WO2022065116A1 - 触媒前駆体、それを用いた触媒、化合物の製造方法及び触媒の製造方法 - Google Patents

触媒前駆体、それを用いた触媒、化合物の製造方法及び触媒の製造方法 Download PDF

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WO2022065116A1
WO2022065116A1 PCT/JP2021/033592 JP2021033592W WO2022065116A1 WO 2022065116 A1 WO2022065116 A1 WO 2022065116A1 JP 2021033592 W JP2021033592 W JP 2021033592W WO 2022065116 A1 WO2022065116 A1 WO 2022065116A1
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catalyst
mass
catalyst precursor
preferable
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English (en)
French (fr)
Japanese (ja)
Inventor
成喜 奥村
将吾 保田
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to KR1020237005503A priority Critical patent/KR20230073177A/ko
Priority to EP21872246.0A priority patent/EP4219003A4/en
Priority to JP2022502523A priority patent/JP7105395B1/ja
Priority to US18/044,144 priority patent/US20240238768A1/en
Priority to CN202180063939.0A priority patent/CN116261487A/zh
Publication of WO2022065116A1 publication Critical patent/WO2022065116A1/ja
Priority to JP2022110990A priority patent/JP2022137174A/ja
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    • 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
    • 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
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J23/8872—Alkali or alkaline earth metals
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J35/52—Hollow spheres
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
    • B01J37/0063—Granulating
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
    • C07C27/12—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen
    • C07C27/14—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen wholly gaseous reactions
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    • 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
    • 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
    • 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
    • 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
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36

Definitions

  • the present invention relates to a novel catalyst having a high activity and a high yield to obtain a desired product, and the catalytic activity is particularly high when an unsaturated aldehyde, an unsaturated carboxylic acid, or a conjugated diene is oxidatively produced.
  • the present invention relates to a catalyst that enables stable and high-yield production even in a high region.
  • the mother liquor may be evaporated to dryness or gelled, but the semi-finished product after the step is in a thickened or solidified state. It is difficult to handle as a manufacturing method on an industrial scale, and the cost of the catalyst tends to be high.
  • Patent Document 3 describes the hollow particle ratio of the granular composite metal oxide catalyst for fluidized bed use. It is stated that the mechanical strength is improved when the content is 23% or less.
  • Patent Document 4 describes that a molding catalyst having high mechanical strength can be obtained by defining the viscosity of the preparation liquid and the bulk density of the calcined product.
  • the mother liquor in the compounding process tends to thicken and it tends to be difficult to send the liquor to the spray dryer, resulting in low productivity.
  • the obtained mother liquor can be stably dried with a spray dryer without thickening the mother liquor in the compounding step, and what kind of physical properties as the catalyst precursor thus obtained are the high yield of the final catalyst. It was unclear whether it was important for the transformation.
  • the present invention proposes a catalyst precursor capable of obtaining a catalyst having high selectivity and a high yield of a target product, and a catalyst using the catalyst precursor.
  • the present invention when the average particle size of the catalyst precursor obtained by drying the mixed solution of the catalytically active component raw materials or the slurry is in a specific range, the final catalyst performance, particularly the catalytic activity, is significantly improved. It was found that the present invention was improved in the above, and the present invention was completed.
  • D50 average particle diameter
  • Mo, Bi, Ni, Co and Fe represent molybdenum, bismuth, nickel, cobalt and iron, respectively
  • X represents tungsten, antimony, tin, zinc, chromium, manganese, magnesium, calcium, silicon, aluminum and cerium, respectively.
  • At least one element selected from titanium, Y is at least one element selected from sodium, potassium, cesmuth, rubidium, and tarium, Z belongs to groups 1 to 16 of the periodic table, and Mo, Bi, It means at least one element selected from elements other than Ni, Co, Fe, X, and Y, and a1, b1, c1, d1, e1, f1, g1, h1, and i1 are molybdenum and bismuth, respectively.
  • the catalyst precursor of the present invention is very effective in improving the catalytic activity and yield in the gas-phase catalytic oxidation reaction.
  • the present invention relates to a catalyst having particularly high catalytic activity, a method for producing the same, and the like.
  • the catalyst is produced via the catalyst precursor, or the catalyst precursor can be used as it is as an oxidation catalyst.
  • the precursor itself is also described as the present invention.
  • Average particle size (D50) is 10 ⁇ m or more and 40 ⁇ m or less
  • the catalyst precursor of the present invention has an average particle size of 10 ⁇ m or more and 40 ⁇ m or less.
  • the average particle size can be measured by a known method, for example, using the following equipment.
  • the particle size distribution is measured from a laser diffraction / scattering particle size distribution measuring device (manufactured by Seishin Enterprise Co., Ltd., trade name “LMS-2000e”), and the particle size distribution is obtained as the volume average (median size). That is, it is the median value in the volume fraction.
  • LMS-2000e laser diffraction / scattering particle size distribution measuring device
  • the particle size distribution is obtained as the volume average (median size). That is, it is the median value in the volume fraction.
  • the scattering range is set to 10 to 20%
  • the measurement time is 3 seconds
  • the number of snaps is 3000
  • the sample material is Fraunhofer
  • the dispersion medium is used. Measure with water and a stirrer pump at 2500 rpm without applying ultrasonic waves.
  • the average particle diameter means a particle diameter in which the cumulative volume fraction is 50%, and may be expressed as D50 in the present specification.
  • the particle diameter at which the cumulative volume fraction is 10% is expressed as D10
  • the particle diameter at which the cumulative volume fraction is 90% is expressed as D90.
  • the measurement method may be either wet or dry, but in the embodiment of the present application, the wet method is used.
  • the average particle size (D50) is outside the range of 10 ⁇ m or more and 40 ⁇ m or less, the performance when used as a catalyst is not stable, and as a result, the catalytic activity may be lowered.
  • the lower limit of the preferable range of the average particle size (D50) is 15 ⁇ m, more preferably 20 ⁇ m, and particularly preferably 23 ⁇ m.
