WO2025164703A1 - Procédé de remplissage de catalyseur, procédé de production d'acide (méth)acrylique et tube de réaction - Google Patents

Procédé de remplissage de catalyseur, procédé de production d'acide (méth)acrylique et tube de réaction

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Publication number
WO2025164703A1
WO2025164703A1 PCT/JP2025/002911 JP2025002911W WO2025164703A1 WO 2025164703 A1 WO2025164703 A1 WO 2025164703A1 JP 2025002911 W JP2025002911 W JP 2025002911W WO 2025164703 A1 WO2025164703 A1 WO 2025164703A1
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WIPO (PCT)
Prior art keywords
catalyst
mass
reaction gas
reaction tube
reaction
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Pending
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PCT/JP2025/002911
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English (en)
Japanese (ja)
Inventor
正範 新田
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Publication of WO2025164703A1 publication Critical patent/WO2025164703A1/fr
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Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • 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
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • 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

Definitions

  • the present invention relates to a method for packing a catalyst, a method for producing (meth)acrylic acid using the catalyst, and a reaction tube packed with the catalyst.
  • the solid catalyst packed into the reaction tubes of fixed-bed reactors can be partially pulverized due to mechanical action or naturally during packaging after production, transportation from the production facility to the catalyst packing device, storage, weighing, and the process of packing the catalyst into the catalyst packing device.
  • this type of pulverized catalyst with small particle size (fine catalyst) was packed into the reaction tube, which could increase pressure loss in the reaction tube due to the inclusion of this fine catalyst.
  • the inclusion of fine catalyst was the cause of reduced reaction performance and increased pressure loss during the catalyst's usage period.
  • Patent Document 1 describes a method for selectively removing only finely powdered catalyst using a catalyst packing container when packing a solid catalyst into a reaction tube.
  • Patent Document 2 describes a method for removing fine powder formed when part of a stacked solid catalyst layer is powdered from the catalyst layer.
  • Patent Document 3 describes a method for improving the mechanical strength of a solid catalyst by coating the surface with cellulose to prevent the catalyst from powdering during transportation and packing into a reactor.
  • Patent Document 4 describes mixing a specified amount of catalyst into used packing material when reusing it, thereby improving the yield of the target product.
  • the present invention aims to provide a catalyst packing method that can improve the yield of the target product in a reaction using a catalyst without requiring a special catalyst production process. It also aims to provide a (meth)acrylic acid production method that can produce (meth)acrylic acid in high yield using such a packed catalyst. It also aims to provide a reaction tube packed with a catalyst that can improve the yield of the target product.
  • the inventors conducted extensive research to solve the above-mentioned problems. As a result, they discovered that the yield of the target product (e.g., (meth)acrylic acid) can be improved by setting the ratio of fine powder catalyst to the catalyst contained in the entire reaction tube within a specific range, and by packing the catalyst so that the ratio of fine powder catalyst present on the reaction gas inlet side is higher and the ratio of fine powder catalyst present on the reaction gas outlet side is lower, relative to the ratio of fine powder catalyst contained in the entire reaction tube.
  • the present invention is summarized as follows:
  • a method for packing a catalyst into a reaction tube provided in a fixed bed reactor comprising:
  • the catalyst includes a solid catalyst that does not pass through a sieve with a nominal opening of 1 mm and a fine catalyst that passes through a sieve with a nominal opening of 1 mm;
  • the fine powder catalyst satisfies the following formulas (1) and (2): Catalyst loading method: 0.010% by mass ⁇ X 1 +X 2 ⁇ 2.300% by mass (1); X 1 ⁇ X 2 ...(2),
  • X1 represents the amount (mass%) of the fine catalyst present in the reaction gas outlet side region relative to 100 mass% of the total amount of the catalyst
  • X2 represents the amount (mass%) of the fine catalyst present in the reaction gas inlet side region relative to 100 mass% of the total amount of the catalyst, provided that the reaction gas outlet side region is a region where 50 mass% of the solid catalyst is present out of 100 mass% of the total amount of the solid catalyst, calculated from the reaction gas outlet side of the reaction tube, and the
  • [4] The catalyst packing method according to any one of [1] to [3], wherein the fine powder catalyst and the solid catalyst have substantially the same composition.
  • [5] The catalyst packing method according to any one of [1] to [4], wherein a packing material is packed into at least one of a region on the reaction gas inlet side of the catalyst layer packed with the catalyst and a region on the reaction gas outlet side of the catalyst layer packed with the catalyst.
  • [6] The catalyst packing method according to any one of [1] to [5], wherein a packing aid is packed together with the catalyst.
  • [7] The catalyst packing method according to any one of [1] to [6], wherein the catalyst contains molybdenum and vanadium.
  • the catalyst packing method according to any one of [1] to [8], wherein the catalyst is a catalyst for producing (meth)acrylic acid.
  • the catalyst includes a solid catalyst that does not pass through a sieve with a nominal opening of 1 mm and a fine catalyst that passes through a sieve with a nominal opening of 1 mm;
  • the fine powder catalyst satisfies the following formulas (1) and (2): Method for producing (meth)acrylic acid: 0.010% by mass ⁇ X 1 +X 2 ⁇ 2.300% by mass (1); X 1 ⁇ X 2 ...(2),
  • X1 represents the amount (mass%) of the fine catalyst present in the reaction gas outlet side region relative to 100 mass% of the total amount of the catalyst
  • X2 represents the amount (mass%) of the fine catalyst present in the reaction gas
  • a reaction tube packed with a catalyst The catalyst includes a solid catalyst that does not pass through a sieve with a nominal opening of 1 mm and a fine catalyst that passes through a sieve with a nominal opening of 1 mm;
  • the fine powder catalyst satisfies the following formulas (1) and (2): Reaction tube: 0.010% by mass ⁇ X 1 +X 2 ⁇ 2.300% by mass (1); X 1 ⁇ X 2 ...(2),
  • X1 represents the amount (mass%) of the fine catalyst present in the reaction gas outlet side region relative to 100 mass% of the total amount of the catalyst
  • X2 represents the amount (mass%) of the fine catalyst present in the reaction gas inlet side region relative to 100 mass% of the total amount of the catalyst, provided that the reaction gas outlet side region is a region where 50 mass% of the solid catalyst is present out of 100
  • the catalyst has a composition represented by the following formula (3): P a Mo b V c Cu d X e Y f Z g (NH 4 ) h O i ...(3),
  • P, Mo, V, Cu, NH4 , and O represent phosphorus, molybdenum, vanadium, copper, ammonium, and oxygen, respectively;
  • X represents at least one element selected from the group consisting of silicon, titanium, germanium, arsenic, antimony, and bismuth;
  • Y represents at least one element selected from the group consisting of niobium, tantalum, tungsten, cerium, zirconium, silver, iron, zinc, chromium, magnesium, cobalt, manganese, barium, and lanthanum;
  • Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium;
  • the present invention provides a catalyst packing method that can improve the yield of the target product in a reaction using a catalyst without requiring a special catalyst production process. Furthermore, the present invention makes it possible to produce (meth)acrylic acid with a high yield by using a catalyst packed in this way. Furthermore, the present invention makes it possible to provide a reaction tube packed with a catalyst that can improve the yield of the target product.
