WO2024080203A1 - 不飽和アルデヒドの製造方法および不飽和アルデヒドの製造装置 - Google Patents

不飽和アルデヒドの製造方法および不飽和アルデヒドの製造装置 Download PDF

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WO2024080203A1
WO2024080203A1 PCT/JP2023/036202 JP2023036202W WO2024080203A1 WO 2024080203 A1 WO2024080203 A1 WO 2024080203A1 JP 2023036202 W JP2023036202 W JP 2023036202W WO 2024080203 A1 WO2024080203 A1 WO 2024080203A1
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reaction
catalyst
unsaturated aldehyde
producing
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French (fr)
Japanese (ja)
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成喜 奥村
主 香川
智志 河村
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to JP2024506138A priority Critical patent/JP7551026B2/ja
Priority to EP23877208.1A priority patent/EP4603472A1/en
Priority to CN202380071590.4A priority patent/CN119948003A/zh
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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
    • C07C45/32—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a method and apparatus for producing the corresponding unsaturated aldehyde by gas-phase catalytic oxidation of an alkene with molecular oxygen or a molecular oxygen-containing gas.
  • Patent Document 1 technology relating to the atomic ratios of iron, cobalt, and nickel is described in Patent Document 1.
  • Technology relating to the atomic ratio of iron to cobalt and/or nickel is described in Patent Document 2.
  • Patent Document 3 technology relating to the atomic ratios of nickel to bismuth, nickel to alkali metal components, and bismuth to alkali metal components is described in Patent Document 3.
  • Patent Document 4 an improvement to the compositional ratio of bismuth to molybdenum is described in Patent Document 4.
  • a hot spot generally refers to the maximum temperature inside the catalyst layer, and usually occurs in the catalyst layer on the gas inlet side where the raw material concentration is high, but it can also occur in the highly active catalyst layer located on the gas outlet side due to deactivation of the inlet side catalyst, sudden external disturbance factors, or various fluctuations in conditions.
  • the disturbance factors referred to here refer to, for example, changes in the flow rate of the heat transfer medium supplied to the reaction bath jacket or fluctuations in the flow rate of the raw material gas due to air temperature.
  • Patent Document 5 discloses a technique for lowering the hot spot temperature by using a catalyst whose activity is adjusted by changing the loading amount and by using a catalyst whose activity is adjusted by changing the calcination temperature of the catalyst.
  • Patent Document 6 discloses a technique for using a catalyst whose activity is adjusted by changing the ratio of the apparent densities of the catalyst.
  • Patent Document 7 discloses a technique for using a catalyst whose activity is adjusted by changing the content of inactive components in the catalyst molded body, as well as changing the volume occupied by the catalyst molded body, the type and/or amount of alkali metal, and the calcination temperature of the catalyst.
  • Patent Document 8 discloses a technique for providing reaction zones whose volume occupied by the catalyst molded body is changed, and mixing an inactive substance in at least one of the reaction zones.
  • Patent Document 9 discloses a technique for using a catalyst whose activity is adjusted by changing the calcination temperature of the catalyst.
  • Patent Document 10 discloses a technique for using a catalyst whose activity is adjusted by changing the volume occupied by the catalyst, the calcination temperature, and/or the type and amount of alkali metal.
  • reaction tubes where the catalyst deterioration is concentrated at the raw gas inlet, reaction tubes where the catalyst deterioration is gradual throughout, and even more surprisingly, reaction tubes where the catalyst at the raw gas outlet is more deteriorated than the catalyst at the inlet.
  • the hot spot temperature of the catalyst layer on the raw gas outlet side may have been abnormally high, which may cause a runaway reaction in some cases. This is thought to be due to the above-mentioned variations in reaction tube diameter in industrial plants, variations in heat removal capacity due to the reactor structure, horizontal and vertical heat transfer medium temperature distribution, and gas flow rate distribution for each reaction tube, which cause differences in the conversion rate of the raw hydrocarbon and the shape of the temperature distribution.
  • Previous manufacturing techniques used a multi-layer packing method in which a low activity catalyst was used on the gas inlet side of the reaction tube and a high activity catalyst was used on the gas outlet side of the reaction tube, with the packing length of the catalyst layer near the gas outlet side being longer than that on the gas inlet side.
  • a high PTf means that the amount of heat generated at the outlet side of the reactor is large, so that the gas temperature at the outlet of the reactor is high, which may result in a decrease in acrolein yield due to the occurrence of a cool flame reaction of acrolein, and may also cause deposition of carbonaceous deposits (coking or fouling) at the outlet side of the reaction tube due to the autoxidation reaction of acrolein, and thus blockage of the inside of the reaction tube.
  • ⁇ PTf/ ⁇ BT becomes high in the method of producing acrolein from propylene is described below.
  • the reactor and process are designed so that the successive oxidation does not occur, since acrylic acid, which is a successive oxidation product, is regarded as a by-product.
  • the amount of inert material packed at the inlet of the raw material gas is reduced
  • the oxygen/propylene ratio at the inlet of the catalyst layer is set low in order to suppress the decrease in the acrolein yield due to the successive oxidation reaction
  • the outlet pressure is set high in order to compensate for the decrease in the activity of the entire catalyst due to the above.
  • PTf is likely to be the highest in all the catalyst layers packed in multiple layers, and PTf is likely to change sharply with respect to BT.
  • the specific calculation method of ⁇ PTf/ ⁇ BT is as follows. That is, when all the measurement points of the most outlet side peak temperature (PTf) and BT at three or more points actually measured within the ranges of A1 and A2 described later are plotted as a scatter diagram, the slope of the approximate straight line by the least squares method, which has an intercept at the most outlet side peak temperature, which is the vertical axis, and is assumed to be a linear function with respect to BT, is defined as ⁇ PTf/ ⁇ BT.
  • the slope of the straight line passing through the two points is defined as ⁇ PTf/ ⁇ BT.
  • the measurement points are set so that the difference (BT2-BT1) between the reaction bath temperature BT1 at the measurement point with the lowest reaction bath temperature (BT) and the reaction bath temperature BT2 at the measurement point with the highest reaction bath temperature is 30% or more of A2-A1.
  • the inventors have thoroughly investigated the current situation and problems described above, and have found that high-yield, stable plant operation is possible by packing the catalyst so as to widen the reaction bath temperature range (hereinafter referred to as the operation window) in which the acrolein yield is stable. Furthermore, they have found that by packing the catalyst so as to create a certain relationship between the sum of the spot heat temperatures of the catalyst layer closest to the outlet and the sum of the spot heat temperatures of all catalyst layers, PTf can change gradually with respect to BT ( ⁇ PTf/ ⁇ BT can be reduced), and the yield of unsaturated aldehydes can be increased, enabling higher-yield, stable plant operation.
