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WO2015037611A1 - Procédé de préparation d'un catalyseur pour la production d'acide méthacrylique - Google Patents

Procédé de préparation d'un catalyseur pour la production d'acide méthacrylique Download PDF

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Publication number
WO2015037611A1
WO2015037611A1 PCT/JP2014/073913 JP2014073913W WO2015037611A1 WO 2015037611 A1 WO2015037611 A1 WO 2015037611A1 JP 2014073913 W JP2014073913 W JP 2014073913W WO 2015037611 A1 WO2015037611 A1 WO 2015037611A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
methacrylic acid
producing
preparation
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/073913
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English (en)
Japanese (ja)
Inventor
加藤　裕樹
近藤　正英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Priority to CN201480049665.XA priority Critical patent/CN105517709A/zh
Priority to KR1020157034441A priority patent/KR101621678B1/ko
Priority to SG11201600745YA priority patent/SG11201600745YA/en
Priority to JP2014545433A priority patent/JP6341094B2/ja
Publication of WO2015037611A1 publication Critical patent/WO2015037611A1/fr
Priority to SA516370674A priority patent/SA516370674B1/ar
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a method for producing a catalyst for producing methacrylic acid.
  • Catalyst raw materials are prepared in a tank, mixed, and heat-treated as necessary to obtain catalyst precursor particles. Thereafter, this is dried to obtain a dried catalyst precursor powder, which is further heat-treated to develop catalytic activity.
  • the preparation and mixing of the raw material solution and the raw material slurry are generally operated in a batch manner.
  • the jacket and the heat-transfer coil are attached so that the temperature in a tank can be adjusted, and the tank which can be heated and cooled with a heat medium is used.
  • a heteropolyacid catalyst containing molybdenum and phosphorus is known as a catalyst for producing methacrylic acid used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen.
  • heteropolyacid catalysts there are known proton-type heteropolyacids whose counter cations are protons, and alkali metal salts of heteropolyacids in which part of the protons are substituted with alkali metals such as cesium, rubidium, and potassium. Yes.
  • proton-type heteropolyacid is also simply referred to as “heteropolyacid”, and proton-type heteropolyacid and / or alkali metal salt of heteropolyacid is also referred to as “heteropolyacid (salt)”.
  • Proton heteropolyacids are water-soluble, but alkali metal salts of heteropolyacids are generally poorly soluble because of the large cation radii (Non-patent Document 1).
  • a method for producing a catalyst that involves the formation of a precipitate in which an insoluble salt such as an alkali metal salt of a heteropoly acid is deposited to obtain a catalyst
  • solids resulting from the catalyst raw material may adhere to the wall surface in the tank used for the production. is there.
  • a solvent such as water may evaporate on the heating surface, and solid matter is likely to precipitate at that time.
  • the solids are desirably removed in order to produce a uniform catalyst. However, it is difficult to suppress or remove the solid matter.
  • the solid substance when the preparation liquid prepared in a plurality of preparation tanks is mixed in the preparation tank to which the solid matter is adhered, the solid substance may be mixed in the catalyst precursor particles obtained after mixing the preparation liquid.
  • the washing tank or the like is chemically washed with alkali each time. There are many problems such as a heavy work load and the necessity of cleaning wastewater treatment.
  • the method for producing a catalyst for producing methacrylic acid comprises: (A) dividing the catalyst raw material into at least two and dispersing or dissolving each catalyst raw material in a solvent in different preparation tanks to obtain a catalyst raw material slurry or catalyst raw material solution as a preparation liquid; (B) a step of mixing all of the catalyst raw material slurry or the catalyst raw material solution in one mixing tank; Including The blending tank and the mixing tank are different.
  • the method for producing methacrylic acid according to the present invention comprises producing a catalyst for producing methacrylic acid by the method according to the present invention, filling the catalyst in a reaction tube, and selecting from the group consisting of methacrolein, isobutyraldehyde, isobutane and isobutyric acid Methacrylic acid is produced by gas phase catalytic oxidation of at least one selected from the above.
  • a catalyst capable of producing methacrylic acid with high selectivity can be provided. Further, it is possible to provide a method for producing a catalyst having a stable quality when a catalyst is repeatedly produced.
  • the method for producing a catalyst for producing methacrylic acid comprises: (a) dividing a catalyst raw material into at least two, and dispersing or dissolving each catalyst raw material in a solvent in different preparation tanks to prepare a catalyst raw material slurry as a preparation liquid Or a step of obtaining a catalyst raw material solution (hereinafter also referred to as a preparation step), and (b) a step of mixing all of the catalyst raw material slurry or the catalyst raw material solution in one mixing tank (hereinafter also referred to as a mixing step), The mixing tank and the mixing tank are different from each other.
  • different tanks are used as two or more mixing tanks used in the mixing process and a mixing tank used in the mixing process.
  • the mixing operation in the mixing process is preferably performed by heating, and the slurry or solution in the mixing tank is heated on the heating surface of the mixing tank and evaporated to generate a solid matter.
  • This solid substance adheres to the inner wall which is a heating surface of a preparation tank.
  • the mixing tank in this state is used as it is as a mixing tank, the deposits adhering to the inner wall are crystallized as nuclei, and the amount of crystals attached increases. As a result, the composition of the catalyst finally obtained is not stable, and the selectivity of methacrylic acid is lowered.