  • FIG. 1 is a schematic diagram of a reaction tube used for packing a catalyst in one embodiment of the present invention.
  • (meth)acrylic acid refers to methacrylic acid or acrylic acid
  • (meth)acrolein refers to methacrolein or acrolein.
  • the catalyst packing method according to this embodiment is a method for packing a catalyst containing a solid catalyst that does not pass through a sieve with a nominal mesh size of 1 mm and a fine powder catalyst that passes through a sieve with a nominal mesh size of 1 mm into a reaction tube of a fixed-bed reactor.
  • the reaction tube is packed with the fine powder catalyst so as to satisfy the following formulas (1) and (2) for the reasons described below, thereby forming a catalyst layer: 0.010% by mass ⁇ X 1 +X 2 ⁇ 2.300% by mass (1); X 1 ⁇ X 2 (2).
  • X1 represents the amount (mass%) of the fine catalyst present in the reaction gas outlet side region relative to 100 mass% of the total amount of catalyst
  • X2 represents the amount (mass%) of the fine catalyst present in the reaction gas inlet side region relative to 100 mass% of the total amount of catalyst.
  • the “reaction gas outlet side region” is a region where 50 mass% of the solid catalyst is present out of 100 mass% of the total amount of solid catalyst, calculated from the reaction gas outlet side of the reaction tube.
  • reaction gas inlet side region is a region where 50 mass% of the solid catalyst is present out of 100 mass% of the total amount of solid catalyst, calculated from the reaction gas inlet side of the reaction tube.
  • finely divided catalyst that passes through a sieve with a nominal mesh size of 1 mm refers to a catalyst that passes through a sieve with a nominal diameter of 200 mm and a nominal height of 45 mm, as specified in JIS Z8801-1, and falls into a receiver when the catalyst is vibrated for 10 minutes in a commercially available sieving machine at a frequency of 50 times per minute and an amplitude of 2 mm.
  • solid catalyst that does not pass through a sieve with a nominal mesh size of 1 mm refers to a catalyst that does not pass through a sieve with a nominal mesh size of 200 mm and a nominal height of 45 mm, as specified in JIS Z8801-1, and falls into a receiver when the catalyst is vibrated for 10 minutes in a commercially available sieving machine at a frequency of 50 times per minute and an amplitude of 2 mm.
  • such catalysts are also simply referred to as "solid catalysts.” Therefore, in the present invention, catalysts other than fine powder catalysts can also be said to be solid catalysts. That is, in the present invention, the catalyst satisfies the above formula (1) and is packed into the reaction tube so that the proportion of the solid catalyst after packing is 97.700 mass% or more and 99.990 mass% or less relative to the total mass of the catalyst.
  • the total amount of catalyst refers to the total mass (100% by mass) of catalyst (i.e., fine powder catalyst and solid catalyst) packed into the reaction tube. Because the mass of the catalyst remains the same before and after packing, the total amount of catalyst can also be said to be the total amount of catalyst present (packed) in the reaction tube after packing.
  • Fig. 1 is a schematic diagram of a reaction tube used for packing a catalyst in one embodiment of the present invention.
  • a catalyst fine powder catalyst and solid catalyst 2 into the reaction tube 1
  • a first region A1 a region from an end Q1 on the reaction gas outlet 1B side to a boundary position P
  • a second region A2 a region from an end Q2 on the reaction gas inlet 1A side to a boundary position P which is a reaction gas inlet side region
  • the boundary position P represents the boundary between the first region A1 and the second region A2 , where each region contains 50 mass % of the solid catalyst.
  • the X1 represents the amount of the fine catalyst present in the first region A1 relative to 100% by mass of the total amount of catalyst
  • the X2 represents the amount of the fine catalyst present in the second region A2 relative to 100% by mass of the total amount of catalyst.
  • the entire region where the catalyst is present after packing is referred to as the catalyst layer 3.
  • the first region and the second region are continuous via a boundary position P, but the first region and the second region do not have to be continuous regions.
  • a region consisting only of the packing material described below may be present between the first region and the second region.
  • the first region and the second region may each contain, in addition to the catalyst, components required for forming the catalyst layer, such as a packing auxiliary material.
  • a space may be provided in at least one of the upper part (the region closer to the reaction gas inlet than the catalyst layer) and the lower part (the region closer to the reaction gas outlet than the catalyst layer) of the catalyst layer in the reaction tube, and any packing material 4 may be filled in part or all of the space.
  • the packing material an auxiliary packing material described later may be appropriately selected and used.
  • the flow direction of the reaction gas into the reaction tube may be either up or down. That is, in FIG. 1 , the reaction gas is caused to flow into the reaction tube from the upper part, but the reaction gas may also be caused to flow into the reaction tube from the lower part.
  • the "reaction gas outlet side region A 1 " and the "reaction gas inlet side region A 2 " are interchanged.
  • the yield of (meth)acrylic acid is improved when the ratio of the finely divided catalyst to the total amount (100 mass%) of catalyst packed in the reaction tube of the fixed-bed reactor is in the range of 0.010 mass% to 2.300 mass%, and when a larger amount of the finely divided catalyst is present in the reaction gas inlet side region A2 of the reaction tube than in the reaction gas outlet side region A1 of the reaction tube.
  • the ratio (X 1 + X 2 ) of the fine powder catalyst to the total amount (100% by mass) of catalyst present in the reaction tube after the catalyst packing is preferably 0.040% by mass or more, more preferably 0.100% by mass or more, from the viewpoint of further improving the (meth)acrylic acid yield.
  • the ratio of the fine powder catalyst is preferably 2.200% by mass or less, more preferably 2.100% by mass or less, and even more preferably 2.000% by mass or less.
  • the fine powder catalyst is present in a larger amount in the reaction gas inlet side region of the reaction tube than in the reaction gas outlet side region. That is, the reaction tube is filled with the fine powder catalyst so as to satisfy X1 ⁇ X2 .
  • X1 (mass%) is 0 or greater than 0, and X2 (mass%) is greater than 0.
