WO2022250030A1 - （メタ）アクロレイン及び（メタ）アクリル酸の一方又は両方の製造方法 - Google Patents

（メタ）アクロレイン及び（メタ）アクリル酸の一方又は両方の製造方法 Download PDF

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WO2022250030A1
WO2022250030A1 PCT/JP2022/021177 JP2022021177W WO2022250030A1 WO 2022250030 A1 WO2022250030 A1 WO 2022250030A1 JP 2022021177 W JP2022021177 W JP 2022021177W WO 2022250030 A1 WO2022250030 A1 WO 2022250030A1
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reaction tube
meth
catalyst
raw material
reaction
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French (fr)
Japanese (ja)
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啓輔 馬場
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to KR1020237039487A priority Critical patent/KR20230170962A/ko
Priority to CN202280036474.4A priority patent/CN117396457A/zh
Priority to JP2023523473A priority patent/JP7613573B2/ja
Publication of WO2022250030A1 publication Critical patent/WO2022250030A1/ja
Priority to US18/516,423 priority patent/US20240101502A1/en
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    • 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
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • 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
    • 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 producing one or both of (meth)acrolein and (meth)acrylic acid.
  • reaction runaway may occur due to the generation of reaction heat exceeding the heat removal capacity of the reactor.
  • Patent Document 1 discloses a shell and tube heat exchanger type provided with a plurality of reaction tubes having a catalyst layer filled with at least a catalyst.
  • a method of setting the conditions for the source gas flow rate and the heat removal capacity of the reactor in consideration of the calorie balance of the heat medium is shown.
  • the necessary amount of catalyst cannot be filled in the reaction tube, and the target production volume cannot be achieved, or the continuous operation period of the reactor may be shortened. have a nature.
  • the reactor may become an excessively large facility for the production volume of the target product, increasing the production cost.
  • the present invention prevents reaction runaway in a heat exchange reactor and suppresses excessive progress of the reaction and local catalyst deterioration, thereby producing (meth)acrolein and (meth)acrylic acid with high selectivity.
  • One challenge is to manufacture one or both.
  • “(Meth)acrolein” is a generic term for acrolein and methacrolein
  • (meth)acrylic acid” is a generic term for acrylic acid and methacrylic acid.
  • the oxidation reaction of the raw material supplied to the reaction tube causes (meth)acrolein and ( A method for producing one or both of meth)acrylic acid
  • the reaction tube has a plurality of catalyst layers with different catalyst filling amounts per unit volume, i layers in the longitudinal direction of the reaction tube, where i is an integer of 2 or more, A method for producing one or both of (meth)acrolein and (meth)acrylic acid, wherein the oxidation reaction satisfies formula (1).
  • m1 is the catalyst filling amount (kg) in the first catalyst layer from the raw material inlet side of the reaction tube
  • mj is the j-th catalyst layer from the raw material inlet side of the reaction tube.
  • j is an integer of 1 or more and i or less
  • F is the supply amount (mol/h) of the raw material to the reaction tube
  • A is the raw material inlet of the reaction tube.
  • the inner surface area (m 2 ) of the reaction tube in contact with the first catalyst layer from the side, and U is based on the inner surface area of the portion of the reaction tube in which both the first catalyst layer and the heating medium are in contact.
  • m1 is the catalyst filling amount (kg) in the first catalyst layer from the raw material inlet side of the reaction tube
  • mk is the k-th layer from the raw material inlet side of the reaction tube. It is the catalyst filling amount (kg) in the catalyst layer
  • k is an integer of 1 or more and i or less.
  • [7] The production method according to any one of [1] to [6], wherein U is 40 to 400 (W/m 2 /K).
  • [8] The production method according to any one of [1] to [7], wherein U is 50 to 300 (W/m 2 /K).
  • [9] The production method according to any one of [1] to [8], wherein F is 1 to 20 (mol/h).
  • [10] The production method according to any one of [1] to [9], wherein F is 2.5 to 15 (mol/h).
  • [11] The production method according to any one of [1] to [10], wherein A is 0.03 to 0.6 (m 2 ).
  • the raw material is at least one selected from propylene, isobutylene, tert-butanol, and methyl tert-butyl ether, and one or both of the (meth)acrolein and (meth)acrylic acid is (meth)acrolein and (meth)acrylic acid, the production method according to any one of [1] to [11].
  • Y represents at least one element selected from the group consisting of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium.
  • Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium.
