WO2024135496A1 - 触媒及びそれを用いた化合物の製造方法 - Google Patents

触媒及びそれを用いた化合物の製造方法 Download PDF

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WO2024135496A1
WO2024135496A1 PCT/JP2023/044644 JP2023044644W WO2024135496A1 WO 2024135496 A1 WO2024135496 A1 WO 2024135496A1 JP 2023044644 W JP2023044644 W JP 2023044644W WO 2024135496 A1 WO2024135496 A1 WO 2024135496A1
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catalyst
mass
parts
binder
catalyst according
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French (fr)
Japanese (ja)
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将吾 保田
主 香川
成喜 奥村
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to KR1020257019497A priority Critical patent/KR20250123799A/ko
Priority to EP23906861.2A priority patent/EP4640312A1/en
Priority to CN202380086651.4A priority patent/CN120379761A/zh
Priority to JP2024521354A priority patent/JP7649426B2/ja
Publication of WO2024135496A1 publication Critical patent/WO2024135496A1/ja
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    • 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
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B01J37/0223—Coating of particles by rotation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C47/22—Acryaldehyde; Methacryaldehyde
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • 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 novel catalyst that is highly active and capable of producing the target product in high yield, and in particular, to a catalyst that enables stable, high-yield production when oxidatively producing unsaturated aldehydes, unsaturated carboxylic acids, or conjugated dienes.
  • acrylic acid is becoming increasingly important as a raw material for absorbent resins, adhesives, and the like.
  • catalyst performance for producing acrylic acid through a gas-phase catalytic oxidation reaction using acrolein as a raw material.
  • companies have made various improvements to catalysts that can produce acrylic acid in high yields and stably over the long term, and the following proposals have been made, for example:
  • Patent documents 1 to 3 disclose improvements to catalyst composition, etc., focusing on the X-ray diffraction peaks of catalytically active components. These catalysts are proposed as catalysts that achieve high activity and high yields. Patent documents 4 and 5 also provide improvement guidelines aimed at improving mechanical strength, and attempt to improve catalyst performance by preventing powdering during filling. Patent document 6 aims to improve the long-term stability of catalytic reactions by setting the standard deviation of catalyst particle size within a specific range. Patent document 7 proposes producing a catalyst that combines high catalytic performance and mechanical strength by controlling the relative centrifugal acceleration when molding using a tumbling granulator.
  • Japanese Patent Application Publication No. 8-299797 Japanese Patent Application Publication No. 2003-251184 Japanese Patent Application Publication No. 2015-120133 Japanese Patent Application Publication No. 2001-79408 International Publication No. 2012/073584 Japanese Patent Application Publication No. 2009-214105 Japanese Patent Application Publication No. 2015-96497
  • the objective of the present invention is to improve the catalytic activity in a method for producing unsaturated aldehydes and unsaturated carboxylic acids using propylene, isobutylene, t-butyl alcohol, etc. as raw materials, and in a gas-phase catalytic oxidation method for producing 1,3-butadiene from butenes.
  • the present invention relates to the following 1) to 9).
  • A is the area of the particle photographed by dynamic image analysis
  • P is the perimeter of said particle.
  • a, b, c, d, e, f, g, and h represent the atomic ratio of each element, and a represents 0 ⁇ a ⁇ 10.0, b represents 0 ⁇ b ⁇ 10.0, c represents 0 ⁇ c ⁇ 6.0, d represents 0 ⁇ d ⁇ 10.0, e represents 0 ⁇ e ⁇ 0.50, f represents 0 ⁇ f ⁇ 1.0, and g represents 0 ⁇ g ⁇ 6.0, relative to 12 molybdenum atoms. Also, h represents the number of oxygen atoms required to satisfy the valence of each of the components.
  • the catalyst according to any one of 1) to 5) above which is a catalyst in which a catalytically active component is supported on an inert carrier.
  • the catalyst according to any one of 1) to 7) above which is used for producing an unsaturated aldehyde, an unsaturated carboxylic acid, or a conjugated diene compound.
  • the present invention makes it possible to maintain high catalytic activity in a method for producing the corresponding unsaturated aldehydes and unsaturated carboxylic acids using propylene, isobutylene, t-butyl alcohol, etc. as raw materials, and in a gas-phase catalytic oxidation method for producing 1,3-butadiene from butenes.
  • FIG. 1 is a schematic diagram showing a method of adding a binder in Example 1.
  • FIG. 2 is a schematic diagram showing a method of adding a binder in Example 2.
  • FIG. 3 is a schematic diagram showing a method of adding a binder in Example 4.
  • FIG. 4 is a schematic diagram showing a method of adding a binder in Example 6.
  • FIG. 5 is a schematic diagram showing a method of adding a binder in Comparative Example 1.
  • FIG. 6 is a schematic diagram showing a method of adding a binder in Comparative Example 2.
  • FIG. 7 is a schematic diagram showing a method of adding a binder in Example 7.
  • the catalyst of the present invention has an SPHT3 (sphericity parameter) value of 0.9820 or less, which is obtained by particle shape measurement using dynamic image analysis.
  • Dynamic image analysis is a method of obtaining particle size distribution and shape distribution (aspect ratio, sphericity, etc.) by continuously photographing particles dispersed in a fluid (solvent, air, etc.) and measuring, binarizing, and analyzing the images.
  • An example of a practical device for carrying out dynamic image analysis is CAMSIZER X2 (manufactured by Microtrac Bell).
  • sphericity and sphericity parameter (SPHT3) are synonymous. The sphericity SPHT3 is analyzed from successively captured particle images.
  • the perimeter P and area A of each particle can be calculated using the following formula (I).
  • a perfect sphere has an SPHT3 of 1, and particles of all other shapes have an SPHT3 value less than 1 and greater than 0.
  • SPHT3 4 ⁇ A ⁇ P2 ...(I)
  • the SPHT3 value of a catalyst when the SPHT3 value of a catalyst is within a certain range, it means that the average SPHT3 value measured for about 100 to 200 particles of the catalyst is within the range.
  • the upper limit of the SPHT3 is more preferably 0.9810, 0.9805, 0.9800, 0.9770, 0.9765, and particularly preferably 0.9760.
  • the lower limit is about 0.8000, and more preferably 0.8500, 0.9000, 0.9200, 0.9310, and particularly preferably 0.9320.
  • the range of SPHT3 is preferably 0.8000 or more and 0.9810 or less, more preferably 0.8500 or more and 0.9805 or less, more preferably 0.9000 or more and 0.9800 or less, more preferably 0.9200 or more and 0.9770 or less, more preferably 0.9310 or more and 0.9765 or less, and most preferably 0.9320 or more and 0.9760 or less.
  • the inventors of the present invention have found that the more the shape of a catalyst deviates from a perfect sphere (i.e., the value of SPHT3 is smaller than 1), the more active it is. This is thought to be because when gas is passed through a reaction tube filled with catalyst to carry out a catalytic reaction, the more the shape of the catalyst deviates from a perfect sphere, the more turbulent the gas flow becomes and the gas remains in the catalyst layer, increasing the contact time with the catalyst, resulting in an improvement in the raw material conversion rate.
  • Another factor that may be contributing to the deviation of the shape of a catalyst from a perfect sphere is the uneven pore distribution of the spherical catalyst and/or the thickness of the active component, which causes localized accumulation of reaction heat.