  • the present invention can be applied not only to the reaction from propylene to acrolein, but also to the reaction from tert-butyl alcohol and/or isobutylene to methacrolein, for example.
  • the present invention relates to the following 1) to 11).
  • a process for producing a corresponding unsaturated aldehyde by partially oxidizing an alkene using a fixed-bed multitubular reactor comprising the steps of:
  • the fixed-bed multi-tubular reactor comprises a plurality of reaction tubes and a reaction bath for adjusting a temperature of the plurality of reaction tubes,
  • the reaction tube is provided with two or more catalyst layers in a gas flow direction,
  • a method for producing an unsaturated aldehyde, in which the reaction bath temperature at which the yield of the unsaturated aldehyde is maximized is A (°C)
  • the reaction bath temperatures at which the yield is 1.0 percentage points lower than the maximized value are A1 (°C) and A2 (°C), respectively, and the following formulas (1) and (2) are satisfied.
  • A1 ⁇ A ⁇ A2 (1) (A2-A1) ⁇ 10 (2) 2) The method for producing an unsaturated aldehyde according to the above 1), wherein the following formula (3) is satisfied for Sf and St when the unsaturated aldehyde is produced at the reaction bath temperature A (°C). (Sf/St) ⁇ 100 ⁇ 42.0 (3)
  • Sf and St are determined by the following steps (a) to (c).
  • thermocouples are arranged at equal intervals throughout the gas flow direction of the two or more catalyst layers provided in the reaction tube, and spot temperatures T1 j (°C) (j is 1 to p) at p measurement points in the reaction tube when an unsaturated aldehyde is produced at a reaction bath temperature A (°C) are obtained using the thermocouples.
  • a spot heating temperature T2j is calculated, which is the spot temperature T1j (°C) minus the reaction bath temperature A (°C), i.e., ( T1j -A). However, if T1j - A is a negative value, the spot heating temperature T2j of the measurement point is set to 0.
  • the sum of the spot heat generation temperatures T2j at all the measurement points in the reaction tube is defined as St.
  • the sum of the spot heat generation temperatures T2k (k is 1 to q, q is the number of measurement points provided in the catalyst layer closest to the outlet, q ⁇ p) at the measurement points provided in the catalyst layer closest to the outlet is defined as Sf.
  • the reaction tube is provided with three catalyst layers in a gas flow direction, 7) The method for producing an unsaturated aldehyde according to any one of 1) to 7) above, wherein a ratio of a sum of the packing lengths of the first and second layers counted from an inlet side of the reaction tube to a packing length of the third layer ((packing length of the first layer + packing length of the second layer) / packing length of the third layer) is 1.5 or more and 3.5 or less.
  • Catalytic reaction rate k -Ln(1-x/100) (II)
  • x is the feed gas conversion rate (%) when the catalyst is packed in a differential reactor and the partial oxidation reaction of the alkene is carried out at a reaction bath temperature of 360°C.
  • An apparatus for producing an unsaturated aldehyde comprising:
  • the present invention includes a fixed-bed multi-tubular reactor having a plurality of reaction tubes and a reaction bath for adjusting the temperature of the plurality of reaction tubes,
  • the reaction tube is provided with two or more catalyst layers in a gas flow direction,
  • An apparatus for producing an unsaturated aldehyde in which the reaction bath temperature at which the yield of the unsaturated aldehyde is maximized is A (°C), and the reaction bath temperatures at which the yield is 1.0 percentage points lower than the maximized value are A1 (°C) and A2 (°C), respectively, such that the following equations (1) and (2) are satisfied.
  • a process for producing a corresponding unsaturated aldehyde by partially oxidizing an alkene using a fixed-bed multitubular reactor comprising the steps of:
  • the fixed-bed multi-tubular reactor comprises a plurality of reaction tubes and a reaction bath for adjusting a temperature of the plurality of reaction tubes,
  • the reaction tube is provided with two or more catalyst layers in a gas flow direction,
  • thermocouples are arranged at equal intervals throughout the gas flow direction of the two or more catalyst layers provided in the reaction tube, and spot temperatures T1 j (°C) (j is 1 to p) at p measurement points in the reaction tube when an unsaturated aldehyde is produced at a reaction bath temperature A (°C) are obtained using the thermocouples.
  • a spot heating temperature T2j is calculated, which is the spot temperature T1j (°C) minus the reaction bath temperature A (°C), i.e., ( T1j -A). However, if T1j - A is a negative value, the spot heating temperature T2j of the measurement point is set to 0.
  • St The sum of the spot heat generation temperatures T2j at all the measurement points in the reaction tube is defined as St.
  • the present invention when producing the corresponding unsaturated aldehyde using an alkene or an alcohol that can produce alkenes through an intramolecular dehydration reaction as a raw material, it is possible to safely and stably maintain a high yield over a long period of time even in an industrial plant.
  • FIG. 1 is a schematic diagram showing an example of an apparatus for producing an unsaturated aldehyde.
  • FIG. 1 is a schematic diagram showing an unsaturated aldehyde manufacturing apparatus 1.
  • the manufacturing apparatus 1 includes a fixed-bed multitubular reactor equipped with a plurality of reaction tubes 20 and a reaction bath 30. Catalyst layers 21, 22, and 23 are provided inside the reaction tubes 20, and different catalysts are disposed in each catalyst layer. The temperature of the reaction tubes 20 can be adjusted by the reaction bath 30.
  • a raw material gas for reaction containing, for example, an alkene is introduced from the top of the manufacturing apparatus 1, and the raw material gas is passed through the reaction tubes 20 to cause a reaction, thereby obtaining a reaction product containing an unsaturated aldehyde.
  • the present invention relates to a method and an apparatus for producing an unsaturated aldehyde, and in essence, to a method for packing a catalyst layer. That is, assuming that the reaction bath temperature at which the yield of the unsaturated aldehyde is maximized is A (°C), and reaction bath temperatures at which the yield is 1.0% points lower than the maximum value are A1 (°C) and A2 (°C), the catalyst is packed so that the above formulas (1) and (2) hold.
  • the yield here means the molar yield.