  • since a mixing tank different from the mixing tank is used, such an influence can be eliminated, and the selectivity of methacrylic acid is improved.
  • the catalyst is produced by repeating at least once using the same preparation tank and mixing tank as they are. That is, after the catalyst is produced by the method according to the present invention, it is preferable to repeat the production of the catalyst by the same method using the preparation tank and the mixing tank used in the catalyst production as they are without washing.
  • the method for producing a catalyst in which a plurality of preparation liquids containing a catalyst raw material are prepared in a preparation process and then the preparation liquid is mixed in a mixing process, precipitates generated by mixing the preparation liquid and solids generated by evaporation of the solution May adhere to the inner wall surface of the mixing tank.
  • the present inventors use the mixing tank in which the solid matter remains as a preparation tank, and when the preparation liquid is prepared again, the solid catalyst and the preparation liquid come into contact with each other, thereby causing the target catalyst.
  • the performance of the catalyst particularly the selectivity to the target product, decreases. If the solids are present in contact with the preparation liquid, the raw material concentration changes, the precipitated solid substance becomes a nucleus, particle generation is promoted, the particle size distribution in the preparation liquid and the catalyst composition change, and the catalyst It is considered that the performance is reduced.
  • the mixing tank to which this solid matter is attached is used as a mixing tank. In some cases, it may come into contact with the preparation liquid and further promote the generation of unnecessary impurities.
  • a preparation liquid does not contact the solid substance produced
  • the method for producing a catalyst for producing methacrylic acid according to the present invention produces methacrylic acid by vapor-phase catalytic oxidation of at least one selected from the group consisting of methacrolein, isobutyraldehyde, isobutane and isobutyric acid with molecular oxygen. It is suitably used for the production of a methacrylic acid production catalyst used at the time.
  • methacrylic acid production catalyst used at the time is suitably used for the production of a methacrylic acid production catalyst used at the time.
  • the catalyst raw material is divided into at least two parts, and each catalyst raw material is dispersed or dissolved in a solvent in different preparation tanks to obtain a catalyst raw material slurry or catalyst raw material solution as a preparation liquid.
  • the method of dividing the catalyst raw material is not particularly limited as long as it is divided into at least two.
  • the amount of each catalyst raw material when the catalyst raw material is divided is also not particularly limited, and may be divided into equal amounts or different amounts.
  • the kind of solvent thrown into each preparation tank may be the same, and may differ.
  • a preparation liquid 1 containing at least phosphorus and molybdenum and a preparation liquid 2 containing a cation raw material it is preferable from the viewpoint of improving the selectivity of methacrylic acid to prepare a preparation liquid 1 containing at least phosphorus and molybdenum and a preparation liquid 2 containing a cation raw material. That is, a catalyst raw material containing at least phosphorus and molybdenum is charged into the preparation tank 1 to obtain a preparation liquid 1 by being dispersed or dissolved in a solvent, and a cationic raw material that is a catalyst raw material is charged into the preparation tank 2; It is preferable to obtain the preparation liquid 2 by dispersing or dissolving in a solvent.
  • the cation raw material is a compound containing an alkali metal, a compound containing an alkaline earth metal, a compound containing a transition metal, a compound containing a base metal, a compound containing nitrogen (a compound containing an ammonium ion, a compound containing an alkyl ammonium ion) And at least one selected from the group consisting of nitrogen heterocyclic compounds.
  • the alkali metal include lithium, sodium, potassium, rubidium, and cesium.
  • the alkaline earth metal include magnesium, calcium, strontium, and barium.
  • the solvent include water, ethyl alcohol, acetone and the like. Two or more kinds of solvents may be mixed and used, but at least water is preferably used.
  • the cation material preferably contains an X element which is at least one element selected from the group consisting of alkali metals and thallium.
  • the heteropolyacid salt contained in the catalyst becomes a salt formed by the heteropolyacid and the monovalent cation, and can take a cubic structure which is an advantageous structure as a catalyst for methacrylic acid production. .
  • the heteropoly acid salt contained in the catalyst is preferably a hardly soluble salt. Therefore, the cation raw material is preferably a heteropolyacid hardly soluble salt. In this case, the heteropolyacid salt considered to be preferable for the selective production of methacrylic acid can be selectively present in the catalyst.
  • heteropolyacid salt examples include heteropolyacids such as 12-molybdophosphoric acid, 12-tungstophosphoric acid, 12-molybdosilicic acid, 12-tungstosilicic acid, 12-molybdoarsenic acid, 12-tungstoaric acid, or their molybdenum, tungsten From potassium, rubidium, cesium, and thallium, such as those in which a part of is substituted with vanadium, or those in which molybdenum, tungsten, or vanadium are mixed and coordinated (in the present invention, these are collectively referred to as “heteropolyacid”)
  • heteropolyacid examples include salts of at least one element selected.
  • a used methacrylic acid production catalyst is used as at least a part of the cation raw material, and at least a part of the preparation liquid 2 is dispersed in a solvent. It is preferable to obtain it by dissolving.
  • the preparation liquid 3 containing the element lost from the used methacrylic acid production catalyst so that the obtained catalyst has the same elemental composition as that of the used methacrylic acid production catalyst. Is further preferable from the viewpoint of obtaining a catalyst exhibiting methacrylic acid selectivity equivalent to the catalyst for producing methacrylic acid before use.