  • the upper limit is preferably 38 ⁇ m, more preferably 35 ⁇ m, and particularly preferably 32 ⁇ m. That is, the most preferable range for the average particle size is 23 ⁇ m or more and 32 ⁇ m or less.
  • the catalyst precursor of the present invention preferably has a hollow particle ratio of 0.0% or more and 4.3% or less as defined below. That is, the catalyst precursor samples are photographed with a microscope at a magnification of 20 times for 1 g, being careful not to overlap with each other, and each of the obtained catalyst precursor samples is determined to be hollow or non-hollow. 200 or more catalyst precursor samples are measured, and the number of hollow catalyst precursors is divided by the number of measured catalyst precursors and multiplied by 100 to obtain the hollow particle ratio of the catalyst precursor.
  • the judgment of hollow or non-hollow is considered to be hollow if the total area of the particles (total area in the part shown in the micrograph) is more than 5% and is shaded by dents or irregularities. Examples are shown in FIGS. 1 and 2.
  • the area ratios of the catalyst precursors shown in order from the left in FIG. 1 to the catalyst particles in the recesses and uneven portions are 11%, 12%, and 6%, respectively. It was determined that none of the catalyst precursors shown in FIG. 2 had dents.
  • To determine hollow particles increase or binarize the contrast of the microscope image, interpolate the part where the catalyst particle to be measured overlaps with other catalyst particles as shown on the left of Fig. 1, and make dents and uneven parts.
  • FIG. 3 is a binarized image of the micrograph shown in FIG.
  • FIG. 4 is a diagram showing the outer shape of the catalyst precursor (hollow particle) with a broken line and the recessed portion with a dot region in the binarized image shown in FIG.
  • the outer shape of the particle is imitated as an ellipse (the ellipse shown by the broken line in FIG. 4) in the micrograph, and the area of the ellipse drawn from the five points on the outer circumference is defined as the total area of the particle.
  • the recessed portion (the portion shown by the dot region in FIG. 4)
  • a commercially available image processing software is used to surround the outer edge of the recessed portion and the area thereof is calculated by the software.
  • the area of the recessed part (dot part) was calculated using Photoshop (registered trademark) manufactured by Adobe Incorporated.
  • the lower limit of the hollow particle ratio of the catalyst precursor is 0.1%, 0.3%, 0.5%, 1.0%, and 1.5% in the order of preference, and the upper limit of the hollow particle ratio of the catalyst precursor is preferable. They are 4.0%, 3.8%, 3.5%, 3.0%, 2.8%, 2.5% and 2.2% in that order. That is, the most preferable range for the hollow particle ratio of the catalyst precursor is 1.5% or more and 2.2% or less.
  • the upper limit of the water content of the granules is 14.5% by mass, 14.0% by mass, 13.0% by mass, 12.0% by mass, and 11.0% by mass in the order of preference. That is, the most preferable range for the water content of the catalyst precursor is 10.0% by mass or more and 11.0% by mass or less.
  • the catalyst precursor of the present invention is granules before the step of molding the catalyst, and is also described as a pre-baked powder in the present invention, and is a slurry obtained by mixing raw materials containing each element constituting the catalyst.
  • spray drying which allows the slurry to be dried into granules in a short time, is particularly preferable.
  • D10 is 10 ⁇ m or more and 25 ⁇ m or less.
  • the lower limit of D10 is 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, and 15 ⁇ m in the more preferable order.
  • the upper limit is 24 ⁇ m, 23 ⁇ m, 22 ⁇ m, 21 ⁇ m, 20 ⁇ m, 19 ⁇ m, and 18 ⁇ m in the more preferable order. That is, the D10 is most preferably 15 ⁇ m or more and 18 ⁇ m or less.
  • the catalyst precursor of the present invention preferably has a D90 of 40 ⁇ m or more and 65 ⁇ m or less.
  • the lower limit of D90 is 42 ⁇ m, 45 ⁇ m, 48 ⁇ m, and 50 ⁇ m in the more preferable order.
  • the upper limit is 64 ⁇ m, 63 ⁇ m, 62 ⁇ m, 61 ⁇ m, and 60 ⁇ m in the more preferable order. That is, the D90 is most preferably 50 ⁇ m or more and 60 ⁇ m or less.
  • a more preferable upper limit of the atomizer rotation speed is 20,000 pm, particularly preferably 19,000 rpm, and most preferably 18,500 rpm.
  • the more preferable lower limit is 10,000 rpm, 12,000 rpm, and 14,000 rpm, respectively, the particularly preferable lower limit is 15,000 rpm, and the most preferable lower limit is 16,000 rpm. That is, the most preferable range of atomizer rotation speed is 16,000 rpm or more and 18,500 rpm or less.
  • the rotation speed of the atomizer is also expressed by the relative centrifugal acceleration, and is preferably 12500 G or more and 50,000 G or less.
  • the more preferable lower limit is 15000G, 17500G, 18500G, 19000G in order
  • the more preferable upper limit is 45000G, 40000G, 37500G, 35000G, 32500G in order. That is, the most preferable range of the atomizer rotation speed is 19000 G or more and 32500 G or less.
  • the inlet temperature and the outlet temperature of the sprayer for spray drying also affect the above parameters (average particle size of the catalyst precursor, hollow particle ratio of the catalyst precursor, water content of the catalyst precursor).
  • the inlet temperature is preferably 200 ° C. or higher and 350 ° C. or lower.
  • the more preferable lower limit is 210 ° C., 220 ° C., 230 ° C., 250 ° C., 270 ° C., 280 ° C., respectively
  • the more preferable upper limit is 340 ° C., 330 ° C., 320 ° C., 310 ° C., respectively. That is, the inlet temperature is most preferably 280 ° C. or higher and 310 ° C. or lower.
  • the outlet temperature is preferably 100 ° C. or higher and 150 ° C. or lower.
  • the more preferable lower limit is 101 ° C., 102 ° C., 103 ° C., 104 ° C., 105 ° C.
  • the more preferable upper limit is 140 ° C., 130 ° C., 120 ° C., respectively. That is, the outlet temperature is most preferably 105 ° C. or higher and 120 ° C. or lower.