  • P, Mo, V, Cu and O represent phosphorus, molybdenum, vanadium, copper and oxygen respectively.
  • X represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron.
  • Y represents at least one element selected from the group consisting of iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium and lanthanum.
  • Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium.
  • (meth)acrolein and (meth)acrolein are produced with high selectivity by preventing runaway reaction in the heat exchange reactor and suppressing excessive progress of the reaction and local catalyst deterioration.
  • One or both of the acrylic acids can be produced.
  • the method for producing one or both of (meth)acrolein and (meth)acrylic acid of the present invention is a method in which a heat exchange type reactor having a reaction tube inside is used, and a raw material supplied to the reaction tube is oxidized while a heat medium is circulated outside the reaction tube.
  • the reaction tube is provided with a plurality of i layers of catalyst layers having different catalyst filling amounts per unit volume in the longitudinal direction of the reaction tube.
  • i is an integer of 2 or more.
  • the production method of the present invention satisfies formula (1) in the oxidation reaction.
  • m1 is the catalyst filling amount (kg) in the first catalyst layer from the raw material inlet side of the reaction tube
  • mj is the ith catalyst layer from the raw material inlet side of the reaction tube.
  • j is an integer of 1 or more and i or less
  • F is the supply amount (mol/h) of the raw material to the reaction tube
  • A is the raw material inlet of the reaction tube.
  • the inner surface area (m 2 ) of the reaction tube in contact with the first catalyst layer from the side, and U is based on the inner surface area of the portion of the reaction tube in which both the first catalyst layer and the heating medium are in contact.
  • the production method of the present invention prevents runaway reaction in the heat exchange reactor and suppresses excessive progress of the reaction and local catalyst deterioration, resulting in high selectivity (meta ) one or both of acrolein and (meth)acrylic acid can be produced.
  • the present invention focuses on the first catalyst layer having the highest raw material concentration, and controls the ratio between the heat generation rate and the heat removal rate in the catalyst layer. Then, the ratio of the heat release rate to the heat removal rate in the first catalyst layer becomes a value suitable for the production of one or both of (meth)acrolein and (meth)acrylic acid, so that each catalyst provided in the reaction tube.
  • the ratio of heat generation rate and heat removal rate of the layer becomes appropriate, and an increase in reaction temperature can be suppressed. As a result, runaway reaction can be suppressed, and one or both of (meth)acrolein and (meth)acrylic acid can be produced with high selectivity.
  • the production method of the present invention is a method of producing (meth)acrolein and (meth)acrylic acid using at least one selected from propylene, isobutylene, tert-butanol, and methyl tert-butyl ether as a raw material, or (meth)acrolein can be suitably applied in a method for producing (meth)acrylic acid as a raw material.
  • it is preferably applied to a method of producing (meth)acrylic acid using (meth)acrolein as a raw material, and more preferably applied to a method of producing methacrylic acid from methacrolein.
  • the production method of the present invention uses a heat exchange reactor having a reaction tube inside.
  • a heat exchange reactor for example, a double tube heat exchanger reactor, industrially a multi-tube heat exchanger reactor can be used.
  • An example of a shell and tube heat exchanger type reactor is shown in FIG.
  • a reactor 1 is equipped with a reaction tube 2 and baffle plates 3 inside.
  • a raw material inlet 4 is provided at the bottom of the reactor 1, and a product outlet 5 is provided at the top.
  • the interior of the reactor 1 is vertically partitioned into three regions by a first partition plate 9 on the raw material inlet 4 side and a second partition plate 10 on the product outlet 5 side.
  • the reaction tubes 2 are provided so as to extend from the first partition plate 9 to the second partition plate 10, and both end surfaces of the reaction tubes 2 are opened to the raw material inlet portion 4 side and the product outlet portion 5 side, respectively.
  • a heating medium bath 8 through which a heating medium flows is provided outside the reaction tube 2 in a region between the first partition plate 9 and the second partition plate 10 in the reactor 1 .
  • a heat medium inlet portion 6 is provided on the side wall of the reactor 1 near the first partition plate 9
  • a heat medium outlet portion 7 is provided on the side wall of the reactor 1 near the second partition plate 10 .
  • the baffle plate 3 is provided in a region between the first partition plate 9 and the second partition plate 10 so as to be perpendicular to the longitudinal direction of the reaction tube 2 .