  • the ratio of X2 to X1 ( X2 : X1 ) is preferably 60:40 to 100:0, more preferably 80:20 to 100:0, even more preferably 90:10 to 100:0, and most preferably 95:5 to 100:0.
  • the fine powder catalyst may also be an irregular shape consisting of an aggregate of multiple granules.
  • the solid catalyst is a catalyst that does not pass through a sieve with a nominal mesh size of 1 mm, but passes through a sieve with a nominal mesh size of 9.5 mm.
  • a catalyst that passes through a sieve with a nominal mesh size of 9.5 mm refers to a catalyst that passes through a sieve with a nominal mesh size of 200 mm and a nominal height of 45 mm, as specified in JIS Z8801-1, when the sieve is vibrated for 10 minutes at a frequency of 50 times per minute and an amplitude of 2 mm in a commercially available sieving machine.
  • a catalyst that passes through a sieve with a nominal mesh size of 9.5 mm includes not only solid catalysts but also finely divided catalysts that pass through a sieve with a nominal mesh size of 1 mm.
  • the catalyst packed into the reaction tube is a catalyst that passes through the sieve with a nominal mesh size of 9.5 mm.
  • the proportion of the catalyst that passes through the sieve with a nominal mesh size of 9.5 mm is more preferably 99.000 mass% or more, and particularly preferably 100 mass%.
  • the shape of the solid catalyst is not particularly limited, and examples include spherical granules, cylinders, pellets, and rings.
  • a solid catalyst is formed by wet or dry molding of a catalyst powder containing catalytic components such as metals into the desired shape.
  • Specific examples of solid catalysts include supported catalysts in which catalyst powder is supported on an inert carrier; tableted catalysts in which catalyst powder is tableted with a molding aid such as graphite; and extruded catalysts in which catalyst powder is extruded with water and a molding aid. Because the basic constituent of these molded solid catalysts is fine catalyst particles, they can be pulverized during packaging, transportation, storage, weighing, and catalyst loading, resulting in the formation of finely divided catalyst particles.
  • the proportion of finely divided catalyst particles it is preferable to classify and separate the finely divided catalyst particles contained in the solid catalyst before loading.
  • the classified finely divided catalyst particles can be mixed with the solid catalyst to achieve a desired ratio.
  • the degree of pulverization during catalyst loading can be adjusted by controlling the molding conditions.
  • the number of solid catalysts in the reaction tube after packing usually, a plurality of solid catalysts are packed into the reaction tube.
  • the average volume of a solid catalyst that passes through a sieve with a nominal mesh size of 9.5 mm i.e., a catalyst that passes through a sieve with a nominal mesh size of 9.5 mm but not through a sieve with a nominal mesh size of 1 mm.
  • the average volume of the catalyst before packing is preferably 20 mm 3 /piece or more and 270 mm 3 /piece or less. When the average volume of the catalyst is 20 mm 3 /piece or more, the pressure loss in the reaction tube can be further reduced.
  • the average volume of the catalyst is 270 mm 3 /piece or less, the catalytic activity tends to be further improved.
  • the average volume of the catalyst is more preferably 30 mm 3 /piece or more, and more preferably 170 mm 3 /piece or less. It should be noted that the average volume of the solid catalyst can be considered to be unchanged before and after packing when the catalyst powder rate of the solid catalyst is 0% by mass (0.000% by mass). When the catalyst powder rate of the solid catalyst is greater than 0.000% by mass, the average volume after packing changes slightly compared to before packing depending on the catalyst powder rate.
  • the total amount of catalyst packed into the reaction tube varies depending on the length and diameter of the reaction tube and the specific gravity of the catalyst, but is preferably 100 g or more, more preferably 200 g or more. On the other hand, the total amount of catalyst is preferably 8,000 g or less, more preferably 7,000 g or less.
  • the amounts of solid catalyst and fine-powder catalyst can be adjusted and filled so that the ratio of fine-powder catalyst to solid catalyst in the reaction tube after filling is the desired value.
  • the catalyst to be filled into the reaction tube can be pre-pulverized, and the resulting fine-powder catalyst can be mixed with the solid catalyst and filled into the reaction tube.
  • the solid catalyst may be pulverized during filling or weighing, resulting in a portion of the catalyst becoming fine-powder catalyst.
  • the ratio of fine-powder catalyst generated by pulverization of the solid catalyst during filling or weighing also referred to as the "catalyst powder fraction"
  • the loading amounts of the solid catalyst and fine-powder catalyst taking this catalyst powder fraction into consideration so that the desired ratio of fine-powder catalyst is achieved after filling.
  • the catalyst powder rate can be measured using the method described in the Examples section below.
  • packing aid used in catalyst layers may be packed along with the catalyst.
  • material of the packing aid there are no particular restrictions on the material of the packing aid, as long as it is heat-resistant above the temperature used in the reaction.
  • packing aids that can be used include silica, alumina, silica-alumina, magnesia, titania, and stainless steel (SUS).
  • SUS stainless steel
  • the shape of the packing aid is also not particularly limited, and examples include spherical, cylindrical, cylindrical, coiled, and plate-shaped shapes. Irregular packing materials such as cascade mini rings, terrarettes, pall rings, saddle-shaped, and medal packs can also be used.
  • the size of the packing aid is not critical, as long as it does not form bridges or significantly increase pressure loss when packed into the reaction tube. It is preferable for the packing aid to be approximately the same size as the solid catalyst. From an economical standpoint, ceramic balls and coil springs are preferred as packing aids, with silica-alumina ceramic balls and SUS coil springs being more preferred. These packing aids may be used alone or in combination. Furthermore, the extracted material after use in the reaction may be reused as these packing aids.
  • the amount of packing aid used in the catalyst layer there are no particular restrictions on the amount of packing aid used in the catalyst layer relative to the total amount of catalyst present in the reaction tube after catalyst packing.
  • the amount of packing aid used is preferably 0.5% by mass or more and 60% by mass or less relative to the total amount of catalyst.
  • the amount of packing aid used is more preferably 50% by mass or less, and even more preferably 40% by mass or less, relative to the total amount of catalyst.
  • the amount of packing aid used is more preferably 1% by mass or more, and even more preferably 2% by mass or more, relative to the total amount of catalyst.
  • the catalyst layer may include areas where only the packing aid is present.
  • the catalyst preferably contains at least molybdenum and vanadium.
  • the catalyst preferably further contains phosphorus, and from the viewpoint of achieving a higher effect of the present invention, it is particularly preferable that the catalyst has a composition represented by the following formula (3).
  • the composition represented by the following formula (3) is a value calculated from the amounts of raw materials charged: P a Mo b V c Cu d X e Y f Z g (NH 4 ) h O i ...(3)
  • P, Mo, V, Cu, NH 4 , and O represent phosphorus, molybdenum, vanadium, copper, ammonium, and oxygen, respectively.