  • the difference between the inlet temperature and the outlet temperature is preferably 50 ° C. or higher and 140 ° C. or lower.
  • the more preferable lower limit is 70 ° C., 80 ° C., 90 ° C., 100 ° C., 105 ° C.
  • the more preferable upper limit is 135 ° C., 130 ° C., 125 ° C., 120 ° C., respectively. That is, the difference between the inlet temperature and the outlet temperature is most preferably 105 ° C. or higher and 120 ° C. or lower.
  • the range of the parameter SD given by the following formula as the method for producing the catalyst precursor of the present invention is preferably 5 or more and 41 or less.
  • the catalyst precursor of the present invention preferably has a specific surface area of 5.0 m 2 / g or more and 10.4 m 2 / g or less.
  • the specific surface area of the catalyst precursor means the surface area per gram of the precursor, which can be measured by a method known to those skilled in the art, and the details thereof are not limited, but for example, the following method can be used. Can be measured. That is, a sample volume of 0.05 mL to 3.0 mL is placed in a sample tube having an inner diameter of 7 mm, and after pretreatment at 300 ° C. for 2 hours or more, a gas adsorption amount measuring device (Belsorp-mini (Microtrac Bell)) is used.
  • the nitrogen molecule diameter is set to 0.364 nm, the relative pressure ratio is 0.4, the adsorption temperature is -196 ° C, the measured pore diameter range is 0.7 nm to 400 nm, and the adsorption gas type nitrogen is used. It is a method of measuring and analyzing the measurement result by the BET method to obtain the specific surface area value.
  • the lower limit of the preferable range of the specific surface area is 7.5, 8.0, 8.5, 9.0 in the preferred order, and the upper limit is 10.3, 10.2, 10.1, 9.8 in the preferred order. , 9.5. That is, the specific surface area is most preferably 9.0 m 2 / g or more and 9.5 m 2 / g or less.
  • the specific surface area of the catalyst itself is preferably 1.00 m 2 / g or more and 2.80 m 2 / g or less.
  • the more preferable lower limit is 1.20 m 2 / g, 1.40 m 2 / g, 1.60 m 2 / g, 1.80 m 2 / g, 2.00 m 2 / g, 2.20 m 2 / g, respectively.
  • the more preferable upper limit is 2.70 m 2 / g, 2.60 m 2 / g, 2.50 m 2 / g, and 2.40 m 2 / g, respectively. That is, the specific surface area of the catalyst is most preferably 2.20 m 2 / g or more and 2.40 or less m 2 / g.
  • the bulk density of the catalyst precursor of the present invention is preferably 0.8 g / mL or more and 1.3 g / mL or less. Further, the more preferable lower limit is 0.9 g / mL and 1.0 g / mL, and the more preferable upper limit is 1.2 g / mL and 1.1 g / mL. Therefore, the most preferable range is 1.0 g / mL or more and 1.1 g / mL or less.
  • the catalyst precursor of the present invention has a composition represented by the following formula (1).
  • Mo, Bi, Ni, Co and Fe represent molybdenum, bismuth, nickel, cobalt and iron, respectively, and
  • X represents tungsten, antimony, tin, zinc, chromium, manganese, magnesium, calcium, silicon, aluminum and cerium, respectively.
  • At least one element selected from titanium, Y is at least one element selected from sodium, potassium, cesmuth, rubidium, and tarium, Z belongs to groups 1 to 16 of the periodic table, and Mo, Bi, It means at least one element selected from elements other than Ni, Co, Fe, X, and Y, and a1, b1, c1, d1, e1, f1, g1, h1, and i1 are molybdenum and bismuth, respectively.
  • the lower limit of b1 is 0.1, 0.2, 0.3, 0.4, 0.5 in the preferred order, and the upper limit is 6, 5, 4, 3, 2, 1 in the preferred order. That is, the most preferable range for b1 is 0.5 or more and 1 or less.
  • the lower limit of c1 is 0.2, 0.5, 0.8, 1.0, 1.5, 1.8, 2.0, and 2.5 in the preferred order, and the upper limit is 8. It is 0, 7.0, 6.0, 5.0, 4.0, 3.5. That is, the most preferable range for c1 is 2.5 or more and 3.5 or less.
  • the lower limit of d1 is 1.0, 2.0, 3.0, 4.0, 5.0 in the preferred order, and the upper limit is 9.5, 9.0, 8.5, 8. in the preferred order. It is 0, 7.5, 7.0, 6.5, 6.0. That is, the most preferable range for d1 is 5.0 or more and 6.0 or less.
  • the lower limit of c1 + d1 is 0.0, 2.0, 4.0, 6.0, 8.0, 8.3 in the preferred order, and the upper limit is 20.0, 15.0, 12. 5, 11.0, 10.0, 9.0. That is, the most preferable range for c1 + d1 is 8.3 or more and 9.0 or less.
  • the lower limit of e1 is 0.1, 0.2, 0.5, 0.8, 1.0, 1.5 in the preferred order, and the upper limit is 4.5, 4.0, 3. 5, 3.0, 2.5, 2.0, 1.9, 1.8. That is, the most preferable range for e1 is 1.5 or more and 1.8 or less.
  • the upper limit of f1 is 1.8, 1.5, 1.0, 0.8, and 0.5 in the preferred order, and the lower limit is preferably 0. That is, the more preferable range for f1 is 0 or more and 0.5 or less, and 0 is the most preferable.
  • the lower limit of g1 is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07 in the preferred order, and the upper limit is 2, 1, 0.
  • the most preferable range for g1 is 0.07 or more and 0.1 or less.
  • the upper limit of h1 is 4.0, 3.0, 2.0, 1.8, 1.5, 1.0, 0.8, 0.5 in the preferred order, and 0 is preferable as the lower limit. That is, the more preferable range for h1 is 0 or more and 0.5 or less, and 0 is the most preferable.
  • tungsten, antimony, zinc, magnesium, calcium and cerium are preferable, and antimony and zinc are particularly preferable.
  • Y in the formula (1) sodium, potassium and cesium are preferable, potassium and cesium are more preferable, and potassium is particularly preferable.