  • the raw material flows into the reactor 1 from the raw material inlet 4 , flows through the reaction tube 2 from the raw material inlet side of the reaction tube 2 , and flows out from the product outlet 5 .
  • the raw material inlet side of the reaction tube 2 means the end surface of the raw material inlet portion 4 side.
  • the heat medium flows in from the heat medium inlet 6, flows meanderingly along the outside of the reaction tube 2 from the raw material inlet 4 side to the product outlet 5 side by the baffle plate 3, and flows out from the heat medium outlet 7.
  • the reaction tube is provided with a plurality of i layers of catalyst layers having different catalyst filling amounts per unit volume in the longitudinal direction of the reaction tube.
  • i is an integer of 2 or more.
  • the reaction tube is provided with two or more catalyst layers in its longitudinal direction, and adjacent catalyst layers have different catalyst filling amounts per unit volume.
  • the catalyst loading amount per unit volume differs means that the catalyst loading amount per unit volume differs by 1% or more.
  • the case where the catalyst layer contains a diluent includes a case where the mixed ratio of the filled catalyst and diluent differs by 1% or more, or a case where the density of the catalyst or diluent differs by 1% or more.
  • the "catalyst layer” is defined as having a thickness of 100 mm or more in the longitudinal direction of the reaction tube.
  • a diluent and a catalyst are mixed and filled so that the catalyst filling amount per unit volume is a desired value, or A method of packing catalysts of different shapes can be mentioned. From the viewpoint of catalyst production cost, a method of mixing and filling the diluent and the catalyst is preferable.
  • the diluent there are no particular restrictions on the diluent as long as it is an inert substance that does not show activity in the oxidation reaction that produces one or both of (meth)acrolein and (meth)acrylic acid.
  • inert substances include silica, alumina, silica-alumina, silicon carbide, titania, magnesia, ceramic balls, and stainless steel.
  • i the number of catalyst layers, as long as it is an integer of 2 or more. From the viewpoint of reducing the load of the catalyst filling operation, i is preferably an integer of 4 or less, more preferably 2.
  • i 2 or more.
  • the catalyst filling amount per unit volume in the first catalyst layer from the raw material inlet side of the reaction tube is equal to that of the second catalyst layer. It is preferably smaller than the catalyst filling amount per unit volume in .
  • the length of the catalyst layer is not particularly limited, but from the viewpoint of the production amount of one or both of (meth)acrolein and (meth)acrylic acid, the length of the first catalyst layer from the raw material inlet of the reaction tube is preferably 0.5 m or more, more preferably 1.5 m or more. From the viewpoint of production cost, the length of the first catalyst layer from the raw material inlet of the reaction tube is preferably 6 m or less, more preferably 4 m or less.
  • the reaction tube may have an inert material layer between the end on the raw material inlet side and the catalyst layer for the purpose of supporting the catalyst layer and preheating the raw material.
  • the inert material layer preferably consists of only the above-described inert material.
  • the catalysts filled in each catalyst layer are composed of common elements, and that the difference in the composition ratio of each elemental component is 10% or less.
  • the catalyst layer When the production method of the present invention is a method for producing (meth)acrolein and (meth)acrylic acid using one or more selected from propylene, isobutylene, tert-butanol, and methyl tert-butyl ether as raw materials, the catalyst layer In, it is preferable to use a catalyst having a composition represented by formula (I). Mo a1 Bi b1 Fe c1 M d1 X e1 Y f1 Z g1 Si h1 O i1 (I) In formula (I), Mo, Bi, Fe, Si and O represent molybdenum, bismuth, iron, silicon and oxygen respectively. M represents at least one element selected from the group consisting of cobalt and nickel.
  • X represents at least one element selected from the group consisting of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc.
  • Y represents at least one element selected from the group consisting of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium.
  • Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium.
  • a catalyst having a composition represented by formula (II) can be used in the catalyst layer.
  • P a2 Mo b2 V c2 Cu d2 X e2 Y f2 Z g2 O h2 (II)
  • P, Mo, V, Cu and O represent phosphorus, molybdenum, vanadium, copper and oxygen respectively.
  • X represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron.
  • Y represents at least one element selected from the group consisting of iron, zinc, chromium, magnesium, tantalum, cobalt, manganese, barium, gallium, cerium and lanthanum.
  • Z represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium.