  • A, A1, and A2 are defined as follows: A: reaction bath temperature A1 at which the yield of unsaturated aldehyde is at its highest, A2: reaction bath temperature at which the yield of unsaturated aldehyde is 1.0% points lower than the yield of unsaturated aldehyde at reaction bath temperature A.
  • A is higher than A1, A2 is higher than A, and (A2-A1) is 10°C or higher.
  • (A2-A1) is more preferably 10°C or higher and 30°C or lower, even more preferably 10°C or higher and 25°C or lower, and most preferably 10°C or higher and 20°C or lower.
  • (A2-A1) is the reaction bath temperature range (operation window) in which the acrolein yield is stable, and the larger (A2-A1) is, the higher the yield of unsaturated aldehyde can be obtained in a wider reaction bath temperature range, which is desirable.
  • the maximum yield (yield at reaction bath temperature A) is, for example, 50% or higher, preferably 70% or higher. It is not necessary to calculate A1 and A2 from the relationship between the actually measured acrolein yield and BT, but they may be calculated from the interpolation or extrapolation of a series of data obtained by measuring the acrolein yield with different BTs.
  • the reason why the acrolein yield decreases at a reaction bath temperature lower than A (°C) is due to a decrease in the reaction rate of the raw material propylene, and the reason why the acrolein yield decreases at a reaction bath temperature higher than A (°C) is due to the generation of carbon dioxide, acrylic acid, etc., which are typified by the successive oxidation reaction of acrolein.
  • the catalyst of the present invention is used in the first stage of a two-stage oxidation reaction (propylene ⁇ acrolein ⁇ acrylic acid), and in that case, the total amount of acrolein and acrylic acid is important, so that the yield of acrylic acid does not decrease rapidly even if the reaction bath temperature becomes high.
  • the reaction bath temperature range in which the yield is stable tends to be relatively wide.
  • the operation window tends to be relatively narrow, making it difficult to control appropriately, and it can be said that the control method was not known even to those skilled in the art as described above.
  • thermal stress of the catalyst can be prevented and the catalyst life can be extended.
  • a slight change in reaction bath temperature or a difference in reaction bath temperature between multiple reaction tubes causes a sharp change in the hot spot on the most active outlet catalyst, thereby preventing thermal runaway and the associated damage and explosion of the reaction tube.
  • the gas temperature at the reactor outlet is high due to the large amount of heat generated at the outlet side of the reactor, which causes a cool flame reaction of acrolein, and the deposition of carbonaceous deposits (coking or fouling) at the outlet side of the reaction tube due to the autoxidation reaction of acrolein, as well as the resulting blockage and catalyst deterioration in the reaction tube, can be suppressed.
  • thermocouples are arranged at equal intervals throughout the gas flow direction of two or more catalyst layers provided in a reaction tube, and spot temperatures T1 i (°C) (i is 1 to p) at p measurement points in the reaction tube when an unsaturated aldehyde is produced at a reaction bath temperature A (°C) are obtained using the thermocouples.
  • Sf means the sum of the heat values of the most outlet catalyst layer
  • St means the sum of the heat values of all catalyst layers, according to Fourier's law of heat conduction. That is, when Sf and St satisfy the relationship of formula (3), it means that the heat value in the most outlet catalyst layer is 42.0% or less of the heat value in all catalyst layers, and the raw material gas is certainly reacting before reaching the highly active most outlet catalyst layer. It is known to those skilled in the art that the reaction rate of alkenes to unsaturated aldehydes by partial oxidation is first order with respect to the partial pressure of the alkene.
  • reaction rate and reactivity decrease toward the lower layer of the reactor, so when multi-layer packing is adopted in this reaction, it is common to select a highly active catalyst at the most outlet side.
  • reaction rate taking into account the effect of catalyst shape and dilution rate by inert carrier decrease toward the lower layer of the reactor, so when multi-layer packing is adopted in this reaction, it is common to select a highly active catalyst at the most outlet side.
  • the lower limit is, in order of preference, 1, 5, 7, 9, 11, 12, 13, 14, 15, 16, 17, and 18, and the upper limit is, in order of preference, 40, 37, 35, 33, 31, 30, 29, and 28.
  • Sf/St ⁇ 100 is preferably 1 or more and 40 or less, more preferably 5 or more and 40 or less, more preferably 7 or more and 40 or less, more preferably 11 or more and 40 or less, more preferably 12 or more and 37 or less, more preferably 13 or more and 35 or less, more preferably 14 or more and 33 or less, more preferably 15 or more and 31 or less, more preferably 16 or more and 30 or less, more preferably 17 or more and 29 or less, and most preferably 18 or more and 28 or less.
  • thermocouples are inserted into the reaction tube at a predetermined interval in the depth direction so that temperature information of the catalyst layer filled with a catalyst and/or the inert layer filled with an inert carrier can be obtained.
  • the method of inserting the thermocouples is not limited as long as it is a method known to those skilled in the art, and examples thereof include the following.
  • the direction in which the thermocouple is inserted is the depth direction of the reaction tube and/or a direction perpendicular to the depth direction of the reaction tube
  • the method of inserting the thermocouple is a method of directly inserting the thermocouple parallel to the reaction tube and/or a method of inserting a case (thermowell) into which the thermocouple is inserted and inserting the thermocouple inside it (i.e., the reaction tube has a double tube structure)
  • the method of moving the thermocouple over time is a fixed type that does not move at all and/or a type that moves to an arbitrary position in the reaction tube over time.
  • the reaction tubes into which the thermocouples are inserted are not all of the reaction tubes in the reactor, but only some of them.
  • reaction tubes Of the several thousand to tens of thousands of reaction tubes, usually 5 to 100, preferably 6 to 50, more preferably 7 to 40, and particularly preferably 8 to 16 reaction tubes are selected.
  • reaction tubes into which thermocouples are inserted may be selected only from some of the sections, or may be selected as evenly as possible from all the sections.
  • at least one reaction tube is selected from 40% or more of all the sections, more preferably from 60% or more of the sections, and even more preferably from 75% or more of the sections.
  • the reaction tube into which the thermocouples are inserted is also simply referred to as a reaction tube.
  • the position of the thermocouples in the depth direction is not particularly limited, but a method of arranging the thermocouples at equal intervals or a method of changing the interval of the thermocouples as necessary can be adopted. When arranging the thermocouples at equal intervals, it is preferable to obtain temperature measurement data at intervals of 10 cm or less in order to accurately obtain Sf and St.