  • Phosphorus is preferable as Z in the formula (1).
  • the drying temperature is not particularly limited as long as it can remove water, and when adjusting the pressure and time, it may be at room temperature (25 ° C), but more reliably and in a short time. In order to remove it, it is preferably 80 ° C. or higher, and more preferably 90 ° C. or higher. When the pressure is not adjusted, the temperature is preferably 100 ° C. or higher, more preferably 150 ° C. or higher. As the preliminary firing, firing is performed at a temperature of about 200 ° C. to 600 ° C. for about 1 to 12 hours.
  • the atmosphere at the time of firing and the rate of temperature rise are not particularly limited as long as they are known to those skilled in the art, but for example, an air atmosphere, an inert atmosphere such as nitrogen, and a containing machine containing more than 0% of organic compounds such as methanol and ethanol. It is a compound atmosphere, and the heating rate is 0.01 ° C./min or more and 10 ° C./min or less.
  • the catalyst in which the pre-baked powder obtained by pre-firing after preparing the catalyst is supported on the inert carrier is particularly effective as the catalyst of the present invention.
  • the material of the inert carrier known materials such as alumina, silica, titania, zirconia, niobia, silica alumina, silicon carbide, carbides, and mixtures thereof can be used, and further, the particle size, water absorption rate, mechanical strength, and the like can be used.
  • the crystallinity and mixing ratio of the crystal phase are not particularly limited, and an appropriate range should be selected in consideration of the final catalyst performance, moldability, production efficiency, and the like.
  • the mixing ratio of the carrier and the pre-baked powder is calculated as the loading ratio from the following formula according to the charged mass of each raw material.
  • Support rate (% by mass) (mass of pre-baked powder used for molding) / ⁇ (mass of pre-baked powder used for molding) + (mass of carrier used for molding) ⁇ x 100
  • the preferred upper limit of the loading ratio is 80% by mass, more preferably 60% by mass.
  • the lower limit is preferably 20% by mass, more preferably 30% by mass. That is, the most preferable range as the loading ratio is 30% by mass or more and 60% by mass or less.
  • the inert carrier silica and / or alumina are preferable, and a mixture of silica and alumina is particularly preferable.
  • binder examples include water, ethanol, methanol, propanol, polyhydric alcohol, polyvinyl alcohol of a high molecular weight binder, an aqueous solution of silica sol of an inorganic binder, and the like, but ethanol, methanol, propanol, and polyhydric.
  • Alcohol is preferable, diol such as ethylene glycol and triol such as glycerin are preferable, and an aqueous solution having a concentration of glycerin of 5% by mass or more is preferable.
  • the amount of these binders used is usually 2 to 60 parts by mass with respect to 100 parts by mass of the pre-baked powder, but 10 to 30 parts by mass is preferable in the case of an aqueous glycerin solution.
  • the binder and the pre-baked powder may be alternately supplied to the molding machine or simultaneously supplied to the molding machine during loading.
  • the starting material for the catalyst precursor of the present invention and each element constituting the catalyst is not particularly limited, but for example, the raw material for the molybdenum component is molybdenum oxide such as molybdenum trioxide, molybdenum acid, or paramolybdenum acid.
  • Molybdic acid such as ammonium and ammonium metamolybdenum or a salt thereof
  • a heteropolyacid containing molybdenum such as phosphomolybonic acid and silicate molybdic acid or a salt thereof can be used.
  • bismuth nitrate bismuth carbonate, bismuth sulfate, bismuth salt such as bismuth acetate, bismuth trioxide, metal bismuth, etc.
  • bismuth salt such as bismuth acetate, bismuth trioxide, metal bismuth, etc.
  • These raw materials can be used as a solid or as a slurry of an aqueous solution, a nitric acid solution, or a bismuth compound produced from the aqueous solution, but it is preferable to use nitrate, a solution thereof, or a slurry produced from the solution.
  • Heteropolyacid, heteropolyacid salt, sulfate, hydroxide, organic acid salt, oxide or a mixture thereof may be used in combination, but ammonium salt and nitrate are preferably used.
  • the compound containing these active ingredients may be used alone or in combination of two or more.
  • the slurry liquid can be obtained by uniformly mixing each active ingredient-containing compound and water.
  • the amount of water used in the slurry liquid is not particularly limited as long as the total amount of the compound to be used can be completely dissolved or uniformly mixed.
  • the amount of water used may be appropriately determined in consideration of the drying method and drying conditions. Usually, it is 100 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the total mass of the compound for preparing a slurry.
  • the amount of water may be large, but if it is too large, the energy cost of the drying process becomes high, and there are many disadvantages such as the case where the water cannot be completely dried.
  • the slurry liquid of the source compound of each component element is (a) a method of collectively mixing each of the above source compounds, (b) a method of collectively mixing and then aging treatment, and (c) stepwise. It is preferable to prepare by a method of mixing, (d) a method of repeating mixing and aging treatment step by step, and a method of combining (a) to (d).
  • the above-mentioned aging means "processing an industrial raw material or a semi-finished product under specific conditions such as a constant time and a constant temperature to acquire, increase, or proceed with a predetermined reaction having required physical properties and chemical properties. It means “operation to measure such things”.
  • the above-mentioned constant time means the range of 5 minutes or more and 24 hours or less
  • the above-mentioned constant temperature means the range of the boiling point or less of the aqueous solution or the aqueous dispersion above room temperature.
  • the method of (c) stepwise mixing is preferable in terms of the activity and yield of the catalyst finally obtained, and more preferably, each raw material to be mixed stepwise with the mother liquor is a completely dissolved solution.
  • the most preferable method is to mix an alkali metal solution and various mixed solutions of nitrate with a mother liquor containing a molybdenum raw material as a mixed solution or a slurry.
  • the shape of the stirring blade of the stirrer used when mixing the essential active ingredients is not particularly limited, and the propeller blade, the turbine blade, the paddle blade, the inclined paddle blade, the screw blade, the anchor blade, the ribbon blade, and the large lattice are not particularly limited. Any stirring blade such as a blade can be used in one stage, or the same blade or different types of blades can be used in two or more stages in the vertical direction.
