the like, and the compound containing molybdenum includes molybdates such as molybdate and ammonium molybdate, molybdenum oxide, molybdenum chloride, and the like. Vanadate, such as vanadate (methanabate), vanadium oxide, vanadium chloride, and the like, and compounds containing element X include potassium oxide, rubidium oxide, oxide Oxides such as cesium, potassium nitrate, rubidium nitrate, cesium nitrate, nitrates such as thallium nitrate, potassium carbonate, rubidium carbonate, carbonates such as cesium carbonate, bicarbonates such as potassium bicarbonate, cesium bicarbonate, potassium hydroxide, rubidium hydroxide, hydroxide Hydroxides such as cesium, potassium chloride, rubidium chloride, cesium fluoride, cesium chloride, halides such as cesium bromide, cesium iodide, and the like. do. In addition, examples of the compound containing element Y include oxo acid, oxo acid salt, oxide, nitrate salt, carbonate salt, hydroxide, halide and the like.

In general, when the target catalyst having the above-mentioned preferred catalyst composition is used for the production of methacrylic acid in the state of a new catalyst before use, the catalyst activity may be lowered due to heat load or the like. According to the regeneration method of the present invention, a deterioration catalyst in which the catalytic activity is thus reduced is subjected to regeneration treatment, two types of aqueous slurries, that is, slurry A and slurry B are mixed, and the mixture is dried and calcined to molybdenum. The atomic ratio (X: Mo) of the element X with respect to the above-mentioned range is made.

According to the regeneration method of the present invention, a regeneration catalyst is obtained through the steps (I) to (III) described above.

In step (I), the deterioration catalyst, nitrate ions, ammonium ions and water are mixed, and the atomic ratio (X: Mo) of the element X to molybdenum in the slurry obtained is 2:12 to 4:12, preferably 2.5: Adjust to 12 to 3.5: 12 to obtain aqueous slurry A. In the above process, by mixing nitrate ions and ammonium ions, the conversion and selectivity achieved by the regeneration catalyst obtained are improved.

In order to supply nitrate ions, for example, nitrates such as nitrate and ammonium nitrate can be used as the nitrate ion source, in addition to nitrate containing an element constituting the target catalyst. In order to supply ammonium ions, an ammonium salt such as ammonia, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium acetate or the like can be used as an ammonium ion source as well as an ammonium salt containing an element constituting the target catalyst. Preferably, as a source of nitrate ions and a source of ammonium ions, nitrate and ammonium salts containing elements constituting the target catalyst are used. More preferably, in order to adjust the ratio of nitrate ion and ammonium ion to the range mentioned later, nitric acid, ammonia, and ammonium nitrate are used.

In the aqueous slurry A prepared in step (I), the amount of the ammonium ion is preferably 0.1 to 3.0 moles, more preferably 0.5 to 2.5 moles, per 1 mole of nitrate ions. If the amount of ammonium ions is out of the above range, there is a fear that the catalytic activity may not be sufficiently recovered.

In preparing the aqueous slurry A, the atomic ratio (X: Mo) of the element X to molybdenum contained in the aqueous slurry A must be adjusted so as to be within the above-mentioned range (X: Mo ratio in the aqueous slurry A). Specifically, the atomic ratio can be adjusted by adding at least one of the compound (element X-containing compound) and the molybdenum compound containing the element X. The mixed amount of the compound is analyzed by fluorescence X-ray analysis, ICP emission analysis, etc. of the catalyst composition (type and amount of components) of the degradation catalyst before regeneration, and based on the catalyst composition of the degradation catalyst, an element X-containing compound and And / or after adding the molybdenum compound, the atomic ratio (X: Mo) of the element X to molybdenum in the composition can be determined to be in the above-described range. Usually, the element X containing compound is added in consideration of the molybdenum amount of a degradation catalyst. In the case where molybdenum is scattered and lost due to heat load by using the catalyst for a long time in the production of methacrylic acid, or the like, the composition of the deterioration catalyst depends on the amount of reduction of the element X and / or molybdenum. It may be set in the range of Mo ratio. In such a case, both the element X-containing compound and the molybdenum compound may not be added.