  • thermocouples When changing the interval of the thermocouples, particularly in an exothermic reaction such as the reaction of the present invention, since the temperature distribution in the catalyst packed bed on the gas inlet side shows a steep rise in the depth direction, it is preferable to arrange the thermocouples so that the interval between the thermocouple positions is narrow, and conversely, the interval between the thermocouple positions is wide in the catalyst packed bed on the gas outlet side.
  • the measurement positions in each reaction tube rather than measuring temperature information at the same depth position for all of the selected multiple reaction tubes, it is preferable to arrange the measurement positions in each reaction tube at different depths, since this makes it easier to grasp the temperature distribution of the entire reactor.
  • the catalyst used in the present invention is preferably a catalyst having a composition represented by the following formula (I). Mo a Bi b Ni c Co d Fe e X f Y g Z h O i (I)
  • Mo, Bi, Ni, Co and Fe represent molybdenum, bismuth, nickel, cobalt and iron, respectively;
  • X represents at least one element selected from tungsten, antimony, tin, zinc, chromium, manganese, magnesium, silicon, aluminum, cerium and titanium;
  • Y represents at least one element selected from sodium, potassium, cesium, rubidium and thallium;
  • Z represents an element belonging to Groups 1 to 16 of the periodic table; and means at least one element selected from elements other than Co, Fe, X, Y, and O, and a, b, c, d, e, f, g, h, and i represent the numbers of atoms of molybdenum, bismuth, nickel,
  • the preferred ranges of b to h are as follows:
  • the lower limit of b is, in order of preference, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, and 0.70
  • the upper limit is, in order of preference, 6.0, 5.0, 4.0, 3.0, 2.0, 1.8, 1.5, 1.2, and 1.0.
  • b is preferably 0.10 or more and 6.0 or less, more preferably 0.10 or more and 5.0 or less, more preferably 0.10 or more and 4.0 or less, more preferably 0.20 or more and 3.0 or less, more preferably 0.30 or more and 2.0 or less, more preferably 0.40 or more and 1.8 or less, more preferably 0.50 or more and 1.5 or less, more preferably 0.60 or more and 1.2 or less, and most preferably 0.70 or more and 1.0 or less.
  • the lower limit of c is, in order of preference, 0.20, 0.50, 0.80, 1.0, 1.5, 1.8, 2.0, 2.5, and 2.8, and the upper limit is, in order of preference, 8.0, 7.0, 6.0, 5.0, 4.0, 3.5, and 3.3.
  • c is preferably 0.20 or more and 8.0 or less, more preferably 0.50 or more and 8.0 or less, more preferably 0.80 or more and 8.0 or less, more preferably 1.0 or more and 7.0 or less, more preferably 1.5 or more and 6.0 or less, more preferably 1.8 or more and 5.0 or less, more preferably 2.0 or more and 4.0 or less, more preferably 2.5 or more and 3.5 or less, and most preferably 2.8 or more and 3.3 or less.
  • the lower limit of d is, in order of preference, 1.0, 2.0, 3.0, 4.0, and 5.0
  • the upper limit is, in order of preference, 9.5, 9.0, 8.5, 8.0, 7.5, 7.0, 6.5, and 6.3.
  • d is preferably 1.0 to 9.5, more preferably 1.0 to 9.0, more preferably 1.0 to 8.5, more preferably 1.0 to 8.0, more preferably 2.0 to 7.5, more preferably 3.0 to 7.0, more preferably 4.0 to 6.3, and most preferably 5.0 to 6.3.
  • the lower limit of c+d is, in order of preference, 0.0, 2.0, 4.0, 6.0, 8.0, and 8.3, and the upper limit is, in order of preference, 20.0, 15.0, 12.5, 11.0, 10.0, and 9.0.
  • c+d is preferably 0.0 or more and 20.0 or less, more preferably 2.0 or more and 15.0 or less, more preferably 4.0 or more and 12.5 or less, more preferably 6.0 or more and 11.0 or less, more preferably 8.0 or more and 10.0 or less, and most preferably 8.3 or more and 9.0 or less.
  • the lower limit of e is, in order of preference, 0.10, 0.20, 0.50, 0.80, 1.0, 1.5, and 1.6
  • the upper limit is, in order of preference, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, and 1.9.
  • e is preferably 0.10 or more and 4.5 or less, more preferably 0.20 or more and 4.0 or less, more preferably 0.50 or more and 3.5 or less, more preferably 0.80 or more and 3.0 or less, more preferably 1.0 or more and 2.5 or less, more preferably 1.5 or more and 2.0 or less, and most preferably 1.6 or more and 1.9 or less.
  • the upper limit of f is preferably 1.8, 1.5, 1.0, 0.80, and 0.50, and the lower limit is preferably 0.
  • f is preferably 0 or more and 1.8 or less, more preferably 0 or more and 1.5 or less, more preferably 0 or more and 1.0 or less, more preferably 0 or more and 0.80 or less, more preferably 0 or more and 0.50 or less, and most preferably 0.
  • the lower limit of g is, in order of preference, 0.010, 0.020, 0.030, 0.040, 0.050, and 0.060, and the upper limit is, in order of preference, 2.0, 1.0, 0.50, 0.40, 0.30, 0.20, 0.15, and 0.090.
  • g is preferably 0.010 or more and 2.0 or less, more preferably 0.010 or more and 1.0 or less, more preferably 0.010 or more and 0.50 or less, more preferably 0.020 or more and 0.40 or less, more preferably 0.030 or more and 0.30 or less, more preferably 0.040 or more and 0.20 or less, more preferably 0.050 or more and 0.15 or less, and most preferably 0.060 or more and 0.090 or less.
  • the upper limit of h is, in order of preference, 4.0, 3.0, 2.0, 1.8, 1.5, 1.0, 0.80, and 0.50, and the lower limit is preferably 0.
  • h is more preferably 0 or more and 4.0 or less, more preferably 0 or more and 3.0 or less, more preferably 0 or more and 2.0 or less, more preferably 0 or more and 1.8 or less, more preferably 0 or more and 1.5 or less, more preferably 0 or more and 1.0 or less, more preferably 0 or more and 0.80 or less, more preferably 0 or more and 0.50 or less, and most preferably 0.
  • X is preferably tungsten, antimony, zinc, magnesium or cerium, and particularly preferably antimony or zinc.
  • Y is preferably sodium, potassium or cesium, more preferably potassium or cesium.
  • Z in the formula (1) is preferably vanadium, copper, niobium, zirconium, calcium, beryllium, strontium, barium, lead or phosphorus.