  • Symm3 is a parameter indicating geometric symmetry that is analyzed from images captured continuously by dynamic image analysis, and is calculated as follows. First, a straight line is drawn in any direction through the center of gravity of the image taken of each particle and intersecting with the outer periphery of the particle. The distances from the center of gravity to the outer periphery of the particle are defined as r1 and r2. When the direction of the straight line is changed, the smallest r1/r2 is defined as min(r1/r2), and the value calculated by applying it to the following formula (II) is defined as Symm3 (symmetry).
  • the Symm3 of the catalyst of the present invention is 0.9860 or less.
  • the upper limit of Symm3 is more preferably 0.9800, 0.9770, 0.9760, and particularly preferably 0.9750.
  • the lower limit is about 0.9600, more preferably 0.9650, and particularly preferably 0.9715. Therefore, the range of Symm3 is more preferably 0.9600 or more and 0.9800 or less, more preferably 0.9600 or more and 0.9770 or less, more preferably 0.9650 or more and 0.9760 or less, and most preferably 0.9715 or more and 0.9750 or less.
  • Symm3 ⁇ 1+min(r1/r2) ⁇ /2...(II)
  • the aspect ratio b/I3 in the present invention is a parameter indicating the shape of each particle continuously photographed by dynamic image analysis, and its calculation method is as follows.
  • P an arbitrary point on the outer periphery of the photographed particle
  • a straight line is drawn from point P through the inside of the particle so as to intersect with a point Q on the outer periphery different from point P
  • the maximum value of the length of the line segment PQ when point Q is moved along the outer periphery is designated as the chord diameter Xc .
  • the minimum value of the chord diameter Xc measured when point P is moved along the outer periphery is designated as the minimum chord diameter Xcmin .
  • the aspect ratio b/I3 is calculated by the following formula (III). In terms of activity, it is more preferable that the catalyst of the present invention has an aspect ratio b/I3 of 0.9540 or less.
  • the upper limit of the aspect ratio is more preferably 0.9500, 0.9400, and 0.9300, and particularly preferably 0.9280.
  • the lower limit is about 0.9200, and more preferably 0.9250.
  • the range of the aspect ratio is more preferably 0.9200 to 0.9540, more preferably 0.9200 to 0.9500, more preferably 0.9200 to 0.9400, more preferably 0.9200 to 0.9300, and most preferably 0.9250 to 0.9280.
  • b/I3 X cmin /X FeMAX ...(III)
  • the catalytic active component has a composition represented by the following formula (1).
  • Mo Mo 12 (V) a (W) b (Cu) c (Sb) d (X) e (Y) f (Z) g (O) h
  • Mo, V, W, Cu, Sb, and O represent molybdenum, vanadium, tungsten, copper, antimony, and oxygen, respectively;
  • X represents at least one element selected from the group consisting of alkali metals and thallium;
  • Y represents at least one element selected from the group consisting of magnesium, calcium, strontium, barium, and zinc;
  • Z represents bismuth, tellurium, silver, selenium, silicon, aluminum, boron, niobium, cerium, tin, chromium, manganese, iron, co
  • a, b, c, d, e, f, g, and h represent the atomic ratio of each element, and a represents 0 ⁇ a ⁇ 10.0, b represents 0 ⁇ b ⁇ 10.0, c represents 0 ⁇ c ⁇ 6.0, d represents 0 ⁇ d ⁇ 10.0, e represents 0 ⁇ e ⁇ 0.50, f represents 0 ⁇ f ⁇ 1.0, and g represents 0 ⁇ g ⁇ 6.0, relative to 12 molybdenum atoms. Also, h represents the number of oxygen atoms required to satisfy the valence of each of the components.
  • the preferred ranges of a to g are as follows:
  • the lower limit of a is, in order of desirability, 0.20, 0.50, 0.80, 1.0, 1.5, 2.0, 2.2, 2.5, and most desirably 2.8
  • the upper limit of a is, in order of desirability, 9.0, 8.0, 7.0, 6.0, 5.0, 4.5, 4.0, 3.5, and most desirably 3.2.
  • the range of a is preferably 0.20 ⁇ a ⁇ 9.0, more preferably 0.50 ⁇ a ⁇ 8.0, more preferably 0.80 ⁇ a ⁇ 7.0, more preferably 1.0 ⁇ a ⁇ 6.0, more preferably 1.5 ⁇ a ⁇ 5.0, more preferably 2.0 ⁇ a ⁇ 4.5, more preferably 2.2 ⁇ a ⁇ 4.0, more preferably 2.5 ⁇ a ⁇ 3.5, and most preferably 2.8 ⁇ a ⁇ 3.2.
  • the lower limit of b is, in order of desirability, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, and 0.90, and is most desirably 1.0
  • the upper limit of b is, in order of desirability, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.5, 2.0, and 1.5, and is most desirably 1.4.
  • the range of b is preferably 0.10 ⁇ b ⁇ 9.0, more preferably 0.10 ⁇ b ⁇ 8.0, more preferably 0.20 ⁇ b ⁇ 7.0, more preferably 0.30 ⁇ b ⁇ 6.0, more preferably 0.40 ⁇ b ⁇ 5.0, more preferably 0.50 ⁇ b ⁇ 4.0, more preferably 0.60 ⁇ b ⁇ 3.0, more preferably 0.70 ⁇ b ⁇ 2.5, more preferably 0.80 ⁇ b ⁇ 2.0, more preferably 0.90 ⁇ b ⁇ 1.5, and most preferably 1.0 ⁇ b ⁇ 1.4.
  • the lower limit of c is, in order of desirability, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, and most desirably 1.0
  • the upper limit of c is, in order of desirability, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, and most desirably 1.4.
  • the range of c is preferably 0.10 ⁇ c ⁇ 5.0, more preferably 0.20 ⁇ c ⁇ 5.0, more preferably 0.30 ⁇ c ⁇ 5.0, more preferably 0.40 ⁇ c ⁇ 5.0, more preferably 0.50 ⁇ c ⁇ 4.0, more preferably 0.60 ⁇ c ⁇ 3.0, more preferably 0.70 ⁇ c ⁇ 2.5, more preferably 0.80 ⁇ c ⁇ 2.0, more preferably 0.90 ⁇ c ⁇ 1.5, and most preferably 1.0 ⁇ c ⁇ 1.4.
  • the lower limit of d is, in order of desirability, 0.11, 0.15, 0.18, 0.20, 0.25, 0.30, and 0.35, and is most desirably 0.40
  • the upper limit of d is, in order of desirability, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, and 1.0, and is most desirably 0.70.
  • the range of d is preferably 0.11 ⁇ d ⁇ 9.0, more preferably 0.11 ⁇ d ⁇ 8.0, more preferably 0.11 ⁇ d ⁇ 7.0, more preferably 0.11 ⁇ d ⁇ 6.0, more preferably 0.11 ⁇ d ⁇ 5.0, more preferably 0.15 ⁇ d ⁇ 4.0, more preferably 0.18 ⁇ d ⁇ 3.0, more preferably 0.20 ⁇ d ⁇ 2.5, more preferably 0.25 ⁇ d ⁇ 2.0, more preferably 0.30 ⁇ d ⁇ 1.5, more preferably 0.35 ⁇ d ⁇ 1.0, and most preferably 0.40 ⁇ d ⁇ 0.70.
  • the upper limit of e is, in order of desirability, 0.40, 0.30, 0.20, and 0.10.
  • the range of e is, in order of desirability, 0 ⁇ e ⁇ 0.40, 0 ⁇ e ⁇ 0.30, and 0 ⁇ e ⁇ 0.20, and the most preferable range is 0 ⁇ e ⁇ 0.10.