As the molybdenum compound and the element X-containing compound supplied for the production of the aqueous slurry A, one or more kinds can be appropriately selected from the molybdenum-containing compound and the element X-containing compound which can be used for the production of the above-described catalyst.

In the preparation of the aqueous slurry A, compounds containing catalyst constituent elements other than molybdenum and element X may be added, if necessary, based on the catalyst composition of the deterioration catalyst. As a compound containing molybdenum and catalyst constituent elements other than element X, 1 or more types can be suitably selected from the compound containing each element which can be used for manufacture of a target catalyst.

Ion-exchange water is normally used as water supplied in manufacture of the aqueous slurry A. The amount of water supplied is usually 1 to 20 parts by weight based on the amount of molybdenum in the aqueous slurry A obtained, that is, 1 part by weight of the total amount of molybdenum contained in the deterioration catalyst and the molybdenum contained in the supplied molybdenum compound.

When manufacturing the aqueous slurry A, the mixing order of each component mentioned above is not specifically limited, It can set suitably.

When producing the aqueous slurry A, the deterioration catalyst may be mixed as it is, and heat treatment may be previously performed on this.

Although the processing temperature in particular of the heat pretreatment of a degradation catalyst is not restrict | limited, Preferably it is 350-600 degreeC. Although the processing time of heat processing is not specifically limited, Usually, it is 0.1 to 24 hours, Preferably it is 0.5 to 10 hours. The thermal pretreatment may be performed in an atmosphere of an oxidizing gas such as an oxygen-containing gas or in an atmosphere of a non-oxidizing gas such as nitrogen.

In addition, when the deterioration catalyst used for manufacture of aqueous slurry A is a shaping | molding catalyst, although a shaping | molding catalyst may be used as it is, a grinding | pulverization process may be previously performed by a conventionally well-known method as needed. However, in the case where the molded catalyst (deteriorated molded catalyst) contains fibers or the like which express the strength of the catalyst, when the fibers or the like are cut or broken, the strength may be reduced. It is desirable to adjust the degree.

In addition, when both a grinding | pulverization process and a thermal pretreatment are performed to the degradation catalyst used for manufacture of aqueous slurry A, the order of both processes is not restrict | limited, Usually, heat processing is performed after grinding | pulverization process.

It is preferable that pH of the liquid phase of the aqueous slurry A obtained by process (I) is 8 or less. When the pH of the liquid phase of aqueous slurry A exceeds 8, there exists a possibility that catalyst activity may not fully recover.

In step (II), the atomic ratio (X: Mo) of the element X to molybdenum in the slurry from which the raw material compound and water of the heteropolyacid compound which comprises a target catalyst are obtained is 0:12-0.5: 12, Preferably it is 0:12. To 0.3: 12, mixed to obtain an aqueous slurry B.

In the production of the aqueous slurry B, as a raw compound of the heteropolyacid compound, the compound containing molybdenum has an atomic ratio (X: Mo) of the element X to molybdenum as described above (X: Mo ratio in the aqueous slurry B). A compound containing at least molybdenum and optionally a compound containing X is used. Therefore, when the atomic ratio (X: Mo) of the element X to molybdenum is set to 0:12, it is not necessary to mix the compound containing the element X.

As a molybdenum compound and an element X containing compound which are supplied to manufacture aqueous slurry B, at least 1 sort (s) can be selected suitably from the molybdenum containing compound and element X containing compound which can be used for manufacture of the target catalyst.

Moreover, when manufacturing aqueous slurry B, you may add the compound containing the catalyst constituent elements other than molybdenum and the element X as needed. As a compound containing molybdenum and catalyst constituent elements other than element X, at least 1 sort (s) can be suitably selected from the compound containing each element which can be used for manufacture of a target catalyst.

Ion-exchange water can be normally used as water supplied to manufacture of aqueous slurry B. The amount of water mixed is usually 1 to 20 parts by weight based on 1 part by weight of the amount of molybdenum present in the resulting aqueous slurry B.