  • the catalytically active component of the catalyst contained in the first layer preferably has a composition represented by the following formula (I-1).
  • the catalyst layer closest to the inlet side of the reaction raw material gas preferably has a composition represented by the following formula (I-1).
  • the catalyst layer closest to the outlet side preferably contains a catalyst having a composition represented by formula (I-1).
  • Mo, Bi, Ni, Co, Fe, Cs, and O represent molybdenum, bismuth, nickel, cobalt, iron, cesium, and oxygen, respectively;
  • X represents at least one element selected from tungsten, antimony, tin, zinc, chromium, manganese, magnesium, silicon, aluminum, cerium, and titanium;
  • Z represents an element belonging to Groups 1 to 16 of the periodic table and is selected from elements other than Mo, Bi, Ni, Co, Fe, Cs, O, and X.
  • preferred b1 to f1, h1, and X and Z are the same as b to f, h, and X and Z in formula (I), including preferred embodiments thereof.
  • the lower limit is, in order of preference, 0.0010, 0.0050, 0.010, 0.015, 0.020, and 0.030
  • the upper limit is, in order of preference, 2.0, 1.0, 0.50, 0.40, 0.30, 0.20, 0.15, 0.090, and 0.060.
  • g1 is preferably 0.0010 or more and 2.0 or less, more preferably 0.0010 or more and 1.0 or less, more preferably 0.0010 or more and 0.50 or less, more preferably 0.0010 or more and 0.40 or less, more preferably 0.0050 or more and 0.30 or less, more preferably 0.010 or more and 0.20 or less, more preferably 0.015 or more and 0.15 or less, more preferably 0.020 or more and 0.090 or less, and most preferably 0.030 or more and 0.060 or less.
  • the catalytically active component of the catalyst contained in the catalyst layer closest to the outlet preferably has a composition represented by the following formula (I-2).
  • the catalytically active component contained in the third catalyst layer has a composition represented by formula (I-2)
  • the catalytically active component contained in the catalyst layer closest to the outlet has a composition represented by formula (I-2).
  • Mo, Bi, Ni, Co, Fe, K and O represent molybdenum, bismuth, nickel, cobalt, iron, potassium and oxygen, respectively;
  • X represents at least one element selected from tungsten, antimony, tin, zinc, chromium, manganese, magnesium, silicon, aluminum, cerium and titanium;
  • Z represents at least one element belonging to Groups 1 to 16 of the periodic table and selected from elements other than Mo, Bi, Ni, Co, Fe, K, O and X.
  • preferred b2 to f2, h2, X, and Z are the same as b to f, h, X, and Z in formula (I), including preferred embodiments thereof.
  • the lower limit is, in order of preference, 0.0010, 0.0050, 0.010, 0.015, 0.020, and 0.030
  • the upper limit is, in order of preference, 2.0, 1.0, 0.50, 0.40, 0.30, 0.20, 0.15, and 0.10.
  • g2 is preferably 0.0010 or more and 2.0 or less, more preferably 0.0010 or more and 1.0 or less, more preferably 0.0010 or more and 0.50 or less, more preferably 0.0050 or more and 0.40 or less, more preferably 0.010 or more and 0.30 or less, more preferably 0.015 or more and 0.20 or less, more preferably 0.020 or more and 0.15 or less, and most preferably 0.030 or more and 0.10 or less.
  • [Filling method] As a method for adjusting the relationship between A, A1, and A2 and a method for adjusting the relationship between St and Sf, various methods can be considered, such as (1) a method for controlling the relative activity of each catalyst layer, (2) a method for controlling the particle size of each catalyst layer, (3) a method for providing an inactive material layer on the outlet side of the reaction tube, and (4) a method for setting the gas temperature at the inlet side of the catalyst layer of the reaction tube high, and these methods can be used alone or in combination.
  • (1) In the method of controlling the relative activity of each catalyst layer the catalyst is loaded into a differential reactor, and the raw material gas conversion rate x obtained at a specific BT is calculated from an integral reaction rate equation.
  • the reaction rate k of this reaction is calculated from the following equation (II).
  • k -Ln (1 - x / 100) (II)
  • k is the reaction rate of this reaction (unitless)
  • Ln is the natural logarithm
  • x is the propylene conversion rate (unit: %).
  • the reaction rate of each catalyst layer is calculated under the same conditions using this method, and then the actual reaction rate ak of each catalyst layer in the plant is calculated using the following formula (III).
  • the dilution ratio is synonymous with the dilution ratio by an inert substance described later
  • the packed length is the length of the packed catalyst layer, expressed in units of cm. It is preferable to use an actual measured value as the packed length, rather than a designed value. In a plant, since there are often multiple reaction tubes, an average value obtained from the measurement results of some of them can also be used.
  • the catalyst can be packed in order from the top of the reaction tube to the bottom, and the space length above each layer can be measured using a tape measure or the like to calculate the packed length.
  • akt/akn is calculated by the following formula (IV).
  • the preferred numerical ranges of akt/akn are, in order of preference, 1.41, 1.42, 1.43, 1.44, and 1.45 in lower limit and 10.00, 7.50, 5.00, 4.00, 3.00, 2.75, 2.65, 2.55, and 2.50 in upper limit.
  • akt/akn is preferably 1.41 or more and 10.00 or less, more preferably 1.41 or more and 7.50 or less, more preferably 1.41 or more and 5.00 or less, more preferably 1.41 or more and 4.00 or less, more preferably 1.41 or more and 3.00 or less, more preferably 1.42 or more and 2.75 or less, more preferably 1.42 or more and 2.65 or less, more preferably 1.42 or more and 2.55 or less, and most preferably 1.45 or more and 2.50 or less.
  • akt/akn (sum of actual reaction rates ak of all catalyst layers) ⁇ (actual reaction rate ak of the catalyst layer closest to the outlet of the reaction tube) (IV)
  • the above-mentioned raw material gas conversion rate x is calculated by the following method.
  • GHSV propylene hourly space velocity
  • the particle size of the catalyst layer closest to the outlet of the reaction tube may be different from the particle size of the catalyst layers of the other catalyst layers, and may be larger or smaller.
  • the operation window can be adjusted to be wide.
  • the particle size of each catalyst layer when the pressure in the reaction tube is high, and/or the reaction bath temperature is low, and/or the inner diameter of the reaction tube is large, and/or the inlet propylene concentration is low, it is preferable to increase the particle size of each catalyst layer, and particularly, it is preferable to increase the particle size of the catalyst layer on the inlet side of the reaction tube.