  • X represents at least one element selected from the group consisting of silicon, titanium, germanium, arsenic, antimony, and bismuth.
  • Y represents at least one element selected from the group consisting of niobium, tantalum, tungsten, cerium, zirconium, silver, iron, zinc, chromium, magnesium, cobalt, manganese, barium, and lanthanum.
  • Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium.
  • the catalyst is preferably a catalyst for producing (meth)acrylic acid.
  • the composition of the fine powder catalyst and solid catalyst there are no particular restrictions on the composition of the fine powder catalyst and solid catalyst, as long as they are catalysts for producing (meth)acrylic acid that are capable of producing (meth)acrylic acid by the gas-phase catalytic oxidation reaction of (meth)acrolein.
  • catalysts containing at least molybdenum and vanadium are preferred, catalysts that further contain phosphorus are more preferred, and catalysts having a composition represented by the above formula (3) are also preferred.
  • the solid catalyst and the fine powder catalyst are preferably composed of the same constituent elements, and more preferably have substantially the same composition.
  • the solid catalyst and the fine powder catalyst have substantially the same composition generally means that the solid catalyst and the fine powder catalyst are composed of the same elements, and the difference in the ratio of each element relative to the major element (e.g., molybdenum) is within 50 mol%.
  • the difference in the ratio of each of the above elements is preferably within 30 mol%, more preferably within 10 mol%, and even more preferably within 1 mol%.
  • the solid catalyst and the fine powder catalyst are considered to have substantially the same composition.
  • the solid catalyst and the fine powder catalyst have substantially the same composition.
  • solid catalysts and/or fine powder catalysts that do not have substantially the same composition as these catalysts (when they contain different elements, or when they contain the same elements, the difference in the ratio of each element to the main element exceeds 50 mol%) may also be present. There are no particular restrictions on the proportion of such catalysts relative to the total amount of catalyst present in the reaction tube after catalyst packing.
  • the proportion of the above catalyst is preferably 50 mass% or less, more preferably 30 mass% or less, even more preferably 10 mass% or less, and particularly preferably 3 mass% or less.
  • the method for preparing the catalyst is not particularly limited as long as it does not result in significant uneven distribution of the catalyst components, and the catalyst can be prepared using known methods. Examples of such methods include precipitation, coprecipitation, and impregnation.
  • Raw materials used in preparing the catalyst include nitrates, carbonates, acetates, ammonium salts, oxides, and halides of each element.
  • molybdenum raw materials include ammonium paramolybdate, molybdenum trioxide, molybdic acid, and molybdenum chloride.
  • Phosphorus raw materials include orthophosphoric acid, phosphorus pentoxide, and ammonium phosphate.
  • Vanadium raw materials include ammonium metavanadate and vanadium pentoxide. These may be used alone or in combination.
  • the heat treatment conditions are not particularly limited, and known heat treatment conditions can be applied.
  • the heat treatment is preferably carried out under a flow of an oxygen-containing gas such as air and/or under a flow of an inert gas.
  • a heat treatment temperature of 300°C or higher sufficiently activates the catalyst.
  • a heat treatment temperature of 500°C or lower can further suppress the collapse of the catalyst structure.
  • the heat treatment temperature is more preferably 360°C or higher, and more preferably 390°C or lower.
  • the heat treatment temperature is measured at a point within a radius of 1 m from the inlet for introducing the heat medium. Furthermore, from the viewpoint of improving the yield of (meth)acrylic acid and controlling the catalyst activity within a manageable range, the heat treatment time is more preferably 5 hours or longer, and more preferably 50 hours or shorter.
  • the heat treatment for activating the catalyst may be carried out before or after the catalyst is packed into the reaction tube.
  • the molded body before its activity is improved by the heat treatment is also referred to as the catalyst. That is, when the catalyst activity is improved by heat treatment after being packed into the reaction tube, the molded body before the heat treatment is also referred to as the catalyst.
  • fixed-bed reactor is not particularly limited, but examples include multi-tubular heat exchanger, single-tubular heat exchanger, self-heat exchanger, multi-stage adiabatic, and adiabatic types.
  • industrially, fixed-bed multi-tubular heat exchanger reactors are preferably used.
  • the length of the reaction tube of the fixed-bed reactor is preferably 1 m or more, more preferably 3 m or more, and preferably 15 m or less, more preferably 10 m or less.
  • the inner diameter of the reaction tube of the fixed-bed reactor is preferably 10 mm or more, more preferably 20 mm or more, and preferably 40 mm or less, more preferably 30 mm or less.
  • the volume of the reaction tube of the fixed-bed reactor is preferably 50 cm or more , more preferably 300 cm or more, and even more preferably 900 cm or more .
  • the volume of the reaction tube is preferably 20,000 cm or less, more preferably 15,000 cm or less, and even more preferably 8,000 cm or less .
  • (meth)acrylic acid can be produced by a gas-phase catalytic oxidation reaction of (meth)acrolein using a catalyst packed by the catalyst packing method according to the present invention.
  • the method for producing (meth)acrylic acid according to this embodiment is a method for producing (meth)acrylic acid by a gas-phase catalytic oxidation reaction, in which (meth)acrolein and molecular oxygen are supplied to a reaction tube equipped with a fixed-bed reactor packed with the catalyst.
  • the catalyst includes a solid catalyst that does not pass through a sieve with a nominal mesh size of 1 mm and a fine powder catalyst that passes through a sieve with a nominal mesh size of 1 mm, and the fine powder catalyst is packed into the reaction tube so as to satisfy the above formulas (1) and (2).
  • the reaction gas (also referred to as "raw material gas") used in the gas-phase catalytic oxidation reaction of (meth)acrolein contains (meth)acrolein, an oxygen source gas, and an optional inert gas.
  • concentration of (meth)acrolein in the raw material gas is not particularly limited, but is preferably 1% to 20% by volume, and more preferably 3% to 10% by volume.
  • the concentration of (meth)acrolein in the raw material gas may be increased in stages to increase the reaction load in stages.
  • the raw material (meth)acrolein may contain small amounts of impurities such as water and lower saturated aldehydes, but these impurities do not substantially affect the reaction.
  • air as the oxygen source gas
  • air enriched with pure oxygen (O 2 ) can also be used.
  • concentration of molecular oxygen in the raw material gas is preferably 0.3 to 4, more preferably 0.4 to 2.5, in terms of molar ratio to (meth)acrolein.
  • the raw material gas may also be diluted by adding an inert gas such as nitrogen, water vapor, or carbon dioxide. These inert gases can also be used as carrier gases when evaporating the raw material (meth)acrolein.