When manufacturing aqueous slurry B, the mixing order of each component mentioned above is not restrict | limited, It can set suitably.

In process (III), the aqueous slurry A obtained at the process (I) and the aqueous slurry B obtained at the process (II) are mixed first. The mixing ratio of aqueous slurry A and aqueous slurry B takes into account the amount of molybdenum and element X contained in both slurries, and the atomic ratio of element X to molybdenum in the heteropolyacid compound constituting the finally obtained regeneration catalyst (X: Mo) can be adjusted to be 0.5: 12 to 2:12.

The mixing order, temperature, stirring conditions, etc. at the time of mixing aqueous slurry A and aqueous slurry B are not restrict | limited, It can set suitably.

When mixing the aqueous slurry A and the aqueous slurry B, or at the time of the aging treatment described later or after the aging treatment, among the compounds containing the constituent elements of the target catalyst, in particular, the compound containing the element Y can be mixed. . In such a case, it is preferable to add a compound containing a catalyst constituent element such as the compound containing element Y in the form of an aqueous suspension of such a compound. These mixing amounts can be suitably set so that the heteropolyacid compound which comprises the regeneration catalyst finally obtained may become a preferable composition of a target catalyst in the state of the new catalyst before use.

In step (III), the mixed slurry obtained by mixing the aqueous slurry A and the aqueous slurry B is then dried. The drying method is not particularly limited, and for example, a method commonly used in this field, such as evaporation drying method, spray drying method, drum drying method, and air flow drying method, may be adopted. In addition, the drying conditions can be appropriately set so that the water content in the mixed slurry is sufficiently reduced, and is not particularly limited. For example, a drying temperature is usually less than 300 degreeC.

It is preferable that the mixed slurry obtained by mixing the aqueous slurry A and the aqueous slurry B is subjected to a aging treatment in which the mixed slurry is aged by heating the mixed slurry at 100 ° C or higher in a sealed container before applying the above-mentioned drying. When the mixed slurry is aged, the catalytic activity can be effectively restored. It is preferable that it is 200 degrees C or less, and, as for the upper limit of the heating temperature in a aging process, it is more preferable that it is 150 degrees C or less. Aging time is usually 0.1 hours or more, preferably 2 hours or more, and preferably 20 hours or less from the viewpoint of productivity in order to recover the catalyst activity satisfactorily.

In step (III), the dried product obtained after drying is then subjected to firing. Firing can be performed by a method usually used in this field, and there is no particular limitation. 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 performed at 300 ° C or lower. Preferably, in order to recover the catalyst life favorably, it is preferable to carry out multistage baking in the atmosphere of an oxidizing gas or a non-oxidizing gas. More preferably, a two-stage firing method is employed in which the first stage firing is performed in an atmosphere of an oxidizing gas, and the second stage firing is then performed in an atmosphere of a non-oxidizing gas.

The oxidizing gas used for firing contains an oxidizing substance. Preferred examples of such gases are oxygen-containing gases. The oxygen concentration in the oxygen containing gas is usually about 1 to about 30 volume percent. As the oxygen source, air or pure oxygen is usually used and diluted with an inert gas as necessary. In addition, the oxidizing gas may contain moisture as necessary. However, the concentration of water in the oxidizing gas is usually 10% by volume or less. The oxidizing gas is preferably air. Firing performed in an oxidizing gas atmosphere is usually carried out under an air flow of such an oxidizing gas. Moreover, the temperature of the baking step performed in an oxidizing gas atmosphere is 360-410 degreeC normally, Preferably it is 380-400 degreeC.

The non-oxidizing gas used in the firing step is a gas that is substantially free of oxidizing substances such as oxygen. Examples of non-oxidizing gases include inert gases such as nitrogen, carbon dioxide, helium, argon and the like. In addition, the non-oxidizing gas may contain moisture as needed. However, the concentration of water in the non-oxidizing gas is usually 10% by volume or less. In particular, nitrogen is preferable as the non-oxidizing gas. Firing performed in a non-oxidizing gas atmosphere is usually carried out under an air stream of such a non-oxidizing gas. In addition, the temperature of the firing step performed in a non-oxidizing gas atmosphere is usually 420 to 500 ° C, preferably 420 to 450 ° C.