  • a baffle obstacle plate
  • the drying method is not particularly limited as long as the slurry liquid can be completely dried, and examples thereof include drum drying, freeze drying, spray drying, and evaporation dryness. Of these, in the present invention, spray drying, which can dry the slurry liquid into powder or granules in a short time, is particularly preferable.
  • the drying temperature of spray drying varies depending on the concentration of the slurry liquid, the liquid feeding rate, and the like, but the temperature at the outlet of the dryer is generally 70 ° C. or higher and 150 ° C. or lower.
  • the catalyst precursor obtained as described above is pre-baked, molded, and then main-baked to control and maintain the molded shape, resulting in a catalyst having particularly excellent mechanical strength for industrial use. It can be obtained and stable catalytic performance can be exhibited.
  • a carrier such as silica or non-supported molding that does not use a carrier
  • Specific molding methods include, for example, tableting molding, press molding, extrusion molding, granulation molding and the like.
  • the shape of the molded product for example, a columnar shape, a ring shape, a spherical shape or the like can be appropriately selected in consideration of operating conditions, and the catalyst precursor is supported on a spherical carrier, particularly an inert carrier such as silica or alumina.
  • a rolling granulation method As the supporting method, a rolling granulation method, a method using a centrifugal flow coating device, a wash coat method and the like are widely known, and the method is not particularly limited as long as the pre-baked powder can be uniformly supported on the carrier.
  • the rolling granulation method is preferable in consideration of the production efficiency of the catalyst and the like. Specifically, it is a device having a flat or uneven disk at the bottom of the fixed cylindrical container, and by rotating the disk at high speed, the carrier charged in the container is rotated and revolved by the carrier itself. This is a method in which the powder component is supported on a carrier by vigorously stirring by repeating the exercise and adding a pre-baked powder to the stirring. In addition, it is preferable to use a binder for supporting.
  • binder examples include water, ethanol, methanol, propanol, polyhydric alcohol, polyvinyl alcohol of a high molecular weight binder, an aqueous solution of silica sol of an inorganic binder, and the like, but ethanol, methanol, propanol, and polyhydric.
  • Alcohol is preferable, diol such as ethylene glycol and triol such as glycerin are more preferable, and an aqueous solution having a concentration of glycerin of 5% by mass or more is further preferable.
  • the amount of these binders used is usually 2 to 60 parts by mass with respect to 100 parts by mass of the pre-baked powder, but 15 to 50 parts by mass is preferable in the case of an aqueous glycerin solution.
  • the binder and the pre-baked powder may be alternately supplied to the molding machine or simultaneously supplied to the molding machine during loading.
  • a small amount of known additives such as graphite and talc may be added during molding.
  • the molding aid, pore forming agent, and carrier added in molding are all active ingredients in the present invention regardless of whether or not they are active in the sense of converting the raw material into some other product. It shall not be considered.
  • the pre-baking method, pre-baking conditions, main firing method, and main firing conditions are not particularly limited, and known treatment methods and conditions can be applied.
  • Preliminary firing and main firing are usually performed at 200 ° C. or higher and 600 ° C. or lower, preferably 300 ° C. or higher and 550 ° C. or lower, for 0.5 hours or longer, preferably under the flow of an oxygen-containing gas such as air or an inert gas. Perform in 1 hour or more and 40 hours or less.
  • the inert gas refers to a gas that does not reduce the reaction activity of the catalyst, and specific examples thereof include nitrogen, carbon dioxide gas, helium, and argon.
  • the optimum conditions for the main firing differ depending on the reaction conditions and the like when producing the unsaturated aldehyde and / or the unsaturated carboxylic acid using the catalyst, and the process parameters of the main firing step, that is, in the atmosphere. Since it is known to those skilled in the art to change the oxygen content, the maximum temperature reached, the firing time, etc., it falls within the scope of the present invention. Further, the main firing step shall be carried out after the above-mentioned pre-baking step, and the maximum reached temperature (main firing temperature) in the main firing step is higher than the maximum reached temperature (pre-baking temperature) in the above-mentioned pre-baking step. It shall be expensive.
  • the firing method is not particularly limited to fluidized beds, rotary kilns, muffle furnaces, tunnel firing furnaces, etc., and an appropriate range should be selected in consideration of the final catalyst performance, mechanical strength, formability, production efficiency, etc. Is.
  • the catalyst of the present invention is preferably used as a catalyst for producing an unsaturated aldehyde compound, an unsaturated carboxylic acid compound, or a conjugated diene compound, and more preferably used as a catalyst for producing an unsaturated aldehyde compound. It is more preferable, and it is particularly preferable to use it as a catalyst for producing achlorine from propylene.
  • the catalyst itself is prevented from being deteriorated by the heat generated by the reaction on the inlet side of the reaction tube.
  • the catalyst of the present invention can be used on any of the catalyst layers on the inlet side of the reaction tube, the outlet side of the reaction tube, and the intermediate layer thereof. Most preferably, it is used as a catalyst. In the multi-layer filling, two-layer or three-layer filling is a particularly preferable embodiment.
  • the catalyst of the present invention When the catalyst of the present invention is used as the catalyst of the first stage, that is, the catalyst for producing an unsaturated aldehyde compound, the oxidation reaction of the second stage can be carried out to obtain an unsaturated carboxylic acid compound.
  • the catalyst of the present invention can be used as the catalyst of the second stage, but it is preferable to use the catalyst represented by the following formula (2). Mo 12 V a2 W b2 Cu c2 Sb d2 X2 e2 Y2 f2 Z2 g2 Oh2 ...
  • Mo, V, W, Cu, Sb and O represent molybdenum, vanadium, tungsten, copper, antimony and oxygen, respectively
  • X2 is at least one element selected from the group consisting of alkali metals and talliums.
  • Y2 is at least one element selected from the group consisting of magnesium, calcium, strontium, barium and zinc, and Z2 is from niobium, cerium, tin, chromium, manganese, iron, cobalt, sumalium, germanium, titanium and arsenic. Represents at least one element selected from the group.