  • the shape, size, etc. of the catalyst there are no particular restrictions on the shape, size, etc. of the catalyst, and it may be spherical, cylindrical, ring-shaped, star-shaped, etc., and may be molded by a conventional tableting machine, extruder, granulator, or the like. can. Also, a supported catalyst in which a catalyst having the above composition is supported on a carrier may be used. As the catalyst, a catalyst having a plurality of shapes may be used, but from the viewpoint of the production cost of the catalyst, it is preferable that the catalysts have the same shape.
  • the method for producing one or both of (meth)acrolein and (meth)acrylic acid of the present invention satisfies formula (1) in the oxidation reaction of the raw materials.
  • the value of ⁇ represents the easiness of temperature change in the first catalyst layer from the raw material inlet side of the reaction tube.
  • the amount of catalyst distributed to the first catalyst layer is appropriate, and the exotherm rate and removal rate are suitable for the production of one or both of (meth)acrolein and (meth)acrylic acid. It is the ratio of the thermal velocities.
  • the upper limit of the value of ⁇ is preferably 0.24 (mol K/h/W) or less, more preferably 0.12 (mol K/h/W) or less. , 0.06 (mol ⁇ K/h/W) or less.
  • the lower limit of the value of ⁇ is preferably 0.002 (mol ⁇ K/h/W) or more. As a result, production costs can be reduced relative to the amount of production of one or both of (meth)acrolein and (meth)acrylic acid.
  • the lower limit of the value of ⁇ is more preferably 0.004 (mol ⁇ K/h/W) or more, more preferably 0.006 (mol ⁇ K/h/W) or more.
  • the formula (1) is preferably satisfied in 50% or more of the total number of the plurality of reaction tubes, and in 80% or more of the total number of the reaction tubes. It is more preferable to fill 90% or more of the total number of the plurality of reaction tubes.
  • the ratio ⁇ of the catalyst filling amount of the first catalyst layer from the raw material inlet side of the reaction tube to the total catalyst filling amount of the reaction tube is represented by the formula (**).
  • m1 is the catalyst filling amount (kg) in the first catalyst layer from the raw material inlet side of the reaction tube
  • mk is the k-th catalyst layer from the raw material inlet side of the reaction tube.
  • k is an integer of 1 or more and i or less.
  • the value of ⁇ is 0.25 or more, the amount of heat generated in the second and subsequent catalyst layers from the raw material inlet side of the reaction tube is more preferably suppressed. Moreover, when the value of ⁇ is 0.5 or less, the productivity of one or both of (meth)acrolein and (meth)acrylic acid is improved.
  • the lower limit of the value of ⁇ is more preferably 0.26 or more, still more preferably 0.27 or more, and particularly preferably 0.28 or more. Also, the lower limit of the value of ⁇ is more preferably 0.48 or less, even more preferably 0.46 or less, and particularly preferably 0.45 or less.
  • the heat exchange reactor has a plurality of reaction tubes
  • the formula (2) is satisfied in 50% or more of the total number of the plurality of reaction tubes, and 80% of the total number of the plurality of reaction tubes It is more preferable to satisfy the above conditions, and more preferably to satisfy 90% or more of the total number of the plurality of reaction tubes.
  • U in the formula (*) is the overall heat transfer coefficient (W/m 2 /K) based on the inner surface area of the portion of the reaction tube where both the first catalyst layer and the heat medium are in contact. .
  • an inert gas composed of 21% by volume of oxygen and 79% by volume of nitrogen is supplied to the reaction tube at a temperature 50 ° C. lower than the heat medium flowing outside the reaction tube to form the first layer of catalyst. It can be calculated from the result of measuring the temperature distribution in a minute area of the layer (hereinafter, the "minute area of the first catalyst layer” may be simply referred to as the "minute area”).
  • the minute area means an area obtained by dividing the reaction tube into 20 mm pieces in the longitudinal direction.
  • the temperature change dT1(K) in the longitudinal direction of the reaction tube in the minute region is expressed by the formula (* **).
  • dT1 U ⁇ inner surface area (m 2 ) of reaction tube in contact with minute region ⁇ dT2/[mass flow rate of inert gas (g/s) ⁇ specific heat of inert gas (J/g/K)] ( ***)
  • U can be calculated by using the method of least squares to find the value of U such that dT1 calculated by the formula (***) and the measured value of dT1 match.
  • U be the arithmetic mean value obtained for 20 adjacent minute regions. Further, the minute area is set so that dT2 is 3° C. or more at at least one point among the 20 points of the minute area.
  • the inert gas is supplied at a temperature 50° C. lower than that of the heat medium flowing outside the reaction tube.