  • the preparation liquid 3 containing each disappearing constituent element is prepared so that the obtained catalyst has the same elemental composition as the methacrylic acid production catalyst before use.
  • the obtained preparation liquid 3 may be put into the preparation tank 1 after the preparation of the preparation liquid 1, may be put into the preparation tank 2 after the preparation of the preparation liquid 2, or is put into the mixing tank. You may mix with each preparation liquid.
  • a catalyst having an element composition different from the element composition before use may be produced.
  • the used catalyst for producing methacrylic acid refers to a catalyst after producing methacrylic acid by the method according to the present invention using the catalyst for producing methacrylic acid produced by the method according to the present invention.
  • the atomic ratio (X / (Mo + P)) of X element which is at least one element selected from the group consisting of alkali metal and thallium, with respect to the total amount of phosphorus and molybdenum is 0-0. 5 is prepared, and a preparation liquid 2 having an atomic ratio of X element (X / (Mo + P)) of 0.1 to 4.0 with respect to the total amount of phosphorus and molybdenum is catalyzed.
  • the atomic ratio (X / (Mo + P)) of the preparation liquid 1 is more preferably 0 to 0.2.
  • the atomic ratio (X / (Mo + P)) of the preparation liquid 2 is more preferably 2.0 to 4.0.
  • the atomic ratio (X / (Mo + P)) of X element which is at least one element selected from the group consisting of alkali metal and thallium, with respect to the total amount of phosphorus and molybdenum is 0 to 0.00.
  • preparation liquid 1 in which the atomic ratio of X element to the total amount of phosphorus and molybdenum (X / (Mo + P)) is 0 to 0.5 is prepared. Then, it is preferable to mix with the preparation liquid 2 thereafter.
  • the atomic ratio (X / (Mo + P)) of the preparation liquid 1 is more preferably 0 to 0.2.
  • the atomic ratio (X / (Mo + P)) of the preparation liquid 2 is more preferably 2.0 to 4.0.
  • the preparation liquid 1 further contains a vanadium element from the viewpoint of manufacturing a catalyst having high methacrylic acid selectivity.
  • the catalyst for producing methacrylic acid contains at least one Y element selected from the group consisting of copper, antimony, arsenic, silicon, boron, silver, bismuth, iron, cobalt and cerium
  • a preparation 4 containing at least one Y element selected from the group consisting of copper, antimony, arsenic, silicon, boron, silver, bismuth, iron, cobalt and cerium may be further prepared and then mixed in a mixing tank. From the viewpoint of production of a catalyst having high selectivity for methacrylic acid.
  • the catalyst for producing methacrylic acid contains antimony
  • preparation liquid 5 containing antimony is further prepared and then mixed in a mixing tank.
  • Antimony is also used as a heteroatom of the heteropolyacid, but in the present catalyst, it is preferably present in a form supported on the heteropolyacid salt, so that it is preferably prepared separately as the preparation liquid 5 and then mixed.
  • an oxidizing agent may be used in order to adjust the oxidation state of the catalyst for producing methacrylic acid.
  • the oxidizing agent include hypochlorous acid, chlorous acid, chloric acid, perchloric acid, halogen, permanganate, cerium ammonium nitrate, chromic acid, dichromic acid, peroxide, and the like. These may use 1 type and may use 2 or more types together.
  • the preparation liquid 1 prepared in the preparation tank 1 is an aqueous solution or an aqueous slurry containing a heteropolyacid.
  • the preparation tank 1 is preferably heated to 70 to 150 ° C., more preferably 75 to 125 ° C., and more preferably 80 to 100 It is more preferable to heat to ° C.
  • the reaction rate is improved by setting the temperature in the mixing tank 1 to 70 ° C. or higher.
  • the heteropoly acid of the target structure is obtained by making the temperature in the preparation tank 1 into 150 degrees C or less.
  • a lid with an exhaust duct is installed on the upper part of the mixing tank 1, and a condenser is installed in the exhaust duct.
  • a device for refluxing the condensed liquid connected can be installed.
  • a lid without an exhaust duct can be installed to prevent the vapor from being released to the atmosphere.
  • the retention time after the preparation of the preparation liquid 1 in the preparation tank 1 is preferably 6 minutes or more and 900 minutes or less.
  • the retention time is 6 minutes or longer, the synthesis reaction of the heteropolyacid proceeds sufficiently.
  • the retention time is 900 minutes or less, the synthesis reaction of the heteropolyacid reaches a sufficient equilibrium.
  • the holding time is more preferably from 60 minutes to 300 minutes, further preferably from 80 minutes to 250 minutes, particularly preferably from 100 minutes to 200 minutes.
  • stirring is preferably performed when the catalyst raw material is dispersed or dissolved in a solvent.
  • the temperature in the preparation tank 2 when preparing the preparation liquid 2 is preferably 0 to 80 ° C, and more preferably 10 to 40 ° C. By setting the temperature within the above range, the catalyst raw material is sufficiently dissolved in the solvent. Moreover, catalyst performance can be improved because this temperature is 80 degrees C or less. The reason is not clear, but it is considered that when the temperature exceeds 80 ° C., the dissolved catalyst raw material is thermally decomposed to change the elemental state and a desired catalyst slurry may not be obtained in the mixing step. It is done.