  • a2, b2, c2, d2, e2, f2, g2 and h2 represent the atomic ratio of each element, and a2 is 0 ⁇ for molybdenum atom 12.
  • a2 ⁇ 10 b2 is 0 ⁇ b2 ⁇ 10
  • c2 is 0 ⁇ c2 ⁇ 6
  • d2 is 0 ⁇ d2 ⁇ 10
  • e2 is 0 ⁇ e2 ⁇ 1
  • g2 is 0 ⁇ It represents g2 ⁇ 6.
  • h2 is the number of oxygen atoms required to satisfy the atomic value of each component.
  • a method generally known as a method for preparing a catalyst of this kind for example, an oxide catalyst, a heteropolyacid or a catalyst having a salt structure thereof can be adopted.
  • the raw materials that can be used in producing the catalyst are not particularly limited, and various materials can be used.
  • molybdate oxides such as molybdenum trioxide, molybdic acid, molybdic acid or salts thereof such as ammonium molybdate, heteropolyacids containing molybdenum such as phosphomolybdic acid and silicate molybdic acid or salts thereof may be used.
  • the raw material for the antimony component that can be produced is not particularly limited, but antimony trioxide or antimonate acetate is preferable.
  • As raw materials for other elements such as vanadium, tungsten and copper, each nitrate, sulfate, carbonate, phosphate, organic acid salt, halide, hydroxide, oxide, metal and the like can be used.
  • the compound containing these active ingredients may be used alone or in combination of two or more.
  • the slurry liquid obtained above is dried to obtain a solid catalyst precursor.
  • the drying method is not particularly limited as long as the slurry liquid can be completely dried, and examples thereof include drum drying, freeze drying, spray drying, and evaporative drying, and the slurry liquid is dried into powder or granules in a short time. Spray drying that can be done is preferred.
  • the drying temperature of spray drying varies depending on the concentration of the slurry liquid, the liquid feeding rate, etc., but generally the temperature at the inlet of the dryer is 140 to 400 ° C, the temperature at the outlet is 70 to 150 ° C, and the inlet temperature is higher than the outlet temperature. It gets higher. Further, it is preferable to dry the dried slurry liquid obtained at this time so that the average particle size is 10 to 700 ⁇ m.
  • the catalyst precursor solid of the second stage obtained as described above can be used as it is in the coating mixture, but it is preferable because the moldability may be improved by firing.
  • the firing method and firing conditions are not particularly limited, and known treatment methods and conditions can be applied. The optimum conditions for calcination vary depending on the catalyst raw material used, the catalyst composition, the preparation method, and the like, but the calcination temperature is usually 100 to 350 ° C., preferably 150 to 300 ° C., and the calcination time is 1 to 20 hours.
  • the firing is usually carried out in an air atmosphere, but may be carried out in an inert gas atmosphere such as nitrogen, carbon dioxide, helium, or argon, or further after firing in the inert gas atmosphere, if necessary.
  • the firing may be performed in an air atmosphere.
  • the solid after firing thus obtained is preferably pulverized before molding.
  • the crushing method is not particularly limited, but it is preferable to use a ball mill.
  • the compound containing the active ingredient in preparing the slurry of the second stage does not necessarily have to contain all the active ingredients, and some of the ingredients may be used before the following molding step. ..
  • the shape of the catalyst in the second stage is not particularly limited, and in order to reduce the pressure loss of the reaction gas in the oxidation reaction, it is molded into a columnar shape, a tablet, a ring shape, a spherical shape, or the like and used. Of these, since improvement in selectivity and removal of heat of reaction can be expected, it is particularly preferable to support the catalyst precursor solid on an inert carrier and use it as a supported catalyst.
  • the rolling granulation method described below is preferable for this support. In this method, for example, in a device having a flat or uneven disk at the bottom of a fixed container, the carrier in the container is vigorously agitated by repeating rotation and revolution motion by rotating the disk at high speed.
  • the method of adding the binder is as follows: 1) it is mixed in advance with the supporting mixture, 2) it is added at the same time as the supporting mixture is added into the fixed container, and 3) it is added after the supporting mixture is added into the fixed container. 4) The method of adding the supporting mixture before adding it into the fixed container, 5) dividing the supporting mixture and the binder, and adding the total amount of 2) to 4) in appropriate combination can be arbitrarily adopted. ..
  • the addition rate is adjusted by using an auto feeder or the like so that the supporting mixture does not adhere to the wall of the fixed container and the supporting mixture does not aggregate with each other and the predetermined amount is supported on the carrier.
  • the binder include water, ethanol, polyhydric alcohol, polyvinyl alcohol as a polymer binder, cellulose such as crystalline cellulose, methyl cellulose and ethyl cellulose, and an aqueous solution of silica sol as an inorganic binder, such as cellulose and ethylene glycol. Diol, triol such as glycerin, etc.
  • an aqueous solution having a concentration of glycerin of 5% by mass or more is particularly preferable.
  • the amount of these binders used is usually 2 to 60 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the supporting mixture.
  • the carrier in the above-mentioned carrier include spherical carriers having a diameter of 1 to 15 mm, preferably 2.5 to 10 mm, such as silicon carbide, alumina, silica alumina, mullite, and random. These carriers are usually used having a porosity of 10 to 70%.
  • the ratio of the carrier to the supporting mixture is usually 10 to 75% by mass, preferably 15 to 60% by mass of the supporting mixture / (supporting mixture + carrier). When the proportion of the carrier mixture is large, the reaction activity of the carrier catalyst is high, but the mechanical strength tends to be low. On the contrary, when the ratio of the supporting mixture is small, the mechanical strength tends to be large, but the reaction activity tends to be small.
  • examples of the molding aid used as necessary include silica gel, diatomaceous earth, and alumina powder.
  • the amount of the molding aid used is usually 1 to 60 parts by mass with respect to 100 parts by mass of the solid catalyst precursor.
  • using a catalyst precursor solid and an inorganic fiber (for example, ceramic fiber or whiskers) inactive against the reaction gas as a strength improving agent is useful for improving the mechanical strength of the catalyst. Glass fiber is preferred.