  • the particle diameter ratio particle diameter of the catalyst in the catalyst layer closest to the outlet of the reaction tube divided by the particle diameter of the catalyst in the other catalyst layers
  • the lower limit is 0.50, 0.60, 0.70, 0.80, 0.90, and 1.00
  • the upper limit is 1.50, 1.40, 1.30, 1.20, and 1.10, in that order.
  • the particle diameter ratio is preferably 0.50 or more and 1.50 or less, more preferably 0.60 or more and 1.50 or less, more preferably 0.70 or more and 1.40 or less, more preferably 0.80 or more and 1.30 or less, more preferably 0.90 or more and 1.20 or less, and most preferably 1.00 or more and 1.10 or less.
  • the weighted average of the catalyst particle diameters weighted by the packing length of each catalyst layer other than the catalyst layer closest to the outlet is defined as the "particle diameter of the catalyst in the other catalyst layers".
  • the pressure on the inlet side of the reaction tube increases by providing the inert material layer closer to the outlet side than the catalyst layer, and the reaction can proceed steadily on the inlet side of the reaction tube.
  • the length of the inert material packed on the outlet side varies depending on the raw material load and the diameter of the reaction tube, but is, for example, 5 cm or more, preferably 10 cm or more, more preferably 20 cm or more, and most preferably 30 cm or more.
  • the length of the inert material packed on the outlet side may be, for example, 50 cm or less.
  • the catalyst is easily activated at the inlet side of the reaction tube by increasing the inlet gas temperature, and the reaction can proceed steadily.
  • the inlet gas temperature is preferably 150° C. or higher, 200° C. or higher, 250° C. or higher, 270° C. or higher, 290° C. or higher, 300° C. or higher, 310° C. or higher, 320° C. or higher, 330° C. or higher, or 340° C. or higher.
  • the inlet gas temperature may be, for example, 360° C. or lower.
  • the method (1) for adjusting the packing length of the catalyst layer will be described in detail with the packing length of the catalyst layer being defined as follows.
  • Ln the packing length of the nth layer counted from the gas inlet side of the reaction tube when n layers of catalyst layers are provided in the gas flow direction of the reaction tube
  • L the total packing length from the 1st layer to the n-1th layer counted from the gas inlet side of the reaction tube.
  • a preferred packing method is when L/Ln is 1.5 or more and 3.5 or less. It is more preferable that the catalyst layer has the above-mentioned catalyst composition.
  • L/Ln More preferable upper limits of this L/Ln are 3.4, 3.3, 3.2, and 3.1, and particularly preferably 3.0. Also, preferable lower limits are 1.6, 1.7, 1.8, and 1.9, and particularly preferably 2.0. Therefore, L/Ln is preferably 1.6 or more and 3.4 or less, more preferably 1.7 or more and 3.3 or less, more preferably 1.8 or more and 3.2 or less, more preferably 1.9 or more and 3.1 or less, and most preferably 2.0 or more and 3.0 or less.
  • the number n of divided catalyst layers is preferably 2 to 5 layers, more preferably 2 to 4 layers, particularly preferably 2 to 3 layers, and most preferably 3 layers.
  • the shape of the catalyst contained in the catalyst layer used in the present invention is not particularly limited, and it can be spherical, cylindrical, ring-shaped, powdery, etc., but spherical is particularly preferred.
  • both the catalyst in the upper layer and the catalyst in the lower layer may be diluted with an inert substance, but it is more preferable not to dilute either the upper or lower layer.
  • the preferred range of the dilution ratio with the inert substance is described below.
  • the dilution ratio here is a numerical value indicating the mass ratio of the catalyst in the catalyst layer composed of the catalyst and the inert substance.
  • a catalyst layer diluted by 80% by mass means that the catalyst is 80% by mass and the inert substance is 20% by mass.
  • the dilution ratio is calculated based on the mass of the catalyst including the inert carrier.
  • n 2 or 3 as an example, but the present invention is not limited to this.
  • the middle layer is a catalyst containing a catalytically active component having a composition represented by formula (I-1) and the dilution ratio is 100 mass %
  • the upper layer is a catalyst obtained by diluting the same catalyst as the middle layer with an inert substance and the dilution ratio is 60 mass % or more and less than 100 mass %
  • the lower layer is a catalyst containing a catalytically active component having a composition represented by formula (I-2) and the dilution ratio is 100 mass %.
  • the inert substance includes known substances such as silica, alumina, titania, zirconia, niobia, silica alumina, silicon carbide, carbides, and mixtures thereof. Among these, silica, alumina, or mixtures thereof are preferred, silica and alumina are particularly preferred, and a mixture of silica and alumina is most preferred.
  • the shape of the inactive substance is not particularly limited, but is preferably spherical.
  • the average particle size of the inactive substance is preferably 3 mm to 10 mm, more preferably 3.5 mm to 9 mm, and particularly preferably 4 mm to 8 mm.
  • the catalyst used in the present invention can be produced, for example, by the following steps a) to e). ⁇ Step a) Preparation>
  • the starting materials of each element constituting the catalytic active component are not particularly limited.
  • molybdenum component raw material molybdenum oxide such as molybdenum trioxide, molybdic acid, molybdic acid or its salt such as ammonium molybdate, heteropolyacid containing molybdenum such as phosphomolybdic acid and silicomolybdic acid or its salt can be used. It is preferable to use ammonium molybdate, which can provide a high-performance catalyst.
  • ammonium molybdate compounds such as ammonium dimolybdate, ammonium tetramolybdate, and ammonium heptamolybdate, and among them, it is most preferable to use ammonium heptamolybdate.
  • Bismuth salts such as bismuth nitrate, bismuth subcarbonate, bismuth sulfate, and bismuth acetate, bismuth trioxide, and metallic bismuth can be used as the bismuth component raw material.
  • Bismuth nitrate is preferable, and when used, a high-performance catalyst can be obtained.
  • raw materials for iron, cobalt, nickel, and other elements oxides or nitrates, carbonates, organic acid salts, hydroxides, etc. that can be converted to oxides by ignition, or mixtures thereof can be used.
  • the iron component raw material and the cobalt component raw material and/or nickel component raw material are dissolved and mixed in water at a desired ratio under conditions of 10 to 80°C, mixed with a separately prepared molybdenum component raw material and Z component raw material aqueous solution or slurry under conditions of 20 to 90°C, heated and stirred for about 1 hour under conditions of 20 to 90°C, and then an aqueous solution in which the bismuth component raw material is dissolved and, if necessary, an X component raw material and a Y component raw material are added to obtain an aqueous solution or slurry containing the catalyst components.