  • (B) mixing step) All of at least two catalyst raw material slurries or catalyst raw material solutions prepared in the preparation step are mixed in one mixing tank.
  • the mixing tank is different from the mixing tank used for the mixing.
  • the liquid transfer method from each preparation tank to the mixing tank is not particularly limited. For example, when two preparation liquids 1 and 2 are transferred to the mixing tank, preparation liquid 1 and preparation liquid 2 are separately provided. The mixed solution 1 and the mixed solution 2 may be simultaneously charged into the mixing tank. In addition, when a plurality of preparation liquids are charged while mixing in a mixing tank, the time required for charging each of the preparation liquids can be freely selected.
  • At least two preparation liquids are mixed in a mixing tank.
  • a preparation liquid 1 containing at least phosphorus and molybdenum, a preparation liquid 2 containing a cation raw material, and antimony are mixed.
  • the preparation liquid 4 containing can be mixed in a mixing tank.
  • the preparation liquid 2 is introduced into the mixing tank after the preparation liquid 1 is introduced into the mixing tank. Moreover, it is preferable to stir when adding each preparation liquid.
  • the mixing in the mixing tank is preferably carried out while maintaining the temperature at 20 to 120 ° C., since each preparation liquid can be mixed to produce a desired precipitate.
  • the temperature is more preferably from 30 to 110 ° C, further preferably from 40 to 105 ° C, particularly preferably from 50 to 100 ° C. Note that, at a temperature lower than 20 ° C., the dissolved catalyst component may be less than the solubility and reprecipitate, so that the desired catalyst component may not be precipitated when the preparation liquid is mixed.
  • the temperature adjustment may be performed in the preparation tank 1 before the preparation liquid 1 is put into the mixing tank, or after the preparation liquid 1 is put into the mixing tank and before the preparation liquid 2 is put in the mixing tank. May be. Further, when the preparation liquid 1 is introduced into the mixing tank, the preparation liquid 1 may be introduced while adjusting the temperature of the preparation tank 1 using a heat exchanger so that the target temperature is obtained when the preparation liquid 2 is introduced. Good.
  • the heat medium cooling water, ethylene glycol aqueous solution, warm water, steam or the like can be used. When heating, it is preferable to use warm water as the heat medium from the viewpoint of preventing the catalyst component from sticking on the heat transfer surface.
  • a lid with an exhaust duct is installed on the upper part of the mixing tank, and a condenser is connected to the exhaust duct.
  • a device for refluxing the condensed liquid can be installed.
  • a lid without an exhaust duct can be installed to prevent the vapor from being released to the atmosphere.
  • the mixing time in the mixing tank is preferably 60 minutes or more and 320 minutes or less. When the time is 60 minutes or longer, the preparation liquid can be mixed uniformly. Moreover, process time can be shortened because this time is 320 minutes or less.
  • the time is preferably 120 minutes or more and 280 minutes or less, more preferably 140 minutes or more and 240 minutes or less, and particularly preferably 160 minutes or more and 220 minutes or less.
  • the mixing time refers to the time when two or more of the preparation liquids 1 and 2 and the remaining catalyst raw materials in the mixing tank are charged and contacted, and the pH adjustment with the ammonium raw material is completed. This is the time until the catalyst raw material is completely mixed.
  • the mixing starts when the preparation liquid 2 or the remaining catalyst raw material is charged.
  • the mixing is started at the time when they are simultaneously added.
  • an ammonium raw material is further added to adjust the pH between 0.5 and 7.
  • the pH is more preferably 1.5 to 3.5, and even more preferably 2 to 3.
  • the pH is a value obtained by measuring the slurry obtained through the mixing step using a castany ACT pH meter D-21 (trade name, manufactured by Horiba, Ltd.).
  • the ammonium raw material include urea, ammonium salt, and ammonia.
  • ammonium salts include ammonium bicarbonate, ammonium carbonate, ammonium nitrate, and ammonium phosphate. These may use 1 type and may use 2 or more types together.
  • an aging step, a concentration step, a cooling step, and the like may be appropriately performed. These steps may be carried out in a mixing tank. However, when solid matter adhesion or the like occurs during these steps, it is preferable to carry out each step using a concentration tank, an aging tank, and a cooling tank. .
  • the mixed solution can be heated in a aging tank to be aged.
  • the aging treatment is preferably performed by heating for 30 minutes or more.
  • the temperature of the aging treatment is preferably 80 to 103 ° C.
  • the aging step is not necessarily performed, but when the mixed solution is in the form of a slurry containing precipitated particles, the particles can be grown by performing this step, and the particles are stabilized.
  • the catalyst can be produced by performing a drying step, a molding step, and a heat treatment step as necessary.
  • the mixed solution containing all the catalyst raw materials obtained in the mixing step can be dried to obtain a dried catalyst product.
  • Conditions such as drying method and drying temperature are not particularly limited, and can be appropriately selected depending on the shape and size of a desired dried product.
  • Examples of the drying method include a drying method using a box-type dryer, a drum drying method, an airflow drying method, an evaporation to dryness method, and a spray drying method.
  • the drying temperature can be, for example, 120 to 500 ° C., and preferably 140 to 400 ° C. Drying can be performed until the slurry or solution is dry.