  • the oxygen source gas, and the inert gas may be supplied separately to the reaction tube, or they may be mixed before being supplied to the reaction tube and supplied as a mixed gas to the reaction tube.
  • the gas-phase catalytic oxidation reaction of (meth)acrolein is preferably carried out under atmospheric pressure to elevated pressure, with the reaction pressure preferably being 0 kPaG to 200 kPaG.
  • the reaction temperature is preferably 230°C to 450°C, more preferably 250°C to 400°C, and even more preferably 250°C to 350°C.
  • the reaction pressure [kPaG] refers to gauge pressure.
  • the contact time between the raw material gas and the catalyst is preferably 1.5 to 15 seconds, with a lower limit of 2 seconds being more preferred and an upper limit of 10 seconds being more preferred.
  • the finely divided catalyst packed into the reaction tube satisfies the above formulas (1) and (2).
  • the yield of (meth)acrylic acid can be improved, as described above.
  • the above description of the catalyst packing method according to the present invention can also be applied to the method for producing (meth)acrylic acid according to the present invention.
  • the reaction tube according to the present invention is a reaction tube filled with a catalyst by the catalyst filling method according to the present invention. That is, the reaction tube according to the present invention is a reaction tube filled with a catalyst, the catalyst comprising a solid catalyst that does not pass through a sieve with a nominal mesh size of 1 mm and a fine powder catalyst that passes through a sieve with a nominal mesh size of 1 mm, and the reaction tube is filled with the fine powder catalyst so as to satisfy the formulas (1) and (2).
  • the yield of the target product can be improved.
  • the above description of the catalyst filling method according to the present invention can also be applied to the reaction tube according to the present invention.
  • the catalyst powdering rate indicates the proportion of finely divided catalyst particles generated by crushing the solid catalyst when the solid catalyst is packed into a reaction tube.
  • the finely divided catalyst particles are those that fall into a receiver when a commercially available sieve shaker is used, equipped with a sieve having a nominal mesh size of 1 mm, a nominal diameter of 200 mm, and a nominal height of 45 mm, as specified in JIS Z8801-1, is vibrated at a frequency of 50 times per minute with an amplitude of 2 mm for 10 minutes.
  • the catalyst powdering rate was measured by the following method.
  • the ratios of the fine catalyst powder to the total amount of catalyst are not actually measured values but are values estimated from the ratio of the fine catalyst powder when the catalyst is packed and the catalyst powdering rate. Taking the catalyst powdering rate into consideration, X1 and X2 were calculated on the assumption that the catalyst is packed uniformly in the reaction tube.
  • Catalyst Production Example 1 Production of Solid Catalyst Z1
  • a powder catalyst having an elemental composition excluding oxygen of P1.5Mo12V0.8Cu0.1K0.7Cs0.4Bi0.3Sb0.3Ce0.2As0.2 was obtained by a manufacturing method similar to that described in Patent Document 4.
  • the elemental composition of the powder catalyst was calculated from the amount of raw materials charged. 3 parts by mass of graphite powder was added to 100 parts by mass of the powder catalyst and mixed thoroughly .
  • the resulting mixture was tableted into a cylindrical shape with an outer diameter of 5.0 mm, a height of 5.0 mm, a catalyst volume of 98.2 mm3 /tablet, and a crushing strength of 70 kgG, to obtain solid catalyst Z1.
  • the catalyst powdering rate of solid catalyst Z1 calculated using the above formula (5) was 0% by mass (0.000% by mass).
  • the catalyst volume is the average volume of the solid catalyst passing through a sieve with a nominal mesh size of 9.5 mm before packing (the same applies hereinafter).
  • Catalyst Production Example 2 Production of Solid Catalyst Z2
  • Solid catalyst Z2 was obtained in the same manner as in Catalyst Production Example 1, except that the mixture obtained in Catalyst Production Example 1 was tableted into cylindrical shapes with an outer diameter of 3.0 mm, a height of 3.0 mm, a catalyst volume of 21.2 mm3 /tablet, and a crushing strength of 70 kgG.
  • the catalyst powder ratio of solid catalyst Z2 was 0% by mass (0.000% by mass).
  • Solid catalyst Z3 was obtained in the same manner as in Catalyst Production Example 1, except that the mixture obtained in Catalyst Production Example 1 was tableted into cylindrical shapes with an outer diameter of 7.0 mm, a height of 7.0 mm, a catalyst volume of 269.4 mm3 /tablet, and a crushing strength of 40 kgG.
  • the catalyst powdering rate of solid catalyst Z3 was 0.020% by mass.
  • solid catalyst Z3 was dropped to form a catalyst layer, and the proportions of finely divided catalyst contained in the lower layer (1500 g) and the upper layer (1500 g) were measured. As a result, it was found that a larger proportion of finely divided catalyst was found in the lower layer, at a ratio of 9:1.
  • Example 1 1500 g of solid catalyst Z1 was packed into a stainless steel reaction tube with an inner diameter of 27 mm and a length of 6 m equipped with a fixed-bed reactor. Next, a mixed catalyst prepared by thoroughly mixing 1500 g of solid catalyst Z1 with 67 g of a fine powder catalyst obtained by crushing solid catalyst Z1 and passing it through a sieve with a nominal mesh size of 1 mm was added from above the packed solid catalyst Z1 to form a catalyst layer (ratio of fine powder catalyst to total catalyst weight of 3067 g: 2.185 mass%). The spaces below and above the catalyst layer in the reaction tube were each packed with 200 g of unused ceramic balls (6 mm diameter) as a packing material (see FIG.
  • the catalyst powdering rate of solid catalyst Z1 was 0% by mass, and therefore, after the catalyst was packed, the ratio of the finely powdered catalyst to the total amount of catalyst (X 1 + X 2 ) remained 2.185% by mass, the same as when the catalyst was packed (immediately before packing). Furthermore, the ratio of the catalyst that passed through a sieve with a nominal mesh size of 9.5 mm present in the reaction tube after the catalyst was packed to the total amount of catalyst was 100% by mass.
  • the temperature of the heat medium bath was raised to 380°C at a rate of 25°C/hr under air flow, and then the catalyst was heat-treated by holding it at 380°C for 12 hours.
  • Example 2 A catalyst layer was formed using a mixture of 1,500 g of solid catalyst Z1 and 31 g of fine powder catalyst, which was thoroughly mixed and charged from above the solid catalyst Z1 (ratio of fine powder catalyst to total catalyst amount of 3,031 g: 1.023 mass%). Except for the above, the catalyst was charged and heat-treated in the same manner as in Example 1, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X 1 + X 2 after catalyst charging remained at 1.023 mass%, the same as when the catalyst was charged. There was no change in the ratio of fine powder catalyst before and after heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst charged in the reaction tube satisfied the above formulas (1) and (2).