  • the amount of these fibers used is usually 1 to 30 parts by mass with respect to 100 parts by mass of the catalyst precursor solid.
  • the molding aid, the pore forming agent, and the carrier added may or may not be active in the sense of converting the raw material into some other product. It shall not be considered as a constituent element of the active ingredient in the present invention.
  • the supported catalyst obtained as described above can be directly used as a catalyst for a gas phase catalytic oxidation reaction, but firing may improve the catalytic activity, which is preferable.
  • the firing method and firing conditions are not particularly limited, and known treatment methods and conditions can be applied.
  • the optimum conditions for calcination vary depending on the catalyst raw material used, the catalyst composition, the preparation method, and the like, but the calcination temperature is usually 100 to 450 ° C., preferably 270 to 420 ° C., and the calcination time is 1 to 20 hours.
  • the firing is usually carried out in an air atmosphere, but may be carried out in an inert gas atmosphere such as nitrogen, carbon dioxide, helium, or argon, or further after firing in the inert gas atmosphere, if necessary.
  • the firing may be performed in an air atmosphere.
  • the catalytic activity can be improved and the yield can be improved, which greatly improves the price competitiveness of the product as compared with known methods. It is valid.
  • an oxidation catalyst and oxidation in the case of producing a conjugated diolefin (1,3-butadiene, etc.) by a catalytic oxidative dehydrogenation reaction from a mixed gas containing a monoolefin (butenes, etc.) having 4 or more carbon atoms and molecular oxygen.
  • the catalyst is also useful as a dehydrogenation catalyst.
  • the catalyst of the present invention can be effective in improving the yield even in a region where the catalytic activity is particularly high or not high, and also such as reduction of ⁇ T (difference between hot spot temperature and reaction bath temperature). The effect of improving the process stability of the partial oxidation reaction accompanied by heat generation can be expected. Furthermore, the catalyst of the present invention may also be effective in reducing by-products that adversely affect the environment and the quality of the final product, such as carbon monoxide (CO) and carbon dioxide (CO 2 ), acetaldehyde, acetic acid and formaldehyde. ..
  • CO carbon monoxide
  • CO 2 carbon dioxide
  • the catalyst of the present invention thus obtained can be used, for example, in producing acrolein and / or acrylic acid by gas-phase catalytic oxidation of propylene with a molecular oxygen-containing gas.
  • the distribution method of the raw material gas may be an ordinary single distribution method or a recycling method, and can be carried out under generally used conditions, and is not particularly limited.
  • propylene as a starting material is 1 to 10% by volume, preferably 4 to 9% by volume
  • molecular oxygen is 3 to 20% by volume, preferably 4 to 18% by volume
  • water vapor is 0 to 60% by volume at room temperature.
  • a mixed gas of 4 to 50% by volume, preferably 20 to 80% by volume of an inert gas such as carbon dioxide and nitrogen, preferably 30 to 60% by volume is filled in a reaction tube, and 250 to 250 to the catalyst of the present invention is filled.
  • the reaction is carried out at 450 ° C. under a pressure of normal pressure to 10 atm and introduced at a space speed of 300 to 5000 h -1 .
  • the improvement of the catalytic activity means that the raw material conversion rate is high when the catalytic reaction is carried out at the same reaction bath temperature and the comparison is made unless otherwise specified.
  • the high yield in the present invention means that the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid is used when the oxidation reaction is carried out using propylene, isobutylene, t-butyl alcohol or the like as a raw material. It means that the total yield of is high. Further, unless otherwise specified, the yield refers to the effective yield described later.
  • the constituent elements of the catalyst precursor refer to all the elements used in the catalyst manufacturing process unless otherwise specified, but disappear, sublimate, volatilize, and burn at the maximum temperature or less in the main firing process.
  • Raw materials and their constituent elements shall not be included in the constituent elements of the active component of the catalyst.
  • the elements constituting the molding aid and the carrier in the molding process and silicon and other inorganic materials are not included as the constituent elements of the active ingredient of the catalyst.
  • the hot spot temperature is the maximum temperature of the temperature distribution in the catalyst packed bed measured by installing a thermocouple in the long axis direction in the multi-tube reaction tube, and the reaction bath temperature is the heat generation of the reaction tube. Is the set temperature of the heat medium used for the purpose of cooling.
  • unsaturated aldehydes and unsaturated aldehyde compounds are organic compounds having at least one double bond and at least one aldehyde in the molecule, such as acrolein and methacrolein.
  • unsaturated carboxylic acid and the unsaturated carboxylic acid compound are organic compounds having at least one double bond and at least one carboxy group in the molecule, or an ester group thereof, for example, acrylic acid, methacrylic acid, and the like. It is methyl methacrylate.
  • a conjugated diene is a diene in which a double bond is separated by one single bond and chemically coupled, and is, for example, 1,3-butadiene.
  • Example 1 (Preparation of catalyst 1) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 60 ° C. (mother solution 1). Next, 0.27 parts by mass of potassium nitrate was dissolved in 2.4 parts by mass of pure water and added to the mother liquor 1. Next, 40 parts by mass of ferric nitrate, 86 parts by mass of cobalt nitrate and 30 parts by mass of nickel nitrate were dissolved in 83 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1.
  • the active carrier was supported and molded into a spherical shape so that the carrying ratio was 50% by mass.
  • the spherical molded product having a particle diameter of 5.3 mm thus obtained was subjected to main firing at 540 ° C. for 4 hours to obtain a catalyst 1.
  • the catalyst precursor of the catalyst 1 had a D10 of 19 ⁇ m, a D50 of 35 ⁇ m, a D90 of 59 ⁇ m, and a hollow particle ratio of the catalyst precursor of 1.0%.
  • Example 2 (Preparation of catalyst 2)
  • the catalyst 2 was obtained in exactly the same manner as the catalyst 1 except that the catalyst was dried at an inlet temperature of 240 ° C., an outlet temperature of 130 ° C., and an atomizer rotation speed of 18000 rpm in the spray drying step.