  • a molding step of molding the catalyst dried product to obtain a catalyst molded product Before performing the heat treatment process to be described later on the catalyst dried product obtained by the drying step, a molding step of molding the catalyst dried product to obtain a catalyst molded product may be performed.
  • the molding method is not particularly limited, and dry and wet molding methods can be applied. Examples of the molding method include tableting molding, press molding, extrusion molding, granulation molding and the like.
  • the shape of the molded product is not particularly limited, and examples thereof include a columnar shape, a ring shape, and a spherical shape. Moreover, at the time of shaping
  • the catalyst activity can be sufficiently developed by heat-treating the catalyst dried product or the catalyst molded product.
  • the heat treatment can be performed under the flow of at least one of air and inert gas.
  • the inert gas refers to a gas that does not decrease the catalytic activity, and examples thereof include nitrogen, carbon dioxide, helium, and argon. These may use 1 type and may mix and use 2 or more types.
  • the shape of the heat treatment container is not particularly limited, it is preferable to use a tubular heat treatment container having a cross-sectional area of 2 square centimeters or more and 100 square centimeters or less.
  • the maximum heat treatment temperature is preferably 300 ° C. or higher, more preferably 320 ° C. or higher. When the maximum temperature of the heat treatment is 300 ° C. or higher, the desorption component contained in the catalyst is sufficiently desorbed.
  • the desorption component refers to an anion component contained in the catalyst raw material, an additive added during molding, or the like.
  • the maximum heat treatment temperature is preferably 700 ° C. or lower, and more preferably 500 ° C. or lower. When the maximum heat treatment temperature is 700 ° C. or lower, decomposition of the catalyst itself can be suppressed.
  • the catalyst produced by the method according to the present invention is particularly suitable as a catalyst for producing methacrylic acid used for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein with molecular oxygen.
  • the elemental composition excluding oxygen of the catalyst produced by the method according to the present invention is preferably a composition represented by the following formula (1).
  • Mo, P, V, Cu, and O are element symbols indicating molybdenum, phosphorus, vanadium, copper, and oxygen, respectively.
  • A represents at least one element selected from the group consisting of silicon, titanium, germanium, arsenic, antimony and cerium
  • B represents bismuth, zirconium, silver, iron, zinc, chromium, magnesium, cobalt, manganese, barium
  • Z represents at least one element selected from the group consisting of potassium, rubidium and cesium, and represents at least one element selected from the group consisting of cerium and lanthanum.
  • a, b, c, d, e, f, g and h represent the atomic ratio of each element.
  • a 12
  • b 0.5 to 3
  • c 0.01 to 3
  • d 0. 01-2
  • h is the atomic ratio of oxygen necessary to satisfy the valence of the nuclear element.
  • the elemental composition is a value calculated from the amount of raw material charged.
  • e is preferably from 0.1 to 3.
  • the catalyst produced by the method according to the present invention is preferably used as a molded body or a support in a fixed bed, but may be used in a fluidized bed as a granule.
  • a catalyst for producing methacrylic acid according to the present invention is filled in a reaction tube, and methacrylic acid is produced by gas phase catalytic oxidation of at least one selected from the group consisting of methacrolein, isobutyraldehyde, isobutane and isobutyric acid. it can.
  • methacrylic acid is produced by gas phase catalytic oxidation of at least one selected from the group consisting of methacrolein, isobutyraldehyde, isobutane and isobutyric acid.
  • the methacrylic acid is brought into contact with a source gas containing at least one selected from the group consisting of methacrolein, isobutyraldehyde, isobutane, and isobutyric acid and molecular oxygen, and the catalyst according to the present invention.
  • a source gas containing at least one selected from the group consisting of methacrolein, isobutyraldehyde, isobutane, and isobutyric acid and molecular oxygen
  • This reaction can be carried out in a fixed bed.
  • the catalyst layer may be one layer or two or more layers. If the catalytic activity is high, the reaction may occur suddenly at the inlet of the raw material gas of the fixed bed reactor, and the temperature may increase due to the heat of reaction, which may prevent stable operation. It can be used by diluting it by mixing it with a non-stable substance.
  • two catalyst layers can be used, and the catalyst can be diluted and used on the reaction gas inlet side.
  • the catalyst dilution ratio may be changed stepwise to form two or more catalyst layers.
  • the concentration of at least one selected from the group consisting of methacrolein, isobutyraldehyde, isobutane and isobutyric acid in the raw material gas is not particularly limited, but is preferably 1 to 20% by volume, more preferably 3 to 10% by volume. These raw materials may contain a small amount of impurities.
  • the concentration of molecular oxygen in the raw material gas is preferably 0.4 to 4 mol per mol of at least one selected from the group consisting of methacrolein, isobutyraldehyde, isobutane and isobutyric acid, and is preferably 0.5 to 3 mol. Mole is more preferred.
  • the molecular oxygen source is preferably air from the viewpoint of economy. If necessary, a gas or the like enriched with molecular oxygen by adding pure oxygen to air may be used.
  • the source gas may be obtained by diluting at least one selected from the group consisting of methacrolein, isobutyraldehyde, isobutane and isobutyric acid and a molecular oxygen source with an inert gas such as nitrogen or carbon dioxide. . Further, water vapor may be added to the source gas. By performing the reaction in the presence of water vapor, methacrylic acid can be obtained with higher selectivity.