In addition, the dried product obtained after the drying prior to the above-described firing is preferably subjected to heat treatment (prefiring) at a temperature of about 180 to 300 ° C. under an atmosphere of an oxidizing gas or a non-oxidizing gas.

The dried product obtained after the drying can be molded into a desired shape (ring shape, pellet shape, spherical shape, columnar shape, etc.) as necessary before the above-described firing or prefiring. Molding treatment can be performed by a method usually used in this field, such as tablet molding and extrusion molding, for example. In the shaping | molding process, water, a shaping | molding adjuvant, a pore agent, etc. can be added to the said dried material as needed. Examples of molding aids include ammonium nitrate in addition to ceramic fibers and glass fibers. In particular, ammonium nitrate is preferably used because it has a function as a pore agent in addition to having a function as a molding aid.

Preferably, it is preferable that the shaping | molding catalyst obtained by the said shaping | molding process performs a temperature-humidity control continuously. A shaping | molding catalyst can be obtained more stable by performing a temperature-humidity control process before adding to baking or prefiring. In particular, the temperature-humidity control process is specifically performed by exposing a shaping | molding catalyst for about 0.5 to 10 hours in the atmosphere of the temperature of 40-100 degreeC, and 10-60% relative humidity. The treatment may be performed, for example, in a bath at a controlled temperature or a humidified condition, or may be performed by spraying a heated, humidified gas onto a molding catalyst. In addition, although air is normally used as an atmospheric gas at the time of performing the said process, inert gas, such as nitrogen, can also be used.

Thus, the regeneration catalyst of the present invention can obtain a regeneration catalyst in which the catalytic activity is well recovered. This regenerating catalyst contains a heteropolyacid compound similarly to the target catalyst, and may contain a free heteropolyacid or a salt of a heteropolyacid. Especially, the catalyst containing the acid salt of heteropoly acid is preferable, and the catalyst containing the acid salt of keggin-type heteropoly acid is more preferable. Moreover, the atomic ratio (X: Mo) of the element X with respect to molybdenum in the heteropolyacid compound which comprises a regenerated catalyst is 0.5: 12-2: 12, Preferably it has the same preferable composition as the target catalyst mentioned above.

Moreover, the regeneration method of the catalyst for methacrylic acid production of this invention regenerates the deterioration catalyst used for manufacture of methacrylic acid. In addition, the regeneration method of the present invention may provide a catalyst that is not used in the production of methacrylic acid, such as a loss generated during the production of the catalyst or a catalyst that does not have the desired performance. In such a case, the same excellent effect as in the case of regenerating the catalyst is obtained.

The method for producing methacrylic acid of the present invention is a compound selected from the group consisting of methacrolein, isobutylaldehyde, isobutane and isobutyric acid in the presence of a catalyst for producing methacrylic acid regenerated by the regeneration method of the present invention (hereinafter " And methacrylic acid raw material "may be added to the gas phase catalytic oxidation reaction. By using the catalyst regenerated by the regeneration method of the present invention, methacrylic acid can be produced at high conversion and selectivity.

Methacrylic acid is usually produced by charging a catalyst in a fixed bed multi-tubular reactor and supplying a raw material gas mixture containing the methacrylic acid raw material and oxygen thereto, but a reaction type such as a fluidized bed or a mobile phase may be employed. As the oxygen source, air is usually used. In addition to the methacrylic acid raw material and oxygen, the raw material gas mixture may contain nitrogen, carbon dioxide, carbon monoxide, water vapor, and the like.

The methacrylic acid raw material does not necessarily need to be a high purity product. For example, methacrolein-containing reaction product gas obtained by gas phase catalytic oxidation of isobutylene or tert-butyl alcohol may be used as methacrolein. In addition, 1 type of methacrylic acid raw materials may be sufficient as the said source gas, and 2 or more types may be sufficient as it.