  • the catalyst precursor of the catalyst 2 had a D10 of 13 ⁇ m, a D50 of 25 ⁇ m, a D90 of 43 ⁇ m, and a hollow particle ratio of the catalyst precursor of 0.0%.
  • Example 3 (Preparation of catalyst 3)
  • the solid content concentration of the mother liquor 1 was 14% by mass, and the mixture was dried in the spray drying step at an inlet temperature of 240 ° C., an outlet temperature of 130 ° C., and an atomizer rotation speed of 18000 rpm in exactly the same manner as that of the catalyst 1.
  • Catalyst 3 was obtained.
  • the catalyst precursor of the catalyst 3 had a D10 of 16 ⁇ m, a D50 of 30 ⁇ m, a D90 of 50 ⁇ m, and a hollow particle ratio of the catalyst precursor of 0.8%.
  • Example 4 (Preparation of catalyst 4)
  • the solid content concentration of the mother liquor 1 was 14% by mass, and the mixture was dried in the spray drying step at an inlet temperature of 240 ° C., an outlet temperature of 130 ° C., and an atomizer rotation speed of 22000 rpm in exactly the same manner as that of the catalyst 1.
  • Catalyst 4 was obtained.
  • the catalyst precursor of the catalyst 4 had a D10 of 14 ⁇ m, a D50 of 24 ⁇ m, a D90 of 40 ⁇ m, and a hollow particle ratio of the catalyst precursor of 0.0%.
  • Example 5 (Preparation of catalyst 5) 100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 60 ° C. (mother solution 1). Next, 0.37 parts by mass of potassium nitrate was dissolved in 3.5 parts by mass of pure water and added to the mother liquor 1. Next, 34 parts by mass of ferric nitrate, 81 parts by mass of cobalt nitrate and 44 parts by mass of nickel nitrate were dissolved in 82 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1.
  • the active carrier was supported and molded into a spherical shape so that the carrying ratio was 50% by mass.
  • the spherical molded product having a particle diameter of 5.3 mm thus obtained was subjected to main firing at 510 ° C. for 4 hours to obtain a catalyst 5.
  • the catalyst precursor of the catalyst 5 had a D10 of 16 ⁇ m, a D50 of 31 ⁇ m, a D90 of 55 ⁇ m, and a hollow particle ratio of the catalyst precursor of 2.3%.
  • Example 6 (Preparation of catalyst 6)
  • the catalyst 6 was obtained in exactly the same manner as the catalyst 1 except that the catalyst was dried at an inlet temperature of 240 ° C., an outlet temperature of 110 ° C., and an atomizer rotation speed of 14000 rpm in the spray drying step.
  • the catalyst precursor of the catalyst 6 had a D10 of 19 ⁇ m, a D50 of 37 ⁇ m, a D90 of 64 ⁇ m, and a hollow particle ratio of the catalyst precursor of 2.3%.
  • Example 7 (Preparation of catalyst 7)
  • the catalyst 7 was obtained in exactly the same manner as the catalyst 1 except that the catalyst was dried at an inlet temperature of 300 ° C., an outlet temperature of 95 ° C., and an atomizer rotation speed of 14000 rpm in the spray drying step.
  • the catalyst precursor of the catalyst 7 had a D10 of 26 ⁇ m, a D50 of 42 ⁇ m, a D90 of 66 ⁇ m, and a hollow particle ratio of the catalyst precursor of 4.8%.
  • Example 2 (Preparation of catalyst 8)
  • the solid content concentration of the mother liquor 1 was 55% by mass, and the same was exactly the same as that of the catalyst 1 except that the mother liquor 1 was dried at an inlet temperature of 300 ° C., an outlet temperature of 95 ° C., and an atomizer rotation speed of 14000 rpm in the spray drying step.
  • Catalyst 8 was obtained.
  • the catalyst precursor of the catalyst 8 had a D10 of 25 ⁇ m, a D50 of 43 ⁇ m, a D90 of 72 ⁇ m, and a hollow particle ratio of the catalyst precursor of 4.5%.
  • nitric acid solution prepared by adding 9.7 parts by mass of nitric acid (60% by mass) to 41 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1.
  • the mother liquor 1 was dried by a spray-drying method at an inlet temperature of 240 ° C., an outlet temperature of 110 ° C., and an atomizer rotation speed of 14000 rpm, and the obtained dry powder was pre-baked under the conditions of 440 ° C. and 4 hours.
  • a 33% by mass glycerin solution was used as a binder by a rolling granulation method, and the loading ratio was 50% by mass on an inert carrier. It was supported and molded into a spherical shape so as to be%.
  • the spherical molded product having a particle diameter of 5.3 mm thus obtained was subjected to main firing at 530 ° C. for 4 hours to obtain a catalyst 9.
  • the oxidation reaction of propylene was carried out by the following method, and the effective yield was determined.
  • a mixed gas of 1.7: 1.3: 9.5 was introduced at a propylene space rate of 100 hr -1 with respect to all catalysts in the reaction tube, and an oxidation reaction of propylene was carried out. After an aging reaction at a reaction bath temperature of 315 ° C.
  • Table 1 shows the inlet temperature, outlet temperature, atomizer rotation speed, relative centrifugal acceleration, solid content concentration of mother liquor 1, and parameter SD in the spray-drying process during the production of the catalyst precursor of each catalyst. .. Table 1 also shows D10, D50, D90, specific surface area, and hollow particle ratio of the catalyst precursors of each catalyst. The D10, D50, D90, specific surface area, and specific surface area shown in Table 1 were evaluated by the methods exemplified in the embodiments.
  • the catalyst prepared by the catalyst precursor of the present invention can obtain the target compounds acrolein and acrylic acid in higher yields than the conventional catalysts.
  • the catalyst of the present invention it is possible to obtain a target compound in a high yield when an unsaturated aldehyde compound, an unsaturated carboxylic acid compound, or a conjugated diene compound is oxidatively produced.

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PCT/JP2021/033592 2020-09-24 2021-09-13 触媒前駆体、それを用いた触媒、化合物の製造方法及び触媒の製造方法 Ceased WO2022065116A1 (ja)

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