  • concentration of water vapor in the raw material gas is preferably 0.1 to 50% by volume, more preferably 1 to 40% by volume.
  • the contact time between the raw material gas and the catalyst produced by the method according to the present invention is preferably 1.5 to 15 seconds, and more preferably 2 to 5 seconds.
  • the reaction pressure is preferably 0.1 MPaG (atmospheric pressure) to 1 MPaG.
  • the reaction temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C.
  • Methacrylic acid selectivity (%) (B / A) ⁇ 100
  • A represents the number of carbon atoms in the entire reaction product
  • B represents the number of carbon atoms in the produced methacrylic acid.
  • Example 1 ((A) Preparation process)
  • 400 parts of pure water, 100 parts of molybdenum trioxide, 7.8 parts of ammonium metavanadate, 8.0 parts of 85 mass% phosphoric acid aqueous solution, 2.1 parts of 60 mass% arsenic acid aqueous solution and copper nitrate (II ) 5.6 parts of the trihydrate was dissolved.
  • the mixture was heated to 95 ° C. while stirring, and stirred for 150 minutes while maintaining the liquid temperature at 95 ° C.
  • the aqueous slurry thus obtained was designated as Formulation 1.
  • 8.5 parts of cesium bicarbonate was added to 20 parts of pure water and stirred to dissolve the cesium bicarbonate.
  • the slurry obtained in the mixing step was transferred to a concentration tank and concentrated at 100 ° C. Further, the concentrated slurry was transferred to a cooling bath and cooled to 40 ° C. Thereafter, the cooled slurry was spray-dried to obtain a dry powder. The dried powder was molded, and the molded product was put into a cylindrical quartz glass baking container having an inner diameter of 3 cm. The temperature was raised at 10 ° C./h under air flow and calcined at 380 ° C. for 15 hours to obtain a catalyst.
  • the elemental composition of the catalyst excluding oxygen was Mo 12 P 1.2 V 1.2 Cu 0.4 As 0.2 Cs 0.8 .
  • the elemental composition of the catalyst is a value calculated from the charged amount of raw material.
  • the obtained catalyst was filled in a reaction tube, and a raw material gas consisting of 5% by volume of methacrolein, 10% by volume of oxygen, 30% by volume of water vapor and 55% by volume of nitrogen was passed at a reaction temperature of 300 ° C. and a contact time of 3.6 seconds. .
  • the product was collected and analyzed by gas chromatography to calculate methacrylic acid selectivity. The results are shown in Table 1.
  • Example 2 Using the preparation tank 1, the preparation tank 2 and the mixing tank used in the production of the catalyst in Example 1 as they are without washing, a catalyst is produced in the same manner as in Example 1, and the production of methacrylic acid using the catalyst. The methacrylic acid selectivity was calculated.
  • the mixing tank In the mixing tank, the mixing time from the start of the addition of the preparation liquid 2 to the addition of ammonium carbonate and the completion of stirring was 180 minutes.
  • the resulting slurry had a pH of 2.5.
  • Table 1 In addition, when the preparation liquid 1 in the preparation tank 1 was thrown into the mixing tank and the inner wall surface of the preparation tank 1 was observed, adhesion of solid matter was confirmed. Moreover, after taking out the contents of a mixing tank, when the inner wall surface of the mixing tank was observed, adhesion of the solid substance derived from the slurry obtained at the mixing process was confirmed.
  • Example 3 The mixing tank 1, the mixing tank 2 and the mixing tank used for catalyst production in Example 2 were used as they were without washing, and the mixing process was performed in the same manner as in Example 1.
  • the mixing time from the start of the addition of the preparation liquid 2 to the addition of ammonium carbonate and the completion of stirring was 190 minutes.
  • the resulting slurry had a pH of 2.9.
  • it without performing concentration operation, it cooled to 40 degreeC in the mixing tank. Otherwise, a catalyst was produced in the same manner as in Example 1, methacrylic acid was produced using the catalyst, and methacrylic acid selectivity was calculated. The results are shown in Table 1.
  • Example 4 ((A) Preparation process)
  • 400 parts of pure water 100 parts of molybdenum trioxide, 7.8 parts of ammonium metavanadate, 6.8 parts of 85 mass% phosphoric acid aqueous solution, 5.1 parts of antimony trioxide, and copper (II) nitrate 3 5.6 parts of hydrate was dissolved.
  • the mixture was heated to 95 ° C. while stirring, and stirred for 180 minutes while maintaining the liquid temperature at 95 ° C. Thereafter, the liquid temperature was set to 50 ° C., and the aqueous slurry thus obtained was used as the preparation liquid 1.
  • 8.5 parts of cesium nitrate was added to 20 parts of pure water in the preparation tank 2 and stirred at 50 ° C. to dissolve the cesium nitrate.
  • Preparation liquid 1 was put into a mixing tank prepared separately from preparation tanks 1 and 2, and the liquid temperature was maintained at 50 ° C.
  • Four baffle plates were installed in the mixing tank, and the preparation liquid 2 was added while stirring the preparation liquid 1 using a rotary blade stirrer. Thereafter, 25.3 parts of a 25 mass% aqueous ammonia solution was added. Further, a solution in which 4.2 parts of iron nitrate was dissolved in 3.0 parts of pure water was added dropwise, followed by stirring for 15 minutes. The pH of the slurry at this time was 3.2.