  • the upper limit of f is, in order of preference, 0.80, 0.50, 0.20, and 0.15, and is most preferably 0.10. That is, the range of f is, in order of preference, 0 ⁇ f ⁇ 0.80, 0 ⁇ f ⁇ 0.50, 0 ⁇ f ⁇ 0.20, and 0 ⁇ f ⁇ 0.15, and the most preferable range is 0 ⁇ f ⁇ 0.10.
  • the upper limit of g is, in order of desirability, 5.0, 4.0, 3.0, 2.0, and 1.0.
  • the range of g is, in order of desirability, 0 ⁇ g ⁇ 5.0, 0 ⁇ g ⁇ 4.0, 0 ⁇ g ⁇ 3.0, and 0 ⁇ g ⁇ 2.0, and the most preferable range is 0 ⁇ g ⁇ 1.0.
  • e, f and g are 0.
  • the inert carrier may be made of known materials such as alumina, silica, titania, zirconia, niobia, silica alumina, silicon carbide, carbide, and mixtures thereof.
  • the particle size, water absorption rate, mechanical strength, crystallinity of each crystal phase, and mixture ratio of the inert carrier are not particularly limited, and an appropriate range should be selected in consideration of the final catalyst performance, moldability, production efficiency, etc.
  • the mixture ratio of the carrier and the pre-calcined powder is generally calculated as the loading rate according to the following formula, depending on the charged mass of each raw material.
  • additives such as molding aids and strength improvers remain in the catalyst after the main calcination, they are included in the total amount (denominator).
  • Support rate (mass%) (mass of pre-calcined powder used in molding)/ ⁇ (mass of pre-calcined powder used in molding)+(mass of support used in molding) ⁇ 100
  • the preferred upper limit of the above-mentioned supporting rate is 80 mass %, and more preferred are 70, 60, 55, 50, 45, 40, 47, 45, 43, 40, 38, 37, 36, and 35 mass %.
  • the lower limit is preferably 10% by mass, and more preferably 15, 18, 20, 23, 25, 28, 30, 31, 32, and 33% by mass. That is, the support rate is preferably 10% by mass or more and 80% by mass or less, and most preferably 33% by mass or more and 35% by mass or less.
  • silica and/or alumina are preferred, and a mixture of silica and alumina is particularly preferred.
  • a binder when supporting.
  • Specific examples of binders that can be used include water, ethanol, methanol, propanol, polyhydric alcohols, polyvinyl alcohol as a polymer binder, and silica sol aqueous solutions as inorganic binders. Ethanol, methanol, propanol, and polyhydric alcohols are preferred, diols such as ethylene glycol and triols such as glycerin are preferred, and an aqueous solution of glycerin with a concentration of 5% by mass or more is preferred.
  • aqueous glycerin solution By using an appropriate amount of an aqueous glycerin solution, moldability is improved, and a high-performance catalyst with high mechanical strength can be obtained.
  • the amount of these binders used is usually 2 to 60 parts by mass relative to 100 parts by mass of the pre-calcined powder, but in the case of an aqueous glycerin solution, 10 to 30 parts by mass is preferred.
  • the binder and the pre-calcined powder may be supplied alternately or simultaneously to the molding machine.
  • the supported catalyst obtained as described above can be used as it is in a gas-phase catalytic oxidation reaction, but calcination is preferable because the catalytic activity may be improved.
  • calcination method or conditions There are no particular limitations on the calcination method or conditions, and known processing methods and conditions can be applied.
  • the optimal calcination conditions vary depending on the catalyst raw material, catalyst composition, preparation method, etc. used, but the calcination temperature is usually 100 to 450°C, preferably 270 to 420°C, and particularly preferably 350 to 390°C, and the calcination time is 1 to 20 hours.
  • Calcination is usually performed in an air atmosphere, but it may be performed in an inert gas atmosphere such as nitrogen, carbon dioxide, helium, or argon, or, after calcination in an inert gas atmosphere, calcination may be further performed in an air atmosphere as necessary.
  • inert gas atmosphere such as nitrogen, carbon dioxide, helium, or argon
  • the catalyst of the present invention is used in a reaction for producing a corresponding unsaturated carboxylic acid from an unsaturated aldehyde such as acrolein or methacrolein as a raw material, particularly in a reaction for producing acrylic acid by gas-phase catalytic oxidation of acrolein with molecular oxygen or a molecular oxygen-containing gas, it is possible to improve catalytic activity and reduce the differential pressure, which is very effective compared to known methods. In addition, in a process of partial oxidation reaction accompanied by heat generation, it is expected to improve stability by reducing hot spot temperature, etc.
  • the catalyst of the present invention is also effective in reducing by-products that adversely affect the environment and the quality of the final product, such as carbon monoxide (CO), carbon dioxide (CO 2 ), acetaldehyde, acetic acid, and formaldehyde.
  • CO carbon monoxide
  • CO 2 carbon dioxide
  • acetaldehyde acetaldehyde
  • acetic acid formaldehyde
  • the method of flowing the raw material gas may be a normal single flow method or a recycle method, and may be carried out under generally used conditions and is not particularly limited.
  • a mixed gas consisting of 1 to 10% by volume, preferably 4 to 9% by volume of unsaturated aldehyde as a starting raw material at room temperature, 3 to 20% by volume, preferably 4 to 18% by volume of molecular oxygen, 0 to 60% by volume, preferably 4 to 50% by volume of steam, and 20 to 80% by volume, preferably 30 to 60% by volume of inert gas such as carbon dioxide or nitrogen is introduced onto the catalyst of the present invention filled in a reaction tube at 240 to 450° C., under a pressure of normal pressure to 10 atm, and at a space velocity of 300 to 5000 h ⁇ 1 to carry out the reaction.
  • the catalyst of the present invention preferably contains inorganic fibers for the purpose of improving mechanical strength, etc.
  • the material of the inorganic fibers is not particularly limited, and for example, glass fibers (glass fibers), ceramic fibers, metal fibers, mineral fibers, carbon fibers, various whiskers, etc. can be used. Among these, glass fibers treated with silane-based chemicals are particularly preferred.
  • the fiber length is not particularly limited as long as it does not impair the effects of the present invention, but the average fiber length is preferably about 1 to 1000 ⁇ m, more preferably about 10 to 500 ⁇ m.
  • two or more kinds of inorganic fibers can be used in combination. Two or more kinds of fibers made of different materials may be used, or two kinds of fibers made of the same material but having different average fiber lengths may be used.
  • vanadium component raw material, molybdenum component raw material, and antimony component raw material are mixed in a desired ratio with a separately prepared aqueous solution or slurry of tungsten component raw material and Z component raw material under conditions of 20 to 95 ° C., and heated and stirred for about 1 hour under conditions of 20 to 90 ° C., and then an aqueous solution in which a copper component raw material is dissolved and, if necessary, an X component raw material and a Y component raw material are added to obtain an aqueous solution or slurry containing a catalyst component.
  • the aqueous solution or slurry obtained in this way is collectively referred to as the prepared liquid (A).
  • the prepared liquid (A) does not necessarily need to contain all the catalyst constituent elements, and some elements or a part of the amount of the elements may be added in a subsequent step. Furthermore, when preparing the preparation liquid (A), if the amount of water in which each component raw material is dissolved, or if an acid such as sulfuric acid, nitric acid, hydrochloric acid, tartaric acid, or acetic acid is added for dissolution, is not appropriate, for example within the range of 5% by mass to 99% by mass, the preparation liquid (A) may take the form of a clay-like mass, which will not serve as an excellent catalyst. Therefore, the preparation liquid (A) obtained is preferably in the form of an aqueous solution or a slurry, in order to obtain an excellent catalyst.