The reaction conditions of the manufacturing method of methacrylic acid can be suitably set according to the kind etc. of the methacrylic acid raw material contained in raw material gas mixture. For example, when methacrolein is used as the methacrylic acid raw material, the methacrolein concentration in the raw material gas mixture 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 space velocity is 500 to 5000 h −1 (standard state reference), the reaction temperature is 250 to 350 ° C., and the reaction pressure is performed under the conditions of 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 source gas is usually 1 to 85% by volume, the water vapor concentration is 3 to 30% by volume, and the molar ratio of oxygen to isobutane is 0.05 to 4, space The reaction is carried out under the conditions that the speed is 400 to 5000 h −1 (standard state reference), the reaction temperature is 250 to 400 ° C., and the reaction pressure is 0.1 to 1 MPa. In addition, when isobutyl aldehyde or isobutyric acid is used as the methacrylic acid raw material, generally the same reaction conditions as those in the case of using methacrolein as the raw material are employed.

[Example]

Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.

In addition, the air used in the Example contains 3.5 volume% of water (corresponding to the water vapor content of the atmosphere), and the nitrogen used in the Example is substantially free of water.

Analysis and evaluation of the catalyst obtained in each of the following examples were performed as follows.

The catalyst composition (constituent atomic ratio) was determined by fluorescence X-ray analysis of the catalyst using a fluorescent X-ray analyzer (ZSX Primus II manufactured by Rigaku Corporation).

Catalyst Test

9 g of the catalyst was charged in a glass micro reactor having an inner diameter of 16 mm, and a raw gas prepared by mixing methacrolein, air, steam, and nitrogen (composition: 4 vol% of methacrolein, 12 vol% of molecular oxygen, 17% by volume of water vapor and 67% by volume of nitrogen were supplied at a space velocity of 670 h −1 , and the reaction was performed at a furnace temperature (the furnace temperature for heating the micro reactor) at 355 ° C. for 1 hour. Thereafter, the raw material gas having the same composition as above was supplied to the microreactor at the same space velocity as above, and the reaction was started again at the furnace temperature of 280 ° C. The exit gas (gas after reaction) 1 hour after this reaction restart is sampled, and it analyzes by gas chromatography, and the methacrolein conversion rate (%) and methacrylic acid selectivity (%) are based on the following formula. ) And yield (%) were calculated | required.

Conversion rate (%) = [(moles of reacted methacrolein) / (moles of supplied methacrolein)] × 100

Selectivity (%) = [(moles of generated methacrylic acid) / (moles of reacted methacrolein)] × 100

Yield (%) = [(moles of generated methacrylic acid) / (moles of supplied methacrolein)] × 100

Reference Example 1 Preparation of New Catalyst

38.2 kg of cesium nitrate [CsNO 3 ], 27.4 kg of 75 wt% orthophosphoric acid, and 25.2 kg of 70 wt% nitric acid were dissolved in 224 kg of ion-exchanged water heated to 40 ° C., to obtain α liquid. On the other hand, after dissolving 297 kg of ammonium molybdate tetrahydrate [(NH 4 ) 6 Mo 7 O 24 4H 2 O] 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 used as β liquid.

The α liquid was added dropwise to the β liquid under stirring while maintaining the temperature of the α liquid and the β liquid at 40 ° C., followed by stirring at 120 ° C. for 5.8 hours in a sealed container, followed by 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] was added while suspended in 23 kg of ion-exchanged water. Thereafter, the mixture was stirred at 120 DEG C for 5 hours in a sealed container. The slurry thus obtained was dried with a spray dryer. To 100 parts by weight of the obtained dry powder, 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 and kneaded, followed by extrusion molding into a cylindrical shape having a diameter of 5 mm and a height of 6 mm. After drying the obtained molded object for 3 hours at the temperature of 90 degreeC, and 30% of a relative humidity, it baked for 3 hours at 435 degreeC in nitrogen stream, and then hold | maintained at 390 degreeC in air stream for 3 hours. Thereafter, the molding catalyst was recovered and used as a new catalyst.