  • the mixing time from the start of the addition of the preparation solution 2 to the addition of the iron nitrate solution and the completion of the stirring was 200 minutes.
  • the mixing tank 1, the mixing tank 2, and the mixing tank were washed carefully before use and started to be used in a state where there was no adhesion of solid matter.
  • a catalyst was produced by the same method as in Example 1, methacrylic acid was produced using the catalyst, and methacrylic acid selectivity was calculated.
  • the elemental composition of the catalyst, except oxygen in the catalyst was Mo 12 P 1 V 1.2 Cu 0.4 Sb 0.3 Fe 0.3 Cs 0.8.
  • the elemental composition of the catalyst is a value calculated from the charged amount of raw material. The results are shown in Table 1.
  • Example 5 Using the preparation tank 1, the preparation tank 2 and the mixing tank used in the production of the catalyst in Example 4 as they are without washing, a catalyst is produced in the same manner as in Example 4, and the production of methacrylic acid using the catalyst. The methacrylic acid selectivity was calculated.
  • the mixing tank the mixing time from the start of the addition of the preparation liquid 2 to the addition of the iron nitrate solution and the completion of the stirring was 200 minutes.
  • the resulting slurry had a pH of 3.7.
  • Table 1 shows that when the preparation liquid 1 in the preparation tank 1 was thrown into the mixing tank and the inner wall surface of the preparation tank 1 was observed, adhesion of solid matter was confirmed.
  • adhesion of the solid substance derived from the slurry obtained at the mixing process was confirmed.
  • Example 6 The mixing tank 1, the mixing tank 2, and the mixing tank used for catalyst production in Example 5 were used as they were without washing, and the mixing process was performed in the same manner as in Example 4.
  • the mixing time from the start of the addition of the preparation solution 2 to the addition of the iron nitrate solution and the completion of the stirring was 200 minutes.
  • the resulting slurry had a pH of 3.7.
  • it without performing concentration operation, it cooled to 40 degreeC in the mixing tank.
  • Example 7 ((A) Preparation process)
  • a used catalyst for producing methacrylic acid which is the catalyst of Example 4 used for calculation of methacrylic acid selectivity for about 1000 hours, was dispersed in 400 parts of pure water.
  • the mixture was heated to 95 ° C. while stirring, and stirred for 150 minutes while maintaining the liquid temperature at 95 ° C.
  • the aqueous slurry thus obtained was designated as Formulation 1.
  • 20 parts of molybdenum trioxide and 1.1 parts of cesium bicarbonate were added to 20 parts of pure water, and the mixture was stirred and dispersed.
  • Preparation liquid 1 was put into a mixing tank prepared separately from preparation tanks 1 and 2, and the liquid temperature was maintained at 95 ° C.
  • Four baffle plates were installed in the mixing tank, and the preparation liquid 2 was added while stirring the preparation liquid 1 using a rotary blade stirrer. Thereafter, stirring was continued for 15 minutes.
  • a solution prepared by dissolving 15 parts of ammonium nitrate in 24 parts of pure water was added. Thereafter, stirring was continued for 15 minutes.
  • the pH of the slurry at this time was 1.9.
  • the mixing time from the start of the addition of the preparation liquid 2 to the addition of ammonium carbonate and the completion of stirring was 190 minutes.
  • a catalyst was produced by the same method as in Example 1, methacrylic acid was produced using the catalyst, and methacrylic acid selectivity was calculated. Note that the elemental composition of the catalyst, except oxygen in the catalyst was Mo 12 P 1 V 1.2 Cu 0.4 Cs 0.8. The elemental composition of the catalyst is a value calculated from the charged amount of raw material. The results are shown in Table 1.
  • Example 1 preparation liquids 1 and 2 were prepared in preparation tanks 1 and 2, respectively, and thereafter, preparation liquids 1 and 2 were mixed using a mixing tank different from the preparation tank. As a result, as shown in Comparative Example 1, it was possible to produce a catalyst having a higher selectivity than the catalyst produced using the preparation tank 1 as a mixing tank.
  • Example 2 the catalyst was produced using the blending tank 1, the blending tank 2 and the mixing tank used in Example 1 as they were, and solid adhesion was confirmed on the inner wall surface of the blending tank 1, Even when the catalyst was repeatedly produced, the selectivity did not decrease, and the catalyst could be produced stably.
  • Comparative Example 2 since the same preparation tank was used as it was after Comparative Example 1 and the preparation tank 1 was used as a mixing tank, the slurry-derived solid matter adhered to the inner wall surface of the preparation tank 1, and the catalyst was influenced by the influence. It can be considered that the selectivity could not be achieved because the product could not be produced stably.
  • Example 4 preparation liquids 1 and 2 were prepared in preparation tanks 1 and 2, respectively, and then mixing liquids 1 and 2 were mixed using a mixing tank different from the preparation tank. As a result, as shown in Comparative Example 3, it was possible to produce a catalyst having a higher selectivity than the catalyst produced using the mixing tank 1 as a mixing tank.
  • Example 5 a catalyst was produced using the mixing tank 1, the mixing tank 2 and the mixing tank used in Example 4 as they were, and solids were confirmed to adhere to the inner wall surface of the mixing tank 1.
  • the selectivity did not decrease, and the catalyst could be produced stably.