  • the drying method is not particularly limited as long as it can completely dry the preparation (A), and examples thereof include drum drying, freeze drying, spray drying, and evaporation to dryness.
  • spray drying is particularly preferred, which can dry the slurry into powder or granules in a short time.
  • the drying temperature of the spray drying varies depending on the concentration of the slurry, the liquid delivery speed, etc., but the temperature at the outlet of the dryer is generally 70 to 150°C.
  • Step c) Pre-calcination The obtained dry powder (B) is calcined under air flow at 200°C to 500°C, preferably 300°C to 400°C, which tends to improve the moldability, mechanical strength, and catalytic performance of the catalyst.
  • the calcination time is preferably 1 hour to 12 hours. In this way, a pre-calcined body (C) is obtained.
  • the obtained pre-calcined body (C) may be obtained as a solid (D) in which the dry powder (B) is aggregated by pre-calcination.
  • the solid (D) is crushed.
  • the crushing method is not particularly limited, and examples thereof include a roller mill, a jet mill, a hammer mill, a rotary mill, and a vibration mill.
  • the average particle size (pre-calcined median size) of the pre-calcined powder (E) obtained at this time is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, even more preferably 30 ⁇ m or less, and particularly preferably 25 ⁇ m or less.
  • the pre-calcined powder (E) after pulverization is described as a catalyst precursor.
  • the pre-calcined body (C) may be used as a catalyst precursor.
  • Step e) Molding There is no particular limitation on the molding method, and the pre-calcined powder (E) may be molded into a spherical shape using a molding machine, but a method in which the pre-calcined powder (E) (including a molding aid and a strength improver, if necessary) is supported on a carrier such as an inactive ceramic is preferred.
  • the supporting method is widely known to include a rolling granulation method, a method using a centrifugal fluidized coating device, a wash coat method, etc., and is not particularly limited as long as the pre-calcined powder (E) can be uniformly supported on the carrier.
  • a device having a flat or uneven disk at the bottom of a fixed cylindrical container rotate the disk at high speed, and vigorously stir the carrier charged in the container by the rotation and revolution of the carrier itself, and add the pre-calcined powder (E) and, if necessary, a molding aid and/or a strength improver and a pore former to support the powder component on the carrier. It is preferable to use a binder when supporting.
  • binders that can be used include water, ethanol, methanol, propanol, polyhydric alcohols, polyvinyl alcohol as a polymer binder, and silica sol aqueous solution as an inorganic binder.
  • Ethanol, methanol, propanol, and polyhydric alcohols are preferred, and diols such as ethylene glycol and triols such as glycerin are more preferred.
  • glycerin aqueous solution moldability is improved and a high-performance catalyst with high mechanical strength can be obtained.
  • a particularly high-performance catalyst can be obtained when an aqueous solution of glycerin with a concentration of 5% by mass or more is used.
  • the amount of these binders used is usually 2 to 80 parts by mass per 100 parts by mass of the pre-calcined powder (E).
  • An inert carrier of about 2 to 8 mm is usually used, and the pre-calcined powder (E) is supported on it.
  • the support rate is determined in consideration of the catalyst use conditions, such as the space velocity of the reaction raw materials and the raw material concentration, and is usually 20% to 80% by mass.
  • the support rate is expressed as the following formula (4) when a molding aid or strength improver is used in molding. In this way, a molded body (F) is obtained.
  • the present inventors have found that it is difficult to maintain mechanical strength in the present invention.
  • inactive inorganic fibers as a strength improver during support molding, and glass fibers are particularly preferable.
  • the amount of these fibers used is usually 1 to 30 parts by mass, preferably 2 to 10 parts by mass, and more preferably 3 to 5 parts by mass, per 100 parts by mass of the catalytically active component solids.
  • the inert carrier may be made of known materials such as alumina, silica, titania, zirconia, niobia, silica alumina, silicon carbide, carbides, and mixtures thereof. There are no particular limitations on the particle size, water absorption rate, mechanical strength, crystallinity of each crystal phase, or mixture ratio of the inert carrier, and appropriate ranges should be selected in consideration of the final catalyst performance, moldability, production efficiency, etc.
  • Step f) Calcination The molded body (F) is calcined at a temperature of 100 to 450°C for about 1 to 12 hours, which tends to improve the catalytic activity and effective yield.
  • the calcination temperature is preferably 270°C to 420°C, more preferably 350°C to 400°C.
  • Air is the preferred gas to be circulated because it is simple, but other inert gases such as nitrogen, carbon dioxide, nitrogen oxide-containing gas for creating a reducing atmosphere, ammonia-containing gas, hydrogen gas, and mixtures thereof can also be used. In this way, the catalyst (G) is obtained.
  • the above SPHT3 value can be adjusted by changing the raw material used in the above a) step, the spray drying conditions in the step b), the calcination temperature and time in the step c), the pulverization method and the median diameter after pulverization in the step d), and the relative centrifugal acceleration, the loading rate, the type of binder, the position where the binder is added, etc. in the step e), but it is difficult to change it significantly by changing a single condition, and it can be achieved by optimizing two or more conditions.
  • the firing temperature is preferably 200° C. to 500° C., but if the temperature is increased, SPHT3 tends to increase. Therefore, in terms of adjusting SPHT3, the firing temperature is preferably less than 380° C. In addition, since SPHT3 may increase if the firing time is long, it is preferable to keep the firing time less than 5 hours.
  • ⁇ d) Grinding method and median diameter in the process> d) The SPHT3 can also be controlled by the method of step 1. When a vibration mill is used, the SPHT3 can be easily adjusted. The SPHT3 can also be adjusted by making the median diameter of the pre-calcined powder equal to or smaller than a certain value.
  • the value of SPHT3 can also be adjusted by changing the relative centrifugal acceleration in step e).
  • the relative centrifugal acceleration may be about 2.0 G or more and 30 G or less, but if it is made higher, SPHT3 tends to become high, so that about 2.0 G or more and 6.0 G or less is optimal. However, this also depends on the relationship between the amount of the support and the pre-calcined powder supported thereon (support rate).
  • SPHT3 can be controlled by making the median diameter of the pre-calcined powder equal to or less than a certain value by the method in step d), SPHT3 can also be adjusted by changing the position at which the binder is added in step e).
  • the binder should be added at a position away from the position at which the granules are added, and it is preferable to provide a binder addition position in the center of the doughnut-shaped catalyst band that is generated when the bottom plate of the tumbling granulator rotates, or to provide multiple binder addition points in the radial direction and add the binder at a uniform flow rate.
  • the above-mentioned method of adjusting SPHT3 can also be applied to adjusting Sym3 and the aspect ratio.
  • Sym3 and the aspect ratio can be adjusted by changing two or more of the conditions a) to f).
  • Catalyst composition of catalyst for producing unsaturated aldehyde or conjugated diene compound When the catalyst of the present invention is used as a catalyst for producing an unsaturated aldehyde or a conjugated diene compound, it is preferable that the catalytically active component has a composition represented by the following formula (2).