  • Example 3 A catalyst layer was formed using a mixture of 1500 g of solid catalyst Z1 and 15 g of fine powder catalyst, which was thoroughly mixed and charged from above the solid catalyst Z1 (ratio of fine powder catalyst to total catalyst amount of 3015 g: 0.498 mass%). Except for the above, the catalyst was charged and heat-treated in the same manner as in Example 1, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X 1 + X 2 after catalyst charging remained at 0.498 mass%, the same as when the catalyst was charged. There was no change in the ratio of fine powder catalyst before and after heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst charged in the reaction tube satisfied the above formulas (1) and (2).
  • Example 4 A catalyst layer was formed using a mixture of 1500 g of solid catalyst Z1 and 3 g of fine powder catalyst, which was thoroughly mixed and charged from above the solid catalyst Z1 (ratio of fine powder catalyst to total catalyst amount of 3003 g: 0.100 mass%). Except for the above, the catalyst was charged and heat-treated in the same manner as in Example 1, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X 1 + X 2 after catalyst charging remained at 0.100 mass%, the same as when the catalyst was charged. There was no change in the proportion of fine powder catalyst before and after the heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst charged in the reaction tube satisfied the above formulas (1) and (2).
  • Example 5 A catalyst layer was formed using a mixture of 1500 g of solid catalyst Z1 and 0.4 g of fine powder catalyst, which was thoroughly mixed and charged from above the solid catalyst Z1 (ratio of fine powder catalyst to total catalyst amount of 3000.4 g: 0.013 mass%). Except for the above, the catalyst was charged and heat-treated in the same manner as in Example 1, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X 1 + X 2 after catalyst charging remained at 0.013 mass%, the same as when the catalyst was charged. There was no change in the proportion of fine powder catalyst before and after the heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst charged in the reaction tube satisfied the above formulas (1) and (2).
  • a catalyst layer was formed using a mixed catalyst obtained by thoroughly mixing 1,500 g of solid catalyst Z1 and 105 g of fine powder catalyst to be additionally packed from above solid catalyst Z1 (ratio of fine powder catalyst to total catalyst amount of 3,105 g: 3.382 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 1, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X1 + X2 after catalyst packing remained at 3.382 mass%, the same as when the catalyst was packed. Note that there was no change in the ratio of fine powder catalyst before and after the catalyst heat treatment, and the fine powder catalyst packed in the reaction tube did not satisfy the above formula (1).
  • a catalyst layer was formed using a mixed catalyst obtained by thoroughly mixing 1,500 g of solid catalyst Z1 and 71 g of fine powder catalyst to be additionally packed from above solid catalyst Z1 (ratio of fine powder catalyst to total catalyst amount of 3,071 g: 2.312 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 1, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X1 + X2 after catalyst packing remained at 2.312 mass%, the same as when the catalyst was packed. Note that there was no change in the ratio of fine powder catalyst before and after the catalyst heat treatment, and the fine powder catalyst packed in the reaction tube did not satisfy the above formula (1).
  • a catalyst layer was formed using a mixture of 1500 g of solid catalyst Z1 and 0.2 g of fine powder catalyst, which was thoroughly mixed and charged from above solid catalyst Z1 (ratio of fine powder catalyst to total catalyst amount of 3000.2 g: 0.007 mass%). Except for the above, the catalyst was charged and heat-treated in the same manner as in Example 1, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X1 + X2 after catalyst charging remained at 0.007 mass%, the same as when the catalyst was charged. There was no change in the ratio of fine powder catalyst before and after heat-treatment of the catalyst, and the fine powder catalyst charged in the reaction tube did not satisfy the above formula (1).
  • Example 6 A catalyst layer was formed using a mixture of 1500 g of solid catalyst Z1, 200 g of unused 6 mm diameter ceramic balls (filling aids, designated "CB" in the table), and 62 g of a fine powder catalyst obtained by crushing solid catalyst Z1 and passing through a 1 mm nominal mesh sieve (ratio of fine powder catalyst to total catalyst weight of 3062 g: 2.025 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 1, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1.
  • the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X1 + X2 after catalyst packing remained at 2.025 mass%, the same as when the catalyst was packed. There was no change in the proportion of fine powder catalyst before and after the heat treatment of the catalyst. Furthermore, since the reaction gas is passed through the upper part of the reaction tube, the finely divided catalyst packed in the reaction tube satisfies the above formulas (1) and (2).
  • Example 7 A catalyst layer was formed using a mixture of 1,500 g of solid catalyst Z1, 200 g of unused 6 mm ⁇ ceramic balls, and 31 g of fine powder catalyst, which was thoroughly mixed together to be additionally packed from above the solid catalyst Z1 (ratio of fine powder catalyst to total catalyst weight of 3,031 g: 1.023 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 6, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X1 + X2 after catalyst packing remained at 1.023 mass%, the same as when the catalyst was packed. There was no change in the proportion of fine powder catalyst before and after heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst packed in the reaction tube satisfied the above formulas (1) and (2).
  • Example 8 A catalyst layer was formed using a mixture of 1500 g of solid catalyst Z1, 200 g of unused 6 mm ⁇ ceramic balls, and 3 g of fine powder catalyst, which was thoroughly mixed and charged from above the solid catalyst Z1 (ratio of fine powder catalyst to total catalyst weight of 3003 g: 0.100 mass%). Except for the above, the catalyst was charged and heat-treated in the same manner as in Example 6, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X1 + X2 after catalyst charging remained at 0.100 mass%, the same as when the catalyst was charged. There was no change in the proportion of fine powder catalyst before and after heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst charged in the reaction tube satisfied the above formulas (1) and (2).
  • Example 9 A catalyst layer was formed using a mixture of 1500 g of solid catalyst Z1, 200 g of unused 6 mm ⁇ ceramic balls, and 1.2 g of fine powder catalyst, which was thoroughly mixed to be additionally packed from above the solid catalyst Z1 (ratio of fine powder catalyst to total catalyst amount of 3001.2 g: 0.040 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 6, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X1 + X2 after catalyst packing remained at 0.040 mass%, the same as when the catalyst was packed. There was no change in the proportion of fine powder catalyst before and after the heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst packed in the reaction tube satisfied the above formulas (1) and (2).
  • the catalyst powdering rate of solid catalyst Z1 was 0 mass%, so X1 + X2 after catalyst packing remained at 2.407 mass%, the same as when the catalyst was packed. Note that there is no change in the proportion of the fine powder catalyst before and after the heat treatment of the catalyst, and the fine powder catalyst packed in the reaction tube does not satisfy the above formula (1) and formula (2) (in Comparative Example 5, X2 is 0 mass%).