  • the aqueous solution or slurry obtained in this manner is collectively referred to as the prepared liquid (A).
  • the prepared liquid (A) does not necessarily need to contain all of the catalytically active component elements, and some of the elements or some of the amounts may be added in a subsequent step. Furthermore, when preparing the prepared liquid (A), if the amount of water in which each component raw material is dissolved, or if an acid such as sulfuric acid, nitric acid, hydrochloric acid, tartaric acid, or acetic acid is added for dissolution, is not suitable for preparation, for example, in the range of 5% to 99% by mass, the acid concentration in the aqueous solution sufficient to dissolve the raw materials, the prepared liquid (A) may take the form of a clay-like lump. In this case, an excellent catalyst cannot be obtained.
  • the prepared liquid (A) is preferably in the form of an aqueous solution or a slurry, as this produces an excellent catalyst.
  • the preparation liquid (A) obtained above is dried to obtain a dry powder.
  • the drying method is not particularly limited as long as it can completely dry the preparation liquid (A), and examples thereof include drum drying, freeze drying, spray drying, and evaporation to dryness.
  • spray drying is particularly preferred, which can dry the slurry into powder or granules in a short time.
  • the drying temperature of the spray drying varies depending on the concentration of the slurry, the liquid sending speed, etc., but is generally 70 to 150°C at the outlet of the dryer. It is also preferable to dry the mixture so that the average particle size of the dry powder obtained at this time is 10 to 700 ⁇ m. In this way, a dry powder (B) is obtained.
  • Step c) Pre-firing>
  • the resulting dry powder (B) is calcined under air flow at 200°C to 600°C, preferably 300°C to 600°C, which tends to improve the moldability, mechanical strength, and catalytic performance of the catalyst.
  • the calcination time is preferably 1 hour to 12 hours. In this way, a pre-calcined powder (C) is obtained.
  • the pre-sintered powder (C) may be molded into a spherical shape using a molding machine, but a method in which the pre-sintered powder (C) (containing a molding aid and a strength improver, if necessary) is supported on a carrier such as an inactive ceramic is preferred.
  • the widely known methods of support include a rolling granulation method, a method using a centrifugal fluidized coating device, and a wash coat method.
  • the method can uniformly support the pre-calcined powder (C) on the carrier, but when considering the production efficiency of the catalyst and the performance of the catalyst prepared, it is more preferable to use an apparatus having a flat or uneven disk at the bottom of a fixed cylindrical container, which is rotated at high speed to vigorously stir the carrier charged in the container by repeated rotation and revolution of the carrier itself, and to which the pre-calcined powder (C) and, if necessary, a molding aid and/or a strength improver are added to support the powder components on the carrier. In this way, a molded body (D) is obtained.
  • binders that can be used include water, ethanol, methanol, propanol, polyhydric alcohols, polyvinyl alcohol as a polymer binder, and silica sol aqueous solution as an inorganic binder.
  • Ethanol, methanol, propanol, and polyhydric alcohols are preferred, and diols such as ethylene glycol and triols such as glycerin are more preferred.
  • a catalyst with particularly high performance can be obtained when an aqueous solution of glycerin with a concentration of 5% by mass or more is used.
  • the amount of these binders used is usually 2 to 80 parts by mass per 100 parts by mass of the pre-calcined powder (C).
  • An inert carrier with a diameter of about 2 to 8 mm is usually used, and the pre-calcined powder (C) is supported on it.
  • the support rate is determined taking into consideration the catalyst use conditions, such as the space velocity of the reaction raw materials and the raw material concentration, and is usually 20% to 80% by mass.
  • the support rate is defined by the following formula (4).
  • Support rate (mass%) 100 x [mass of pre-calcined powder (C) used for molding / (mass of pre-calcined powder (C) used for molding + mass of inert carrier used for molding)] (4)
  • the molded body (D) obtained in step d) tends to have improved catalytic activity and selectivity by calcining it at a temperature of 200 to 600°C for about 1 to 12 hours.
  • the calcination temperature is preferably 400°C to 600°C, more preferably 500°C to 600°C.
  • Air is the preferred gas to be passed through for simplicity, but it is also possible to use inert gases, gases for creating a reducing atmosphere, and mixtures thereof.
  • inert gases include nitrogen and carbon dioxide.
  • gases for creating a reducing atmosphere include nitrogen oxide-containing gases, ammonia-containing gases, and hydrogen gas. In this way, the catalyst (E) is obtained.
  • the catalytic gas phase oxidation reaction of an alkene in the present invention is carried out by introducing a mixed gas consisting of 6 to 12 volume % of an alkene (more preferably 6 to 10 volume %), 5 to 18 volume % of molecular oxygen, 0 to 60 volume % of water vapor and 20 to 70 volume % of an inert gas such as nitrogen or carbon dioxide onto the catalyst prepared as described above at a temperature in the range of 250 to 450° C. and a pressure of normal pressure to 10 atm, preferably normal pressure to 5 atm, more preferably normal pressure to 3 atm, for a contact time of 0.5 to 10 seconds.
  • the volume ratio of oxygen to alkene in the raw material gas is preferably 1.0 or more and 1.8 or less. More preferred upper limits of oxygen/alkene are 1.7 and 1.6, respectively, and more preferably 1.5. More preferred lower limits are 1.1, 1.2, and 1.3, respectively. From the above, oxygen/alkene is more preferably 1.1 or more and 1.7 or less, even more preferably 1.2 or more and 1.6 or less, and most preferably 1.3 or more and 1.5 or less.
  • alkene includes alcohols that produce alkenes in their intramolecular dehydration reaction, such as tertiary butyl alcohol.
  • a higher space velocity of the reaction substrate, such as an alkene, relative to the catalyst volume is preferable from the viewpoint of production efficiency, but if it is too high, the yield of the target product may decrease or the catalyst life may be shortened. Therefore, in practice, the space velocity of the reaction substrate relative to the catalyst volume is preferably 40 to 200 hr -1 , more preferably 60 to 180 hr -1 .
  • NL represents the volume of the reaction substrate under standard conditions.
  • the conversion rate of the alkene is preferably near the conversion rate at which a high acrolein yield is obtained, and is usually 90 to 99.9%, preferably 95 to 99.5%, more preferably 96 to 99%.