  • Mo, Bi, Ni, Co and Fe represent molybdenum, bismuth, nickel, cobalt and iron, respectively;
  • X represents at least one element selected from tungsten, antimony, tin, zinc, chromium, manganese, magnesium, calcium, silicon, aluminum, cerium and titanium;
  • Y represents at least one element selected from sodium, potassium, cesium, rubidium and thallium;
  • Z represents an element belonging to Groups 1 to 16 of the periodic table; and the above Mo, Bi, means at least one element selected from elements other than Ni, Co, Fe, X, and Y, and b1, c1, d1, e1, f1, g1, h1, and i1 respectively represent the number of atoms of molybdenum, bismuth, nickel, cobalt, iron, X, Y, Z, and oxygen, and satisfy
  • the preferred ranges of b1 to h1 are as follows.
  • the lower limit of b1 is preferably 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, and 0.7
  • the upper limit is preferably 6.0, 5.0, 4.0, 3.0, 2.0, 1.8, 1.5, 1.2, and 1.0. That is, the range of b1 is preferably 0.1 to 6.0, more preferably 0.1 to 5.0, more preferably 0.1 to 4.0, more preferably 0.2 to 3.0, more preferably 0.3 to 2.0, more preferably 0.4 to 1.8, more preferably 0.5 to 1.5, more preferably 0.6 to 1.2, and most preferably 0.7 to 1.0.
  • the lower limit of c1 is preferably 0.2, 0.5, 0.8, 1.0, 1.5, and 1.7
  • the upper limit is preferably 8.0, 7.0, 6.0, 5.0, 4.0, 3.5, 3.3, 3.0, 2.7, and 2.5. That is, the range of c1 is preferably 0.2 to 8.0, more preferably 0.2 to 7.0, more preferably 0.2 to 6.0, more preferably 0.2 to 5.0, more preferably 0.2 to 4.0, more preferably 0.5 to 3.5, more preferably 0.8 to 3.3, more preferably 1.0 to 3.0, more preferably 1.5 to 2.7, and most preferably 1.7 to 2.5.
  • the lower limit of d1 is preferably 1.0, 2.0, 3.0, 4.0, 5.0, 5.5, and 5.8, and the upper limit is preferably 9.5, 9.0, 8.5, 8.0, 7.5, 7.0, 6.8, and 6.6. That is, the range of d1 is preferably 1.0 to 9.5, more preferably 1.0 to 9.0, more preferably 2.0 to 8.5, more preferably 4.0 to 8.0, more preferably 5.0 to 7.0, more preferably 5.5 to 6.8, and most preferably 5.8 to 6.6.
  • the lower limit of c1+d1 is preferably 1.2, 2.0, 4.0, 6.0, 8.0, and 8.3, and the upper limit is preferably 20.0, 15.0, 12.5, 11.0, 10.0, and 9.0.
  • the range of c1+d1 is preferably 1.2 or more and 20.0 or less, more preferably 2.0 or more and 15.0 or less, more preferably 4.0 or more and 12.5 or less, more preferably 6.0 or more and 11.0 or less, more preferably 8.0 or more and 10.0 or less, and most preferably 8.3 or more and 9.0 or less.
  • the lower limit of e1 is preferably 0.1, 0.2, 0.5, 0.8, 1.0, 1.5, and 1.6, and the upper limit is preferably 4.5, 4.0, 3.5, 3.0, 2.5, and 2.3.
  • the range of e1 is preferably 0.1 to 4.5, more preferably 0.2 to 4.5, more preferably 0.5 to 3.5, more preferably 0.8 to 3.0, more preferably 1.0 to 2.5, more preferably 1.5 to 2.5, and most preferably 1.6 to 2.3.
  • the upper limit of f1 is preferably 1.8, 1.5, 1.0, 0.8, and 0.5, and the lower limit is preferably 0. That is, the range of f1 is preferably 0 to 1.8, 0 to 1.5, 0 to 1.0, 0 to 0.8, and 0 to 0.5, and most preferably f1 is 0.
  • the lower limit of g1 is preferably 0.010, 0.020, and 0.030, and the upper limit is preferably 2, 1, 0.5, 0.4, 0.3, 0.2, 0.15, 0.10, 0.075, and 0.050. That is, the range of g1 is preferably 0.010 to 2, more preferably 0.010 to 1, more preferably 0.010 to 0.5, more preferably 0.010 to 0.4, more preferably 0.010 to 0.3, more preferably 0.010 to 0.2, more preferably 0.010 to 0.15, more preferably 0.010 to 0.10, more preferably 0.020 to 0.075, and most preferably 0.030 to 0.050.
  • the upper limit of h1 is preferably 4.0, 3.0, 2.0, 1.8, 1.5, 1.0, 0.8, and 0.5, and the lower limit is preferably 0. That is, the range of h1 is preferably 0 to 4.0, 0 to 3.0, 0 to 2.0, 0 to 1.8, 0 to 1.5, 0 to 1.0, 0 to 0.8, and 0 to 0.5, and most preferably h1 is 0.
  • X is preferably tungsten, antimony, zinc, magnesium or cerium, and particularly preferably antimony or zinc.
  • Y is preferably sodium, potassium or cesium, more preferably potassium or cesium, and particularly preferably cesium.
  • Z is preferably vanadium, copper, niobium, zirconium, calcium, beryllium, strontium, barium, lead or phosphorus.
  • the starting materials for the elements constituting the catalyst represented by the above formula (2) are not particularly limited.
  • the starting material for the molybdenum component there can be used molybdenum oxides such as molybdenum trioxide, molybdic acid, ammonium paramolybdate, ammonium metamolybdate, or a salt thereof, a molybdenum-containing heteropolyacid such as phosphomolybdic acid, silicomolybdic acid, or a salt thereof, and the like.
  • the raw materials for the bismuth component can include bismuth salts such as bismuth nitrate, bismuth carbonate, bismuth sulfate, and bismuth acetate, bismuth trioxide, and metallic bismuth. These raw materials can be used as solids, or as an aqueous solution, a nitric acid solution, or a slurry of the bismuth compound produced from these aqueous solutions, but it is preferable to use the nitrate salt, or a solution thereof, or a slurry produced from the solution.
  • bismuth salts such as bismuth nitrate, bismuth carbonate, bismuth sulfate, and bismuth acetate, bismuth trioxide, and metallic bismuth.
  • the starting materials for the other component elements may be ammonium salts, nitrates, nitrites, carbonates, subcarbonates, acetates, chlorides, inorganic acids, salts of inorganic acids, heteropolyacids, salts of heteropolyacids, sulfates, hydroxides, organic acid salts, oxides, or mixtures thereof of the metal elements generally used in this type of catalyst, with ammonium salts and nitrates being preferred.
  • the slurry liquid can be obtained by uniformly mixing each active ingredient-containing compound with water.
  • the amount of water used in the slurry liquid can be determined appropriately taking into account the drying method and drying conditions.
  • the amount of water used is 100 parts by mass or more and 2000 parts by mass or less per 100 parts by mass of the total mass of the compounds used to prepare the slurry. The more water there is, the better, but if there is too much water, the energy cost of the drying process will be high and there is a risk that complete drying will not be possible.
  • the slurry liquid of the source compounds of each of the above-mentioned component elements is preferably prepared by (i) mixing the above-mentioned source compounds all at once, (ii) mixing them all at once and then aging them, (iii) mixing them in stages, (iv) repeating mixing and aging in stages, or a combination of (i) to (iv).
  • the aging refers to "processing industrial raw materials or semi-finished products under specific conditions such as a certain time and a certain temperature to obtain or increase the required physical or chemical properties or to promote a certain reaction.”