  • U is not particularly limited as long as ⁇ satisfies the formula (1). /m 2 /K) or more, and more preferably 70 (W/m 2 /K) or more.
  • U is preferably 400 (W/m 2 /K) or less, more preferably 300 (W/m 2 /K) or less. , 150 (W/m 2 /K) or less.
  • U is defined as above. It is preferable to satisfy 50% or more of the total number of the plurality of reaction tubes, more preferably 80% or more of the total number of the plurality of reaction tubes, and 90% or more of the total number of the plurality of reaction tubes. More preferred.
  • Methods for adjusting U include, for example, changing the flow conditions of the heat medium, changing the flow rate of the nitrogen gas, changing the ratio and shape of the catalyst in the first medium layer, and changing the material and shape of the diluent in the first catalyst layer. A change, a change of the material of a reaction tube, a diameter, or thickness is mentioned.
  • F in the formula (*) is the supply amount (mol/h) of the raw material to the reaction tube.
  • F is the supply amount (mol/h) of the raw material per one of the plurality of reaction tubes.
  • F is not particularly limited as long as ⁇ satisfies the formula (1), but from the viewpoint of maintaining the productivity of one or both of (meth)acrolein and (meth)acrylic acid, 1 (mol / h) or more is preferably 2.5 (mol/h) or more, and more preferably 6.5 (mol/h) or more.
  • F is preferably 20 (mol/h) or less, more preferably 15 (mol/h) or less, and 10.5 (mol/h). ) or less.
  • F preferably satisfies the above regulation in 50% or more of the total number of the plurality of reaction tubes, and 80% of the total number of the plurality of reaction tubes. It is more preferable to satisfy the above conditions, and more preferably to satisfy 90% or more of the total number of the plurality of reaction tubes.
  • a in the formula (*) is the inner surface area (m 2 ) of the reaction tube in contact with the first catalyst layer from the raw material inlet side of the reaction tube.
  • A is not particularly limited as long as ⁇ satisfies the formula ( 1 ). 2 ) or more, more preferably 0.09 (m 2 ) or more.
  • A is preferably 0.6 (m 2 ) or less, more preferably 0.4 (m 2 ) or less, and 0.4 (m 2 ) or less. It is more preferably 25 (m 2 ) or less.
  • A is defined above. It is preferable to satisfy 50% or more of the total number of the plurality of reaction tubes, more preferably 80% or more of the total number of the plurality of reaction tubes, and 90% or more of the total number of the plurality of reaction tubes. More preferred.
  • the raw material can be supplied to the reaction tube as a raw material gas containing the raw material.
  • the raw material concentration in the raw material gas is preferably 1 to 20% by volume, more preferably 3 to 10% by volume.
  • the raw material is at least one selected from propylene, isobutylene, tert-butanol, and methyl tert-butyl ether.
  • (meth)acrolein is the raw material in the case of the method for producing (meth)acrylic acid.
  • the raw material gas preferably contains 5 to 15% by volume of oxygen. Air is preferable as the oxygen source from the viewpoint of economy. If necessary, oxygen-enriched gas or the like obtained by adding pure oxygen to air may be used. Further, the raw material gas preferably contains 5 to 50% by volume of water vapor. The raw material gas may be obtained by diluting the raw material, oxygen and water vapor with an inert gas such as nitrogen or carbon dioxide. Further, the raw material gas may contain a small amount of impurities such as lower saturated aldehydes, but the amount is preferably as small as possible.
  • the space velocity of the raw material in the catalyst layer is preferably 200 to 5000 h ⁇ 1 .
  • the reaction pressure is preferably atmospheric pressure to several atmospheres.
  • the temperature of the heat medium flowing outside the reaction tube is preferably 230 to 450.degree.
  • the lower limit of the temperature of the heat medium is more preferably 250°C or higher, and the upper limit is more preferably 400°C or lower.
  • the method of the present embodiment can improve the selectivity of (meth)acrylic acid in the synthesis of (meth)acrolein and/or (meth)acrylic acid.
  • ⁇ and ⁇ are as follows.
  • m1 is the catalyst loading amount (kg) in the first catalyst layer from the raw material inlet side of the reaction tube
  • mj is the catalyst loading amount in the j-th catalyst layer from the raw material inlet side of the reaction tube.
  • (kg) is an integer of 1 or more and i or less
  • F is the supply amount (mol/h) of the raw material to the reaction tube
  • A is the first catalyst layer from the raw material inlet side of the reaction tube.