  • Comparative Example 4 since the same mixing tank was used as it was after Comparative Example 3 and the mixing tank 1 was used as a mixing tank, the slurry-derived solid matter adhered to the inner wall surface of the mixing tank 1, and the catalyst was influenced by the influence. It can be considered that the selectivity could not be achieved because the product could not be produced stably.
  • the method for producing a methacrylic acid production catalyst according to the present invention is industrially useful because a catalyst having a high methacrylic acid selectivity can be produced stably and repeatedly.

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Abstract

　L'invention concerne un catalyseur avec lequel de l'acide méthacrylique peut être produit à une sélectivité élevée. L'invention concerne également un procédé de préparation d'un catalyseur de qualité constante, durant une préparation répétée d'un catalyseur. Le procédé de préparation d'un catalyseur pour la production d'acide méthacrylique est caractérisé en ce qu'il comprend (a) une étape de division d'un matériau de départ de catalyseur en au moins deux parties, de dispersion ou de dissolution de chacun des matériaux de départ de catalyseur à l'intérieur de cuves de préparation respectivement différentes de façon à obtenir une dispersion de matériaux de départ de catalyseur ou une solution de matériaux de départ de catalyseur en tant que liquide préparé, et (b) une étape de mélange de la dispersion de matériaux de départ de catalyseur ou solution de matériaux de départ de catalyseur entière à l'intérieur d'une cuve de mélange unique, les cuves de préparation et la cuve de mélange étant différentes.
PCT/JP2014/073913 2013-09-11 2014-09-10 Procédé de préparation d'un catalyseur pour la production d'acide méthacrylique Ceased WO2015037611A1 (fr)

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WO2018037998A1 (fr) * 2016-08-22 2018-03-01 三菱ケミカル株式会社 Procédé de production d'un catalyseur pour la production d'acide méthacrylique, procédé de production d'acide méthacrylique et procédé de production d'ester d'acide méthacrylique
JP2019504760A (ja) * 2016-11-16 2019-02-21 エルジー・ケム・リミテッド 触媒の製造方法
CN111939952A (zh) * 2020-08-21 2020-11-17 中国科学院兰州化学物理研究所 一种多级孔催化剂及其制备方法与应用
JPWO2019163984A1 (ja) * 2018-02-26 2021-01-14 三菱ケミカル株式会社 α，β−不飽和カルボン酸製造用触媒の製造方法、並びにα，β−不飽和カルボン酸及びα，β−不飽和カルボン酸エステルの製造方法
WO2022163727A1 (fr) 2021-01-27 2022-08-04 日本化薬株式会社 Catalyseur et procédé de production d'acide carboxylique insaturé l'utilisant
WO2023162794A1 (fr) * 2022-02-25 2023-08-31 三菱ケミカル株式会社 PROCÉDÉ DE PRODUCTION D'UN ARTICLE MOULÉ CATALYSEUR UTILISÉ LORS DE LA PRODUCTION D'ACIDE CARBOXYLIQUE α,β-INSATURÉ, ET PROCÉDÉ DE PRODUCTION D'ACIDE CARBOXYLIQUE α,β-INSATURÉ ET D'ESTER D'ACIDE CARBOXYLIQUE α,β-INSATURÉ L'UTILISANT

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WO2022163725A1 (fr) 2021-01-27 2022-08-04 日本化薬株式会社 Catalyseur et procédé de production d'acide carboxylique insaturé à l'aide dudit catalyseur
CN114797982A (zh) * 2022-05-26 2022-07-29 中国科学技术大学 一种用于异丁烷一步法制甲基丙烯酸的催化剂、其制备方法及应用

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JP2019504760A (ja) * 2016-11-16 2019-02-21 エルジー・ケム・リミテッド 触媒の製造方法
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JP7001982B2 (ja) 2018-02-26 2022-02-04 三菱ケミカル株式会社 α，β－不飽和カルボン酸製造用触媒の製造方法、並びにα，β－不飽和カルボン酸及びα，β－不飽和カルボン酸エステルの製造方法
CN111939952A (zh) * 2020-08-21 2020-11-17 中国科学院兰州化学物理研究所 一种多级孔催化剂及其制备方法与应用
CN111939952B (zh) * 2020-08-21 2022-04-19 中国科学院兰州化学物理研究所 一种多级孔催化剂及其制备方法与应用
WO2022163727A1 (fr) 2021-01-27 2022-08-04 日本化薬株式会社 Catalyseur et procédé de production d'acide carboxylique insaturé l'utilisant
KR20230137338A (ko) 2021-01-27 2023-10-04 닛뽄 가야쿠 가부시키가이샤 촉매 및 그것을 이용한 불포화 카본산의 제조 방법
WO2023162794A1 (fr) * 2022-02-25 2023-08-31 三菱ケミカル株式会社 PROCÉDÉ DE PRODUCTION D'UN ARTICLE MOULÉ CATALYSEUR UTILISÉ LORS DE LA PRODUCTION D'ACIDE CARBOXYLIQUE α,β-INSATURÉ, ET PROCÉDÉ DE PRODUCTION D'ACIDE CARBOXYLIQUE α,β-INSATURÉ ET D'ESTER D'ACIDE CARBOXYLIQUE α,β-INSATURÉ L'UTILISANT

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