The new catalysts included heteropolyacid compounds 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. Table 1 shows the results of the activity test of this new catalyst.

Reference Example 2

Preparation of Degradation (Used) Catalyst

The deterioration catalyst was obtained using the new catalyst obtained in the reference example 1 for the gas phase catalyst oxidation reaction of methacrolein for a predetermined time. The heteropolyacid compounds constituting the deterioration catalyst contained phosphorus, molybdenum, vanadium, antimony, copper and cesium in an atomic ratio of 1.3, 9.6, 0.5, 0.48, 0.3 and 1.4, respectively. Table 1 shows the results of the activity test of this deterioration catalyst.

Example 1

Process (I): Preparation of Aqueous Slurry A

100 g of the deterioration catalyst obtained in Reference Example 2 was added to 200 g of ion-exchanged water, and the mixture was stirred. Next, in order to compensate for the deficient component of the deterioration catalyst for the new catalyst, 15.8 g of molybdenum trioxide (MoO 3 ) as a molybdenum source, 1.3 g of 75% by weight orthophosphoric acid as a person, and 0.1 g of ammonium metavanadate as a vanadium source were added. 17.9 g of cesium nitrate and 27.0 g of ammonium nitrate (NH 4 NO 3 ) were further added. The mixture was heated to 70 ° C. and maintained at the same temperature for 1 hour. Subsequently, 6.23 g of 25 weight% ammonia water was added, and it kept at 70 degreeC for 1 hour. Thereafter, the mixture was stirred at 120 ° C for 5 hours in an airtight container to form an aqueous slurry A1. The molar ratio of ammonium ions to nitrate ions in aqueous slurry A1 was 1.0: 1, and the pH of the liquid phase of aqueous slurry A1 was 2.8. In addition, the atomic ratios of the metal elements contained in the aqueous slurry A1 were 1.5, 12, 0.50, 0.5, 0.3, and 3.2 of phosphorus, molybdenum, vanadium, antimony, copper, and cesium, respectively, and the atomic ratio of cesium to molybdenum was 3.2: 12.

Process (II): Preparation of Aqueous Slurry B

12.9 g of 75% by weight orthophosphoric acid and 12.3 g of 67.5% by weight nitric acid were dissolved in 105 g of ion-exchanged water heated to 40 ° C, to obtain a liquid. On the other hand, after dissolving ammonium molybdate tetrahydrate 139g in 165g of ion-exchange water heated at 40 degreeC, 3.85g of ammonium metavanadate was suspended and this was made into b liquid. While maintaining the temperature of solution a and solution b at 40 ° C, solution a was added dropwise to solution b under stirring to obtain an aqueous slurry B1. The atomic ratios of the metal elements contained in this aqueous slurry B1 were 1.5, 12, and 0.50 for phosphorus, molybdenum, and vanadium, respectively, and 0 for antimony, copper, and cesium, and the atomic ratio of cesium to molybdenum was 0:12.

Process (III): Mixing of Aqueous Slurry A and Aqueous Slurry B

The whole amount of the said aqueous slurry B1 was mixed with the whole amount of the said aqueous slurry A1, and it stirred at 120 degreeC in the airtight container for 5 hours. Subsequently, 4.80 g of antimony trioxide and 4.76 g of copper nitrate trihydrate were added to 11.0 g of ion-exchanged water, and then stirred in a sealed container at 120 ° C. for 5 hours. The mixed slurry thus obtained was dried at 135 ° C. 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 and kneaded with respect to 100 parts by weight of the obtained dried product, followed by extrusion molding into a cylindrical shape having a diameter of 5 mm and a height of 6 mm. The resultant molded catalyst was dried at a temperature of 90 ° C. and a relative humidity of 30% for 3 hours, and then calcined by holding at 435 ° C. for 4 hours in 390 ° C. in an air stream, and then kept at 435 ° C. for 4 hours in a nitrogen stream. Regeneration catalyst (1) was obtained.