  • the inner surface area (m 2 ) of the reaction tube with which the layers are in contact, and U is the overall heat transfer coefficient (W/m 2 /K).
  • m1 is the catalyst filling amount (kg) in the first catalyst layer from the raw material inlet side of the reaction tube
  • mk is the catalyst filling amount in the k-th catalyst layer from the raw material inlet side of the reaction tube. is the amount (kg)
  • k is an integer of 1 or more and i or less.
  • composition ratio of catalyst The atomic ratio of each element was obtained by analyzing a component obtained by dissolving the catalyst in ammonia water by ICP (high frequency inductively coupled plasma) emission spectrometry.
  • ICP high frequency inductively coupled plasma
  • the overall heat transfer coefficient U is obtained by supplying an inert gas consisting of 21% by volume of oxygen and 79% by volume of nitrogen to the reaction tube at a temperature 50 ° C. lower than the heat medium flowing outside the reaction tube, and forming the first layer of catalyst. It was calculated from the results of measuring the temperature distribution in minute regions of the layer.
  • ⁇ is the substance amount (mol) of supplied methacrolein
  • ⁇ is the substance amount (mol) of reacted methacrolein
  • ⁇ is the substance amount (mol) of produced methacrylic acid.
  • ⁇ Tmax the temperature difference between the temperature of the portion exhibiting the highest temperature in the catalyst layer and the heat medium flowing outside the reaction tube was used.
  • ⁇ Tmax was measured as follows. The temperature of the catalyst layer was measured by a thermocouple inserted in a protective tube placed in the center of the cross section perpendicular to the longitudinal direction of the reaction tube. The protection tube is isolated from the reaction system, and the position where the temperature is measured can be changed by adjusting the length of the thermocouple to be inserted. The difference between the temperature of the catalyst layer and the temperature of the heat medium measured at this time was defined as ⁇ T, and the ⁇ T distribution was calculated. The maximum ⁇ T in the obtained ⁇ T distribution was defined as ⁇ Tmax.
  • Methacrylic acid was produced by the following oxidation reaction of methacrolein using a shell-and-tube heat exchanger type reactor equipped with a heating medium bath shown in FIG.
  • the reactor has a reaction tube made of SUS304 with an inner diameter of 27.2 mm and a length of 6 m.
  • a catalyst having a composition ratio of P 1.1 Mo 12 V 0.6 Cu 0.1 Fe 0.05 Cs 1.3 excluding oxygen and having a cylindrical shape with a diameter of 6 mm and a height of 5 mm was placed. was used to form two catalyst layers.
  • the first catalyst layer from the raw material inlet side of the reaction tube was filled with a mixture of 1000 g of catalyst and 250 g of alumina spheres with a diameter of 5 mm as a diluent.
  • the second catalyst layer was filled with 2500 g of catalyst.
  • Table 1 shows the length of each catalyst layer and the value of ⁇ .
  • An inert material layer made of alumina spheres with a diameter of 5 mm was formed between the end of the reaction tube on the raw material inlet side and the catalyst layer.
  • a raw material gas composed of 6.0% by volume of methacrolein, 10% by volume of oxygen, 10% by volume of water vapor and 74.0% by volume of nitrogen is supplied.
  • Table 1 shows the methacrolein supply amount F, the overall heat transfer coefficient U, the value of ⁇ , and the methacrolein reaction rate at this time.
  • Table 1 shows the amount F of methacrolein supplied, the overall heat transfer coefficient U, the value of ⁇ , and the methacrolein reaction rate. After that, continuous operation was carried out while maintaining the reaction rate by adjusting the temperature of the heat transfer medium. Moreover, the methacrylic acid selectivity before shutdown was 77%.
  • the temperature change dT1′ (K) in the longitudinal direction of the reaction tube in the minute area is defined as the difference between the temperature of the heat medium flowing outside the reaction tube and the average temperature in the minute area as dT2′ (K), and the reaction rate per volume (mol/m 3 /s), the reaction heat (J/mol), and the volume (m 3 ) of the minute region is M2(W), which is obtained by the formula (***)'.
  • dT1′ [U ⁇ inner surface area (m 2 ) of reaction tube in contact with minute region ⁇ dT2′+sum of M2 for all reactions occurring in reaction tube]/[mass flow rate of source gas (g/s) ⁇ source gas specific heat (J/g/K)] (***)'
  • Example 1 Using the prepared simulation, it was confirmed that the same ⁇ Tmax, methacrolein reaction rate, and methacrylic acid selectivity as in Example 1 were obtained under the same heat medium flow conditions as in Example 1.