  • the mixed catalyst to be additionally packed from above the solid catalyst Z1 was a thorough mixture of 1500 g of the solid catalyst Z1, 200 g of unused 6 mm ⁇ ceramic balls, and 0.1 g of the fine powder catalyst (ratio of the fine powder catalyst to the total catalyst amount of 3000.1 g: 0.003 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 6, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of the solid catalyst Z1 was 0 mass%, so X1 + X2 after the catalyst packing remained at 0.003 mass%, the same as when the catalyst was packed. Note that there was no change in the proportion of the fine powder catalyst before and after the catalyst heat treatment, and the catalyst packed in the reaction tube did not satisfy the above formula (1).
  • Example 10 1500 g of solid catalyst Z2 was packed into a reaction tube similar to that used in Example 1. Next, a mixed catalyst prepared by thoroughly mixing 1500 g of solid catalyst Z2, 200 g of unused 3 mm ⁇ ceramic balls, and 62 g of a finely divided catalyst obtained by crushing solid catalyst Z2 and passing it through a 1 mm nominal mesh sieve was added from above the packed solid catalyst Z2 to form a catalyst layer (ratio of finely divided catalyst to total catalyst weight of 3062 g: 2.025 mass%).
  • the catalyst was then heat-treated in the same manner as in Example 1, and a gas-phase catalytic oxidation reaction of methacrolein was carried out in the same manner as in Example 1, except that the temperature of the heat medium bath was changed to 280°C.
  • the results are shown in Table 1.
  • the catalyst powdering rate of solid catalyst Z2 was 0 mass%, so X1 + X2 after the catalyst packing remained at 2.025 mass%, the same as when the catalyst was packed. There was no change in the proportion of finely divided catalyst before and after the heat treatment of the catalyst.
  • the fine powder catalyst packed in the reaction tube satisfied the above formulas (1) and (2) (hereinafter, in Examples 10 to 13 and Comparative Examples 7 and 8 using solid catalyst Z2, X1 is 0 mass% in each case). Furthermore, the proportion of the catalyst passing through a sieve with a nominal opening of 9.5 mm present in the reaction tube after the catalyst was packed relative to the total amount of the catalyst was 100 mass%.
  • Example 11 A catalyst layer was formed using a mixture of 1,500 g of solid catalyst Z2, 200 g of unused 3 mm ⁇ ceramic balls, and 31 g of fine powder catalyst, which was thoroughly mixed together to be additionally packed from above the solid catalyst Z2 (ratio of fine powder catalyst to total catalyst weight of 3,031 g: 1.023 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 10, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z2 was 0 mass%, so X 1 + X 2 after catalyst packing remained at 1.023 mass%, the same as when the catalyst was packed. There was no change in the proportion of fine powder catalyst before and after heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst packed in the reaction tube satisfied the above formulas (1) and (2).
  • Example 12 A catalyst layer was formed using a mixture of 1500 g of solid catalyst Z2, 200 g of unused 3 mm ⁇ ceramic balls, and 3 g of fine powder catalyst, which was thoroughly mixed together to be additionally packed from above the solid catalyst Z2 (ratio of fine powder catalyst to total catalyst weight of 3003 g: 0.100 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 10, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z2 was 0 mass%, so X 1 + X 2 after catalyst packing remained at 0.100 mass%, the same as when the catalyst was packed. There was no change in the proportion of fine powder catalyst before and after heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst packed in the reaction tube satisfied the above formulas (1) and (2).
  • Example 13 A catalyst layer was formed using a mixture of 1500 g of solid catalyst Z2, 200 g of unused 3 mm ⁇ ceramic balls, and 0.4 g of fine powder catalyst, which was thoroughly mixed to be additionally packed from above the solid catalyst Z2 (ratio of fine powder catalyst to total catalyst amount of 3000.4 g: 0.013 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 10, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z2 was 0 mass%, so X 1 + X 2 after catalyst packing remained at 0.013 mass%, the same as when the catalyst was packed. There was no change in the proportion of fine powder catalyst before and after the heat treatment of the catalyst. Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst packed in the reaction tube satisfied the above formulas (1) and (2).
  • a catalyst layer was formed using a mixture of 1,500 g of solid catalyst Z2, 200 g of unused 3 mm ⁇ ceramic balls, and 74 g of fine powder catalyst, which was thoroughly mixed and charged from above solid catalyst Z2 (ratio of fine powder catalyst to total catalyst amount of 3,074 g: 2.407 mass%). Except for the above, the catalyst was charged and heat-treated in the same manner as in Example 10, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z2 was 0 mass%, so X1 + X2 after catalyst charging remained at 2.407 mass%, the same as when the catalyst was charged. Note that there was no change in the proportion of fine powder catalyst before and after the catalyst heat treatment, and the fine powder catalyst charged in the reaction tube did not satisfy the above formula (1).
  • a catalyst layer was formed using a mixture of 1500 g of solid catalyst Z2, 200 g of unused 3 mm ⁇ ceramic balls, and 0.02 g of fine powder catalyst, which was thoroughly mixed and charged from above solid catalyst Z2 (ratio of fine powder catalyst to total catalyst amount of 3000.02 g: 0.0007 mass%). Except for the above, the catalyst was charged and heat-treated in the same manner as in Example 10, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1. As described above, the catalyst powdering rate of solid catalyst Z2 was 0 mass%, so X1 + X2 after catalyst charging remained at 0.0007 mass%, the same as when the catalyst was charged. Note that there was no change in the proportion of fine powder catalyst before and after the catalyst heat treatment, and the fine powder catalyst charged in the reaction tube did not satisfy the above formula (1).
  • Example 14 1500 g of solid catalyst Z3 was packed into a reaction tube similar to that used in Example 1. Next, from above the packed solid catalyst Z3, a mixed catalyst was added, prepared by thoroughly mixing 1500 g of solid catalyst Z3, 200 g of an unused stainless steel spring (SUS430, indicated as "SS" in the table) with a height of 6 mm, a wire diameter of 1 mm, and a gap of 0.5 mm, and 68 g of a fine catalyst obtained by crushing solid catalyst Z3 and passing it through a sieve with a nominal mesh size of 1 mm, to form a catalyst layer (ratio of fine catalyst to total catalyst weight of 3068 g: 2.236 mass%).
  • SUS430 an unused stainless steel spring
  • the catalyst was then heat-treated in the same manner as in Example 1, and the gas-phase catalytic oxidation reaction of methacrolein was carried out in the same manner as in Example 1, except that the temperature of the heat medium bath was set to 300°C.