The obtained regeneration catalyst (1) contains a heteropolyacid compound, and the atomic ratio of the metal elements excluding oxygen of the heteropolyacid compound is 1.5, 12, 0.50, 0.5, 0.3, and 1.4 of phosphorus, molybdenum, vanadium, antimony, copper and cesium, respectively. And the atomic ratio of cesium to molybdenum was 1.4: 12. Table 1 shows the results of the activity test of this regenerated catalyst (1).

Example 2

Aqueous slurry was carried out in the same manner as in Step (I) of Example 1, except that the amount of 25% by weight of ammonia water 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. A2 was obtained. The molar ratio of ammonium ions to nitrate ions in aqueous slurry A2 was 0.9: 1, and the pH of the liquid phase of aqueous slurry A2 was 1.6. In addition, the atomic ratio (atom ratio of cesium to molybdenum) of the metal element contained in aqueous slurry A2 is the same as the aqueous slurry A1 obtained in Example 1.

Next, using this aqueous slurry A2 and the aqueous slurry B1 obtained by carrying out similarly to the process (II) of Example 1, operation similar to the process (III) of Example 1 was performed and the regeneration catalyst (2) was obtained.

The regeneration catalyst (2) comprises a heteropolyacid compound, wherein the atomic ratios of the metal elements excluding oxygen of the heteropolyacid compound are 1.5, 12, 0.50, 0.5, 0.3, and 1.4 of phosphorus, molybdenum, vanadium, antimony, copper and cesium, respectively; The atomic ratio of cesium to molybdenum was 1.4: 12. Table 1 shows the results of the activity test of this regenerated catalyst (2).

Example 3

100 g of the deterioration 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 shortage component of the deterioration catalyst for the new catalyst, after adding 15.8 g of molybdenum trioxide as the molybdenum source, 1.3 g of 75% by weight orthophosphoric acid as the personnel, and 0.1 g of ammonium metavanadate as the vanadium source, It heated up at 40 degreeC. Thereafter, 37.6 g of 25 wt% ammonia water was added and maintained at 40 ° C. for 1 hour, followed by 19.1 g of 67.5 wt% nitric acid, and maintained at 40 ° C. for 1 hour. Subsequently, the aqueous solution which dissolves 17.9 g of cesium nitrate was added to 54 g of ion-exchange water heated at 40 degreeC, it hold | maintained at 40 degreeC for 15 minutes, and obtained aqueous slurry A3. The molar ratio of ammonium ions to nitrate ions in aqueous slurry A3 was 1.9: 1, and the pH of the liquid phase of aqueous slurry A3 was 6.3. Further, the atomic ratios of the metal elements contained in the aqueous slurry A3 were 1.5, 12, 0.50, 0.5, 0.3, and 3.2 of phosphorus, molybdenum, vanadium, antimony, copper, and cesium, respectively, and the atomic ratio of cesium to molybdenum was 3.2: 12.

Next, using this aqueous slurry A3 and the aqueous slurry B1 obtained by carrying out similarly to the process (II) of Example 1, operation similar to the process (III) of Example 1 was performed and the regeneration catalyst (3) was obtained.

The obtained regeneration catalyst (3) contains a heteropolyacid compound, and the atomic ratio of the metal elements excluding oxygen of the heteropolyacid compound is 1.5, 12, 0.50, 0.5, 0.3 and 1.4 of phosphorus, molybdenum, vanadium, antimony, copper and cesium, respectively. And the atomic ratio of cesium to molybdenum was 1.4: 12. Table 1 shows the results of the activity test of this regenerated catalyst (3).