  • Table 1 shows the length of the catalyst layer, the filling amount of the catalyst, the value of ⁇ , the value of U and the value of ⁇ in each example and comparative example. Note that the heat medium flow conditions and the raw material gas supply conditions were the same as those in the first embodiment. Table 1 shows ⁇ Tmax, methacrolein conversion and methacrylic acid selectivity obtained by simulation.
  • Example 1 in which the oxidation reaction of methacrolein was performed under the conditions satisfying formula (1), was able to perform continuous operation for 40 days with higher methacrylic acid selectivity than Comparative Example.
  • Examples 2-4 also showed stable ⁇ Tmax and good methacrylic acid selectivity.
  • Comparative Example 1 the calorific value of the catalyst layer increased rapidly, and the operation was stopped after two days, resulting in a low methacrylic acid selectivity.
  • Comparative Examples 2 and 3 had a higher ⁇ Tmax than those of Examples, indicating that the amount of heat generated in the first catalyst layer was large relative to the heat removal capacity of the reactor.
  • (meth)acrolein and (meth)acrylic acid are produced with high selectivity by preventing runaway reaction in the heat exchange reactor and suppressing excessive progress of the reaction and local catalyst deterioration. It is industrially useful because one or both can be produced.

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PCT/JP2022/021177 2021-05-25 2022-05-24 （メタ）アクロレイン及び（メタ）アクリル酸の一方又は両方の製造方法 Ceased WO2022250030A1 (ja)

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CN202280036474.4A CN117396457A (zh) 2021-05-25 2022-05-24 （甲基）丙烯醛和（甲基）丙烯酸中的一者或两者的制造方法
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Citations (4)

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JPH04210937A (ja) * 1990-02-08 1992-08-03 Nippon Shokubai Co Ltd メタクリル酸の製造方法
JP2005170909A (ja) * 2003-12-15 2005-06-30 Mitsubishi Chemicals Corp （メタ）アクリル酸または（メタ）アクロレインの製造方法
JP2010132584A (ja) * 2008-12-03 2010-06-17 Mitsubishi Rayon Co Ltd 多管式熱交換器型反応器を用いた気相酸化反応の運転方法
JP2014019675A (ja) * 2012-07-20 2014-02-03 Nippon Kayaku Co Ltd 不飽和アルデヒドおよび／または不飽和カルボン酸の製造方法

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JPS55113730A (en) * 1979-02-26 1980-09-02 Mitsubishi Petrochem Co Ltd Preparation of acrolein and acrylic acid
JP3943284B2 (ja) * 1999-05-27 2007-07-11 株式会社日本触媒 アクリル酸の製造方法
EP1460053A4 (en) * 2001-12-27 2006-03-22 Mitsubishi Chem Corp VAPOR CATALYST OXIDATION PROCESS AND PROCESS FOR PRODUCING (METH) ACROLEIN OR (METH) ACRYLIC ACID
JP4108521B2 (ja) * 2002-04-09 2008-06-25 三菱化学株式会社 多管式反応器
JP4145607B2 (ja) * 2002-08-23 2008-09-03 三菱化学株式会社 多管式反応器を用いた気相接触酸化方法
MY192057A (en) * 2017-02-17 2022-07-25 Mitsubishi Chem Corp Catalyst for production of methacrylic acid, catalyst precursor for production of methacrylic acid, method for producing said catalyst and catalyst precursor, method for producing methacrylic acid, and method for producing methacrylate ester

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Publication number Priority date Publication date Assignee Title
JPH04210937A (ja) * 1990-02-08 1992-08-03 Nippon Shokubai Co Ltd メタクリル酸の製造方法
JP2005170909A (ja) * 2003-12-15 2005-06-30 Mitsubishi Chemicals Corp （メタ）アクリル酸または（メタ）アクロレインの製造方法
JP2010132584A (ja) * 2008-12-03 2010-06-17 Mitsubishi Rayon Co Ltd 多管式熱交換器型反応器を用いた気相酸化反応の運転方法
JP2014019675A (ja) * 2012-07-20 2014-02-03 Nippon Kayaku Co Ltd 不飽和アルデヒドおよび／または不飽和カルボン酸の製造方法

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