  • the results are shown in Table 1. Since the packing powder ratio of solid catalyst Z3 was 0.020 mass%, the amount of fine catalyst produced from a total of 3000 g of solid catalyst Z3 was 0.6 g. Here, since the 68 g of the fine powder catalyst is contained in the reaction gas inlet side region, the fine powder catalyst packed in the reaction tube satisfies the above formula (2). In addition, since the reaction gas is circulated from the top of the reaction tube, the fine powder catalyst packed in the reaction tube satisfies the above formula (1). Furthermore, the ratio of the catalyst that passes through a sieve with a nominal mesh size of 9.5 mm and is present in the reaction tube after the catalyst packing to the total amount of catalyst was 100 mass%.
  • Example 15 A catalyst layer was formed using a mixture of 1500 g of solid catalyst Z3, 200 g of an unused stainless steel spring (SUS430) with a height of 6 mm, a wire diameter of 1 mm, and a gap of 0.5 mm, and 5 g of fine powder catalyst, which was thoroughly mixed to form a catalyst layer (ratio of fine powder catalyst to the total catalyst weight of 3005 g: 0.186 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 14, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1.
  • the packing powder ratio of solid catalyst Z3 was 0.020 mass%, the amount of fine powder catalyst produced from a total of 3000 g of solid catalyst Z3 was 0.6 g. Since the 5 g of fine powder catalyst was contained in the reaction gas inlet region, the fine powder catalyst packed in the reaction tube satisfies the above formula (2). Furthermore, since the reaction gas was circulated from the top of the reaction tube, the fine powder catalyst packed in the reaction tube satisfies the above formula (1).
  • a catalyst layer was formed using a mixture of 1500 g of solid catalyst Z3, 200 g of an unused stainless steel spring (SUS430) with a height of 6 mm, a wire diameter of 1 mm, and a gap of 0.5 mm, and 75 g of fine powder catalyst, which was thoroughly mixed together to form a catalyst layer (ratio of fine powder catalyst to the total catalyst weight of 3075 g: 2.458 mass%). Except for the above, the catalyst was packed and heat-treated in the same manner as in Example 14, and a gas-phase catalytic oxidation reaction of methacrolein was carried out. The results are shown in Table 1.
  • the packing powder ratio of solid catalyst Z3 was 0.020 mass%, the amount of fine powder catalyst produced from a total of 3000 g of solid catalyst Z3 was 0.6 g. Since the 75 g of fine powder catalyst was included in the reaction gas inlet region, the fine powder catalyst packed in the reaction tube satisfied the above formula (2). On the other hand, there is no change in the proportion of the fine powder catalyst before and after the heat treatment of the catalyst, and the fine powder catalyst packed in the reaction tube does not satisfy the above formula (1).
  • the proportion of catalyst that passed through a sieve with a nominal mesh size of 9.5 mm and was present in the reaction tube after the catalyst was packed was 100% by mass relative to the total amount of catalyst.
  • the yield of methacrylic acid is improved by setting the ratio of the powder catalyst to the total amount of catalyst (X 1 +X 2 ) within the range of formula (1) and further filling the powder catalyst so as to satisfy formula (2), as in Examples 1 to 5.
  • Reaction tube 1A Reaction gas inlet 1B: Reaction gas outlet 2: Catalyst 3: Catalyst layer 4: Filler P: Boundary position Q1 : End portion on the reaction gas outlet side Q2 : End portion on the reaction gas inlet side A1 : Reaction gas outlet side region (first region) A2 : Reactant gas inlet side region (second region)

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Abstract

L'invention concerne un procédé de remplissage de catalyseur avec lequel il est possible d'améliorer le rendement d'un produit cible dans une réaction à l'aide d'un catalyseur sans réaliser un processus de fabrication de catalyseur spécial. L'invention concerne un procédé pour le remplissage d'un tube de réaction 1 ménagé dans un réacteur à lit fixe avec un catalyseur 2, le catalyseur contenant un catalyseur solide et un catalyseur en poudre fine, et le catalyseur en poudre fine satisfaisant les relations 0,010 % en masse ≤ X1 + X2 ≤ 2,300 % en masse et X1 < X2 (X1 représentant la quantité (% en masse) du catalyseur en poudre fine présente dans une région côté de sortie de gaz de réaction A1 par rapport à 100 % en masse de la quantité totale du catalyseur, et X2 représente la quantité (% en masse) du catalyseur en poudre fine présente dans une région côté d'entrée de gaz de réaction A2 par rapport à 100 % en masse de la quantité totale du catalyseur, la région de côté de sortie de gaz de réaction étant une région dans laquelle 50 % en masse de la quantité totale de 100 % en masse du catalyseur solide est présente par intégration à partir du côté 1B de sortie de gaz de réaction, et la région de côté d'entrée de gaz de réaction étant une région dans laquelle 50 % en masse de la quantité totale de 100 % en masse du catalyseur solide est présente par intégration à partir du côté 1A d'entrée de gaz de réaction.
PCT/JP2025/002911 2024-02-01 2025-01-30 Procédé de remplissage de catalyseur, procédé de production d'acide (méth)acrylique et tube de réaction Pending WO2025164703A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002306970A (ja) * 2001-04-12 2002-10-22 Mitsubishi Rayon Co Ltd メタクリル酸製造用触媒、その製造方法、および、メタクリル酸の製造方法
WO2010001732A1 (fr) * 2008-06-30 2010-01-07 株式会社日本触媒 Procédé de conditionnement d'une substance particulaire solide dans un réacteur multitubulaire à lit fixe
WO2013147032A1 (fr) * 2012-03-29 2013-10-03 株式会社日本触媒 Procédé de production d'acide acrylique utilisant un réacteur multitubulaire à lit fixe
WO2021141122A1 (fr) * 2020-01-08 2021-07-15 三菱ケミカル株式会社 Procédé de fabrication de catalyseur pour fabrication d'acide méthacrylique, procédé de fabrication d'acide méthacrylique, procédé de fabrication d'ester d'acide méthacrylique, et dispositif de fabrication de catalyseur pour fabrication d'acide méthacrylique

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WO2013147032A1 (fr) * 2012-03-29 2013-10-03 株式会社日本触媒 Procédé de production d'acide acrylique utilisant un réacteur multitubulaire à lit fixe
WO2021141122A1 (fr) * 2020-01-08 2021-07-15 三菱ケミカル株式会社 Procédé de fabrication de catalyseur pour fabrication d'acide méthacrylique, procédé de fabrication d'acide méthacrylique, procédé de fabrication d'ester d'acide méthacrylique, et dispositif de fabrication de catalyseur pour fabrication d'acide méthacrylique

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