  • the certain time refers to a range of 5 minutes to 24 hours
  • the certain temperature refers to a range above room temperature and below the boiling point of the aqueous solution or aqueous dispersion.
  • the method (iii) of mixing in stages is preferred in terms of the activity and yield of the final catalyst, and the more preferred method is a method in which each raw material to be mixed in stages into the mother liquor is a solution in which it is completely dissolved, and the most preferred method is a method in which an alkali metal solution and various mixed solutions of nitrates are mixed into a mother liquor in which the molybdenum raw material is prepared as a liquid or slurry.
  • any stirring blade such as a propeller blade, turbine blade, paddle blade, inclined paddle blade, screw blade, anchor blade, ribbon blade, large lattice blade, etc. can be used in one stage or in two or more stages of the same or different blades in the vertical direction.
  • baffles baffle plates may be installed in the reaction tank as necessary.
  • the slurry liquid thus obtained is dried.
  • the drying method there are no particular restrictions on the drying method as long as it can completely dry the slurry liquid, but examples include drum drying, freeze drying, spray drying, and evaporation to dryness.
  • spray drying is particularly preferred, as it can dry the slurry liquid into powder or granules in a short period of time.
  • the drying temperature for spray drying varies depending on the concentration of the slurry liquid, the liquid delivery speed, etc., but generally the temperature at the outlet of the dryer is 70°C or higher and 150°C or lower.
  • the catalyst precursor obtained as described above can be pre-calcined, molded, and then finally calcined, making it possible to control and maintain the molded shape, resulting in a catalyst with excellent mechanical strength, particularly for industrial applications, and capable of exhibiting stable catalytic performance.
  • the molding can be performed by either supported molding, in which the catalyst is supported on an inert carrier such as silica, or non-supported molding, in which no carrier is used.
  • Specific molding methods include, for example, granulation molding.
  • the shape of the molded product can be selected appropriately, for example, from spherical, ellipsoidal, etc., taking into account the operating conditions.
  • the catalyst precursor is supported on a spherical carrier, especially an inert carrier such as silica or alumina, and has an average particle size of 3.0 mm to 10.0 mm, preferably 3.0 mm to 8.0 mm.
  • the catalyst is a spherical supported catalyst with an average particle size of 3.0 mm to 8.0 mm.
  • a supporting method the rolling granulation method, the method using a centrifugal fluidized coating device, the wash coat method, etc. are widely known, and there is no particular limitation as long as the pre-calcined powder can be supported uniformly on the carrier, but when considering the production efficiency of the catalyst, the rolling granulation method is preferable.
  • the method is a method in which a carrier charged in a fixed cylindrical container is vigorously stirred by repeated rotation and revolution of the carrier itself by using an apparatus having a flat or uneven disk at the bottom of the container, and the carrier is supported on the carrier by adding the pre-calcined powder to the container.
  • a binder for supporting the carrier.
  • binders include water, ethanol, methanol, propanol, polyhydric alcohols, polyvinyl alcohol as a polymer binder, and silica sol aqueous solutions as inorganic binders.
  • Ethanol, methanol, propanol, and polyhydric alcohols are preferred, diols such as ethylene glycol and triols such as glycerin are more preferred, and an aqueous solution of glycerin with a concentration of 5% by mass or more is even more preferred.
  • an aqueous glycerin solution By using an appropriate amount of an aqueous glycerin solution, the moldability is improved, and a catalyst with high mechanical strength and high performance can be obtained.
  • the amount of these binders used is usually 2 to 60 parts by weight per 100 parts by weight of the pre-calcined powder, but in the case of a glycerin aqueous solution, 15 to 50 parts by weight is preferred.
  • the binder and the pre-calcined powder may be fed alternately or simultaneously to the molding machine. Also, during molding, small amounts of known additives such as graphite, talc, etc. may be added. Note that molding aids, pore-forming agents, and carriers added during molding are not considered as constituent elements of the active component in the present invention, regardless of whether they have activity in the sense of converting the raw materials into some other product.
  • the pre-firing method and pre-firing conditions, or the main firing method and main firing conditions are not particularly limited, and known processing methods and conditions can be applied.
  • Pre-firing and main firing are usually performed under an oxygen-containing gas such as air or an inert gas flow at 200°C to 600°C, preferably 300°C to 550°C, for 0.5 hours or more, preferably 1 hour to 40 hours.
  • the inert gas refers to a gas that does not reduce the reaction activity of the catalyst, and specific examples include nitrogen, carbon dioxide, helium, and argon.
  • the optimal conditions, particularly in the main firing differ depending on the reaction conditions when producing unsaturated aldehydes and/or unsaturated carboxylic acids using a catalyst, and changing the process parameters of the main firing process, i.e., the oxygen content in the atmosphere, the maximum temperature reached, and the firing time, is known to those skilled in the art, and is therefore considered to be within the scope of the present invention.
  • the main calcination process is carried out after the above-mentioned pre-calcination process, and the maximum temperature reached in the main calcination process (main calcination temperature) is higher than the maximum temperature reached in the above-mentioned pre-calcination process (pre-calcination temperature).
  • calcination method such as a fluidized bed, rotary kiln, muffle furnace, or tunnel calcination furnace, and the method should be appropriately selected taking into account the final catalyst performance, mechanical strength, moldability, production efficiency, etc.
  • the method of adjusting the SPHT3, Symm3, and aspect ratio of the catalyst for producing unsaturated aldehydes or conjugated diene compounds can be achieved by appropriately adjusting two or more of the conditions for preparation, drying, pre-calcination, grinding, molding, and main calcination, in the same manner as the catalyst for producing unsaturated carboxylic acids.
  • the catalyst of the present invention is preferably used as a catalyst for producing unsaturated aldehyde compounds, unsaturated carboxylic acid compounds, or conjugated diene compounds, and is preferably used according to its composition as described above.
  • the catalyst having the composition of the above formula (1) is particularly useful as a catalyst for producing unsaturated carboxylic acids using unsaturated aldehydes as starting materials.
  • the catalyst having the composition of the above formula (2) is particularly useful as a catalyst for producing unsaturated aldehydes using propylene, isobutylene, t-butyl alcohol, etc. as starting materials, or conjugated diolefins using monoolefin starting materials as starting materials.
  • the method of flowing the raw material gas may be a normal single flow method or a recycle method, and may be carried out under generally used conditions and is not particularly limited.
  • a mixed gas consisting of 1 to 10% by volume, preferably 4 to 9% by volume of starting raw materials at room temperature, 3 to 20% by volume, preferably 4 to 18% by volume of molecular oxygen, 0 to 60% by volume, preferably 4 to 50% by volume of steam, and 20 to 80% by volume, preferably 30 to 60% by volume of inert gas such as carbon dioxide or nitrogen is introduced onto the catalyst of the present invention filled in a reaction tube at 240 to 450° C., under a pressure of normal pressure to 10 atm, and at a space velocity of 300 to 5000 h ⁇ 1 to carry out the reaction.
  • inert gas such as carbon dioxide or nitrogen
  • the catalysts of the above-mentioned types are arranged so that the activity becomes higher from the raw material inlet to the outlet in the raw material gas flow direction.
  • the number of divisions n is not particularly limited, but is usually 2 to 5, preferably 2 to 3.
  • the above-mentioned different types of catalysts do not only mean the case where the catalyst composition is different, but also include the case where the support rate on the inert carrier is different or the case where the dilution rate is different.