Comparative Example 1

200 g of the deterioration catalyst obtained in Reference Example 2 was added to 400 g of ion-exchanged water and stirred. Next, in order to compensate for the deficient component of the deterioration catalyst for the new catalyst, 31.5 g of molybdenum trioxide as a molybdenum source, 2.7 g of 75% by weight orthophosphoric acid as the number of people, and 0.2 g of ammonium metavanadate as a vanadium source were added, 69.2 g of ammonium nitrate were added. The mixture was raised to 70 ° C. and kept at the same temperature for 1 hour. Thereafter, 41.2 g of 25% by weight ammonia water was added, and the mixture was maintained at 70 ° C for 1 hour. The mixture was stirred at 120 ° C. for 5 hours in a closed vessel to give an aqueous slurry C1. The molar ratio of ammonium ions to nitrate ions in the aqueous slurry C1 was 1.7: 1, and the pH of the liquid phase of the aqueous slurry C1 was 4.2. In addition, the atomic ratios of the metal elements contained in the aqueous slurry C1 were 1.5, 12, 0.5, 0.5, 0.3, and 1.4 of phosphorus, molybdenum, vanadium, antimony, copper, and cesium, respectively, and the atomic ratio of cesium to molybdenum was 1.4: 12.

The aqueous slurry C1 thus obtained was dried at 135 ° C. to obtain a dried product. 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 and kneaded with respect to 100 parts by weight of the dried product, followed by extrusion molding into a cylindrical shape having a diameter of 5 mm and a height of 6 mm. The resultant molded catalyst was dried at a temperature of 90 ° C. and a relative humidity of 30% for 3 hours, and then calcined by holding at 435 ° C. for 4 hours at 390 ° C. in an air stream and then at 435 ° C. for 4 hours in a nitrogen stream. Thereafter, the shaping catalyst was recovered to obtain a regeneration catalyst (C1) for comparison.

The regeneration catalyst (C1) comprises a heteropolyacid compound, wherein the atomic ratio of the metal elements excluding oxygen of the heteropolyacid compound is 1.5, 12, 0.5, 0.5, 0.3, and 1.4 of phosphorus, molybdenum, vanadium, antimony, copper and cesium, respectively; The atomic ratio of cesium to molybdenum was 1.4: 12. Table 1 shows the results of the activity test for this regenerated catalyst (C1).

Figure pat00002

Claims (5)

  1. It is a regeneration method of the catalyst for methacrylic acid production containing the heteropolyacid compound containing phosphorus, molybdenum, and at least 1 element X selected from the group which consists of potassium, rubidium, cesium, and thallium,
    The atomic ratio (X: Mo) of the element X with respect to molybdenum in the heteropolyacid compound which comprises following process (I)-(III) and comprises a regenerated catalyst is characterized by being 0.5: 12-2: 12. A regeneration method of a catalyst for producing methacrylic acid.
    Step (I): The deterioration catalyst, nitrate ions, ammonium ions and water recovered from the process for producing methacrylic acid are mixed so that the atomic ratio (X: Mo) of element X to molybdenum is 2:12 to 4:12. Process of obtaining the aqueous slurry A adjusted so as to be.
    Process (II): The process of mixing the raw material compound of a heteropolyacid compound, and water, and obtaining the aqueous slurry B adjusted so that the atomic ratio (X: Mo) of the element X with respect to molybdenum may be 0:12 to 0.5: 12.
    Process (III): The process of drying and baking a mixture after mixing the aqueous slurry A obtained by process (I) and the aqueous slurry B obtained by process (II).
  2. The process according to claim 1, wherein the aqueous slurry A obtained in step (I) contains 0.1 to 3.0 moles of ammonium ions per mole of nitrate ions.
  3. The method according to claim 1 or 2, wherein the pH of the liquid phase of the aqueous slurry A obtained in the step (I) is 8 or less.
  4. The heteropolyacid compound according to any one of claims 1 to 3, wherein the heteropolyacid compound comprises at least one element selected from the group consisting of vanadium, copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium. How to include more.
  5. Regenerating the catalyst for producing methacrylic acid by the method according to claim 1, and
    Gas phase catalytic oxidation of at least one compound selected from the group consisting of methacrolein, isobutylaldehyde, isobutane and isobutyric acid in the presence of the regenerated catalyst
    Method for producing methacrylic acid comprising a.
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