  • the activity of the entire catalyst layer will decrease, and the reaction bath temperature required to obtain the target product with the usual raw material conversion rate may rise too much. If the reaction bath temperature becomes too high, the hot spot may become hot, causing catalyst deterioration and performance degradation. In some cases, early deterioration of the catalyst on the gas inlet side may cause a high-temperature hot spot in the highly active catalyst layer on the gas outlet side, causing a sudden decrease in the selectivity and yield of the target product. Therefore, it is necessary to consider the balance of the catalyst on the gas inlet side and the gas outlet side, and to prevent the catalyst layer on the outlet side from being too short, causing the activity of the entire catalyst layer to decrease and the reaction bath temperature to rise excessively.
  • the reaction bath temperature is set appropriately depending on the catalyst characteristics, usage conditions, required catalyst life, etc., so it cannot be generalized, but the reaction bath temperature at the beginning of the reaction is preferably 350°C or less, and more preferably 340°C or less.
  • the lower limit is 300°C or more, and more preferably 310°C or more.
  • the reaction bath temperature at the beginning of the reaction is preferably 300°C or more and 350°C or less, and more preferably 310°C or more and 340°C or less.
  • the reaction bath temperature is the set temperature, which is set to obtain an appropriate raw material conversion rate.
  • Acrolein yield (mol%) (number of moles of acrolein produced/number of moles of propylene supplied) x 100
  • the powder obtained by mixing 5 parts by mass of crystalline cellulose with 100 parts by mass of the pre-calcined powder was adjusted to the inert carrier (alumina, a spherical material having a diameter of 4.5 mm mainly composed of silica) so that the loading rate defined by the above formula (4) was 50% by mass.
  • the inert carrier alumina, a spherical material having a diameter of 4.5 mm mainly composed of silica
  • a 20% by mass aqueous glycerin solution was used as a binder, and the supported catalyst was obtained by supporting and molding the catalyst into a spherical shape having a diameter of 5.20 mm.
  • the supported catalyst was calcined at a calcination temperature of 530° C. for 4 hours under an air atmosphere to obtain catalyst A1.
  • the activity of catalyst A1 was evaluated as follows.
  • the propylene flow rate at the outlet was calculated by a calibrated gas chromatograph, and the propylene conversion rate x was calculated.
  • the reaction rate k of catalyst A1 calculated based on this by the above formula (II) was 0.63.
  • Catalyst B2 The pre-calcined powder obtained in the preparation of catalyst B1 was molded into a 4.0 mm diameter spherical material containing alumina and silica as the main components as an inert carrier so that the loading rate was 60 mass %, and catalyst B2 having a diameter of 5.00 mm was obtained in the same manner as catalyst B1.
  • the reaction rate k of catalyst B2 was 0.43.
  • This pre-calcined powder was molded using a 4.4 mm diameter spherical material mainly composed of alumina and silica as an inert carrier so that the loading rate was 40 mass%, and catalyst C1 with a diameter of 4.80 mm was obtained in the same manner as catalyst A1.
  • the reaction rate k of catalyst C1 was 0.42.
  • This pre-calcined powder was treated in exactly the same manner as in the preparation of catalyst A1 to obtain catalyst D1 with a diameter of 5.30 mm.
  • the reaction rate k of catalyst D1 was 0.62.
  • the reaction rate k of catalyst E1 was 0.60.
  • Example 1 A jacket for circulating molten salt as a heat medium and a thermocouple for measuring the catalyst layer temperature were installed on the tube axis of a stainless steel reactor with an inner diameter of 25 mm, and a thermocouple temperature sheath with an outer diameter of 3 mm was installed. From the raw gas inlet side toward the gas outlet side, 120 cm of diluted catalyst (70% diluted by mass, calculated in the same manner below) in which catalyst B1 and a silica-alumina mixture inactive spherical carrier were mixed in a mass ratio of 70:30 was packed as the upper layer (raw gas inlet side), 120 cm of undiluted catalyst B1 was packed as the middle layer, and 160 cm of undiluted catalyst A1 was packed as the lower layer.
  • diluted catalyst 70% diluted by mass, calculated in the same manner below
  • akt/akn was 1.71. This resulted in a three-layered catalyst layer.
  • the feedstock was passed through the reactor so that the space velocity of propylene was 190 hr -1 , and the pressure at the outlet side of the reactor tube during total gas flow was 110 kPaG. After 300 hours had elapsed since the start of the reaction, the reaction bath temperature was changed to carry out the oxidation reaction of propylene.
  • the results of examining the reaction results by changing the reaction bath temperature are shown in Table 1.
  • the peak temperature of each catalyst layer means the temperature at the highest position in each catalyst layer in the temperature profile in the reactor tube obtained by measuring the temperature at a predetermined interval (5 cm interval in this embodiment).
  • rows in Table 1 in which there is no peak temperature or reaction result of each layer in A1 and A2 mean that A1 and A2 are calculated values calculated by interpolation or extrapolation of the measured data (the same applies hereinafter).
  • the calculation process of Sf/St at BT330°C, where the acrolein yield is the highest is shown in Table 1-2.
  • the feed material was circulated so that the space velocity of propylene was 130 hr -1 , and the pressure at the outlet side of the reaction tube during the entire gas flow was 85 kPaG, and the reaction was started in the same manner as in Example 1, and the reaction results were examined.
  • the results are shown in Table 3.
  • thermocouple temperature sheath with an outer diameter of 6 mm was inserted into a stainless steel reactor with an inner diameter of 27 mm, and 15 cm of silica-alumina spheres with a diameter of 5.2 mm were packed from the raw gas inlet side.
  • the reaction was started in the same manner as in Example 1, except that the feed material was circulated so that the space velocity of propylene was 100 hr -1 and the pressure at the outlet side of the reaction tube during total gas flow was 35 kPaG, and the reaction results were examined. The results are shown in Table 4.
  • the reaction was started in the same manner as in Example 1, except that the space velocity of propylene was 180 hr -1 and the pressure at the outlet side of the reaction tube during the entire gas flow was 90 kPaG, and the reaction results were examined. The results are shown in Table 5.
  • the present invention can improve yields and suppress runaway reactions in unsaturated aldehyde manufacturing plants. This allows industrial plants to maintain stable yields and operate stably over the long term.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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EP23877208.1A EP4603472A1 (en) 2022-10-12 2023-10-04 Method for producing unsaturated aldehyde, and apparatus for producing unsaturated aldehyde
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