  • raw material conversion rate (%) (number of moles of reacted acrolein)/(number of moles of supplied acrolein) ⁇ 100
  • Yield (%) (moles of acrylic acid produced)/(moles of acrolein fed) ⁇ 100
  • Selectivity (%) (moles of acrylic acid produced)/(moles of acrolein reacted) ⁇ 100
  • the median diameter of the pre-calcined powder shown in this example is the volume-based median value when the equivalent circle diameter Xarea of the powder dispersed in air is measured using a CAMSIZER X2 manufactured by Microtrac-Bell Co., Ltd.
  • the equivalent circle diameter Xarea can be calculated from the following formula (IV) when the measured particle area is A.
  • X area (4A/ ⁇ ) (1/2) ...(IV)
  • Example 1 ⁇ Production of Catalyst 1> 148 parts by mass of ammonium paratungstate was completely dissolved in 5241 parts by mass of pure water heated to 95 ° C. While stirring this solution, 166 parts by mass of ammonium metavanadate, 1000 parts by mass of ammonium molybdate, and 70.5 parts by mass of antimony acetate were gradually added and thoroughly stirred. Next, 143 parts by mass of copper sulfate was added to 427 parts by mass of pure water heated to 80 ° C., and the solution was completely dissolved and added to the above solution, and mixed by stirring. This preparation liquid (A) was dried by a spray drying method, and the obtained dried powder (B) was pre-fired at 350 ° C.
  • the obtained pre-fired body (C) was pulverized with a vibration mill to obtain a pre-fired powder (E).
  • the median diameter of the obtained pre-fired powder (E) was 22.7 ⁇ m. 5% by mass of crystalline cellulose and 5% by mass of milled fiber EFH150-31 manufactured by Central Glass Co., Ltd. were added to the pre-calcined powder (E) and mixed thoroughly, and then a 20% by mass glycerin solution was used as a binder by the rolling granulation method, and the mixture was molded into an inactive spherical carrier made of a mixture of silica and alumina so that the loading rate was 33% by mass.
  • FIG. 1 is a schematic diagram showing the binder addition method in Example 1, showing a top view of a rolling granulator 10.
  • the rolling granulator 10 is charged with spherical carriers, and the carriers are stirred by rotating the bottom plate 11 clockwise as indicated by the arrow CW in FIG. 1.
  • granules containing the pre-calcined powder (E) were charged at position A on the bottom plate 11 of the rolling granulator 10 to which the spherical carriers were charged.
  • a binder addition point B was provided at a position 240 degrees from the granule drop point A in the direction of rotation of the bottom plate 11 of the tumbling granulator 10, and the binder addition ports were divided into six locations in the radial direction of the doughnut-shaped catalyst band 20 generated when the bottom plate 11 of the tumbling granulator 10 rotated, and the binder was dropped at a uniform flow rate from each of them.
  • the centrifugal acceleration at that time was 4.2 G.
  • main calcination was carried out under conditions of 375° C. for 4 hours to obtain a spherical catalyst 1 of the present invention.
  • the composition of catalyst 1 is Mo 12 V 3.0 W 1.2 Cu 1.2 Sb 0.50 .
  • Example 2 ⁇ Production of Catalyst 2> 148 parts by mass of ammonium paratungstate was completely dissolved in 5241 parts by mass of pure water heated to 95 ° C. While stirring this solution, 166 parts by mass of ammonium metavanadate, 1000 parts by mass of ammonium molybdate, and 70.5 parts by mass of antimony acetate were gradually added and thoroughly stirred. Next, 143 parts by mass of copper sulfate was added to 427 parts by mass of pure water heated to 80 ° C., and the solution was completely dissolved and added to the above solution, and mixed by stirring. This preparation liquid (A) was dried by a spray drying method, and the obtained dried powder (B) was pre-fired at 350 ° C.
  • pre-fired body (C) was pulverized with a ball mill to obtain a pre-fired powder (E).
  • the median diameter of the obtained pre-fired powder (E) was 26.1 ⁇ m.
  • 5% by mass of crystalline cellulose and 5% by mass of Central Glass Milled Fiber EFH150-31 were added to the pre-calcined powder (E) and mixed thoroughly, and then a 20% by mass glycerin solution was used as a binder by the rolling granulation method, and the mixture of silica and alumina was molded into an inactive spherical carrier so that the loading rate was 33% by mass.
  • FIG. 2 is a schematic diagram showing the method of adding the binder in Example 2, and is the same as FIG. 1 except that the binder addition position B is different.
  • main calcination was carried out under conditions of 390° C. for 4 hours to obtain a spherical catalyst 2 of the present invention.
  • the composition of catalyst 2 is Mo 12 V 3.0 W 1.2 Cu 1.2 Sb 0.50 .
  • Example 3 ⁇ Production of Catalyst 3> 148 parts by mass of ammonium paratungstate was completely dissolved in 5241 parts by mass of pure water heated to 95 ° C. While stirring this solution, next, 166 parts by mass of ammonium metavanadate and 1000 parts by mass of ammonium molybdate were added and dissolved. Then, a suspension of 70.5 parts by mass of antimony acetate and 150 parts by mass of 10% by weight ammonia water was gradually added and thoroughly stirred. Next, 143 parts by mass of copper sulfate was added to 427 parts by mass of pure water heated to 80 ° C., and the solution was completely dissolved.
  • the mixture (A) was dried by a spray drying method, and the obtained dried powder (B) was pre-fired at 350 ° C. for 4 hours to obtain a pre-fired body (C).
  • the obtained pre-fired body (C) was pulverized with a ball mill to obtain a pre-fired powder (E).
  • the median diameter of the obtained pre-fired powder (E) was 26.8 ⁇ m.
  • a single-flow liquid pump was used to add the binder, and a single binder addition port was provided at a position 180 degrees ahead of the granule drop point A in the direction of rotation of the bottom plate 11 of the rolling granulator 10, and the binder was dropped into the center of the radial direction of the donut-shaped catalyst band 20 generated when the bottom plate 11 of the rolling granulator 10 rotated. That is, the position of addition of the binder in this example was the same as that of Example 2 shown in FIG. 2. The centrifugal acceleration at that time was 26G. Next, main calcination was carried out under conditions of 390° C. for 4 hours to obtain a spherical catalyst 3 of the present invention.
  • the composition of catalyst 3 is Mo 12 V 3.0 W 1.2 Cu 1.2 Sb 0.50 .
  • Example 4 ⁇ Production of Catalyst 4> 148 parts by mass of ammonium paratungstate was completely dissolved in 5241 parts by mass of pure water heated to 95 ° C. While stirring this solution, 166 parts by mass of ammonium metavanadate and 1000 parts by mass of ammonium molybdate were added, and after confirming dissolution, 70.5 parts by mass of antimony acetate was gradually added and thoroughly stirred. Next, 143 parts by mass of copper sulfate was added to 427 parts by mass of pure water heated to 80 ° C., and the solution was completely dissolved and added to the above solution, and mixed by stirring.
  • This preparation liquid (A) was dried by a spray drying method, and the obtained dried powder (B) was pre-fired at 350 ° C. for 4 hours to obtain a pre-fired body (C).
  • the obtained pre-fired body (C) was pulverized with a ball mill to obtain a pre-fired powder (E).
  • the median diameter of the obtained pre-fired powder (E) was 37.5 ⁇ m.
  • FIG. 3 is a schematic diagram showing the binder addition method in Example 4, and is the same as FIG. 1 except that the binder addition position B is different.
  • main calcination was carried out under conditions of 390° C. for 4 hours to obtain a spherical catalyst 4 of the present invention.
  • the composition of the catalyst 4 is Mo 12 V 3.0 W 1.2 Cu 1.2 Sb 0.50 .
  • Example 5 ⁇ Production of Catalyst 5> 148 parts by mass of ammonium paratungstate was completely dissolved in 5241 parts by mass of pure water heated to 95 ° C. While stirring this solution, 166 parts by mass of ammonium metavanadate and 1000 parts by mass of ammonium molybdate were added, and after confirming dissolution, 70.5 parts by mass of antimony acetate was gradually added and thoroughly stirred. Next, 143 parts by mass of copper sulfate was added to 427 parts by mass of pure water heated to 80 ° C., and the solution was completely dissolved and added to the above solution, and mixed by stirring.
  • This preparation liquid (A) was dried by a spray drying method, and the obtained dried powder (B) was pre-fired at 350 ° C. for 4 hours to obtain a pre-fired body (C).
  • the obtained pre-fired body (C) was pulverized with a ball mill to obtain a pre-fired powder (E).
  • the median diameter of the obtained pre-fired powder (E) was 37.5 ⁇ m.
  • a single-flow liquid pump was used to add the binder, and a single binder addition port was provided at a position 180 degrees ahead of the granule drop point A in the direction of rotation of the bottom plate 11 of the rolling granulator 10, and the binder was dropped into the center of the radial direction of the donut-shaped catalyst band 20 generated when the bottom plate 11 of the rolling granulator 10 rotated. That is, the position of addition of the binder in this example was the same as that of Example 2 shown in FIG. 2. The centrifugal acceleration at that time was 26G. Next, main calcination was carried out under conditions of 390° C. for 4 hours to obtain a spherical catalyst 5 of the present invention.
  • the composition of catalyst 5 is Mo 12 V 3.0 W 1.2 Cu 1.2 Sb 0.50 .
  • This preparation liquid (A) was dried by a spray drying method, and the obtained dried powder (B) was pre-fired at 350 ° C. for 4 hours to obtain a pre-fired body (C).
  • the obtained pre-fired body (C) was pulverized with a ball mill to obtain a pre-fired powder (E).
  • the median diameter of the obtained pre-fired powder (E) was 36.0 ⁇ m.
  • crystalline cellulose 5% by mass was added to the pre-calcined powder (E), and after thorough mixing, a 20% by mass glycerin solution was used as a binder by the rolling granulation method, and the mixture was molded into an inactive spherical carrier consisting of a mixture of silica and alumina so that the loading rate was 33% by mass.
  • FIG. 4 is a schematic diagram showing the binder addition method in Example 6, and is the same as FIG. 1 except that the binder addition position B is different.
  • the main calcination was carried out under conditions of 390° C. for 4 hours, to obtain a spherical catalyst 6 of the present invention.
  • the composition of the catalyst 6 is Mo 12 V 3.0 W 1.2 Cu 1.2 Sb 0.50 .
  • This preparation liquid (A) was dried by a spray drying method, and the obtained dried powder (B) was pre-fired at 350 ° C. for 4 hours to obtain a pre-fired body (C).
  • the obtained pre-fired body (C) was pulverized with a ball mill to obtain a pre-fired powder (E).
  • the median diameter of the obtained pre-fired powder (E) was 29.8 ⁇ m.
  • FIG. 5 is a schematic diagram showing the method of adding the binder in Comparative Example 1, and is the same as FIG. 1 except that the binder addition position B is different.
  • main calcination was carried out under conditions of 390° C. for 4 hours, and a spherical catalyst 7 was obtained.
  • the composition of the catalyst 7 is Mo 12 V 3.0 W 1.2 Cu 1.2 Sb 0.50 .
  • pre-fired body (C) was pulverized with a ball mill to obtain a pre-fired powder (E).
  • the median diameter of the obtained pre-fired powder (E) was 28.2 ⁇ m.
  • 5% by mass of crystalline cellulose and 5% by mass of Central Glass Milled Fiber EFH150-31 were added to the pre-calcined powder (E), and after thorough mixing, a 20% by mass glycerin solution was used as a binder by the rolling granulation method, and the mixture was molded into an inactive spherical carrier consisting of a mixture of silica and alumina so that the loading rate was 25% by mass.
  • FIG. 6 is a schematic diagram showing a method of adding a binder in Comparative Example 2, which is similar to FIG. 1 except that the position B where the binder is added is different.
  • main calcination was carried out under conditions of 390° C. for 4 hours, and a spherical catalyst 8 was obtained.
  • the composition of the catalyst 8 is Mo 12 V 3.0 W 1.2 Cu 1.2 Sb 0.50 .
  • This preparation liquid (A) was dried by a spray drying method, and the obtained dried powder (B) was pre-fired at 350 ° C. for 4 hours to obtain a pre-fired body (C).
  • the obtained pre-fired body (C) was pulverized with a ball mill to obtain a pre-fired powder (E).
  • the median diameter of the obtained pre-fired powder (E) was 17.0 ⁇ m.
  • a single-flow liquid pump was used to add the binder, and a single binder addition port was provided at a position 180 degrees ahead of the granule drop point A in the direction of rotation of the bottom plate 11 of the rolling granulator 10, and the binder was dropped into the center of the radial direction of the donut-shaped catalyst band 20 generated when the bottom plate 11 of the rolling granulator 10 rotated. That is, the position of addition of the binder in this example was the same as that of Example 2 shown in FIG. 2. The centrifugal acceleration at that time was 26G. Next, main calcination was carried out under conditions of 390° C. for 4 hours, and a spherical catalyst 9 was obtained.
  • the composition of the catalyst 9 is Mo 12 V 3.0 W 1.2 Cu 1.2 Sb 0.50 .
  • Example 7 (Preparation of Catalyst 10) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 60 ° C. (mother liquor 1). Next, 0.37 parts by mass of cesium nitrate was dissolved in 3.3 parts by mass of pure water and added to mother liquor 1. Next, 37 parts by mass of ferric nitrate, 90 parts by mass of cobalt nitrate and 33 parts by mass of nickel nitrate were dissolved in 85 parts by mass of pure water heated to 80 ° C. and added to mother liquor 1.
  • 5% by mass of crystalline cellulose was added to the pre-calcined powder, and after thorough mixing, the mixture was spherically supported on an inactive carrier consisting of a mixture of silica and alumina using a 33% by mass glycerin solution as a binder by a rolling granulation method so that the support rate was 50% by mass.
  • a sprayer was used to add the binder, and the binder was sprayed so that the binder was evenly applied to the catalyst passing a position 90 degrees ahead from the drop point A of the granules in the rotation direction of the bottom plate 11 of the rolling granulator 10.
  • the centrifugal acceleration at that time was 26 G.
  • Figure 7 is a schematic diagram showing the method of adding the binder in Example 7, and is the same as Figure 1 except that the binder addition position B is different.
  • main calcination was carried out under conditions of 520° C. for 4 hours to obtain a catalyst 10.
  • the present invention can maintain high catalytic activity, particularly when acrolein is used as a raw material to produce acrylic acid through a gas-phase catalytic oxidation reaction. This is extremely useful, as it allows plants for producing acrylic acid to operate stably for long periods of time.

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PCT/JP2023/044644 2022-12-20 2023-12-13 触媒及びそれを用いた化合物の製造方法 Ceased WO2024135496A1 (ja)

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EP23906861.2A EP4640312A1 (en) 2022-12-20 2023-12-13 Catalyst and method for producing compound using same
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