WO2024043330A1 - 内部オレフィンの製造方法、及び触媒の活性を再生する方法 - Google Patents

内部オレフィンの製造方法、及び触媒の活性を再生する方法 Download PDF

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WO2024043330A1
WO2024043330A1 PCT/JP2023/030695 JP2023030695W WO2024043330A1 WO 2024043330 A1 WO2024043330 A1 WO 2024043330A1 JP 2023030695 W JP2023030695 W JP 2023030695W WO 2024043330 A1 WO2024043330 A1 WO 2024043330A1
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catalyst
olefin
reaction
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temperature
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French (fr)
Japanese (ja)
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秀仁 池端
慎吾 高田
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Kao Corp
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Kao Corp
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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/20—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C07C5/2506—Catalytic processes
    • C07C5/2512—Catalytic processes with metal oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for producing internal olefins and a method for regenerating the activity of a catalyst.
  • Internal olefins are widely used as oil drilling oil base oils, raw materials for chemical products, etc. Internal olefins are produced from 1-olefins and the like by double bond isomerization, metathesis reactions, and the like. For example, Japanese Patent Publication No.
  • Patent Document 1 describes a method for isomerizing a 1-alkene to an internal alkene: a) combining at least one 1-alkene with a catalyst in a liquid phase at a temperature of about 50°C to about 200°C, wherein the catalyst comprises (i) at least one Group 8 alkene; formed by contacting a transition metal salt and (ii) at least one alkyl aluminum compound to obtain a first mixture; and b) combining the first mixture of step a) with at least one acid-washed clay at a temperature of about 100°C to about 300°C to form a final mixture.
  • the catalyst comprises (i) at least one Group 8 alkene; formed by contacting a transition metal salt and (ii) at least one alkyl aluminum compound to obtain a first mixture
  • Patent Document 2 describes a method for isomerizing olefins, in which at least one olefin-containing raw material is added to the olefin in a reaction zone, and the olefin exhibits double bond isomerization activity.
  • a method is described comprising contacting with a catalyst to obtain an olefin isomerization product, the catalyst comprising a ⁇ -alumina titania catalyst having a surface area greater than 200 m 2 /g.
  • the present invention relates to a method for producing an internal olefin, which includes a step of subjecting a raw material olefin to an isomerization reaction in the presence of the catalyst R described below.
  • Catalyst R A catalyst subjected to an olefin isomerization reaction at a reaction temperature (T 1 ) is heated at a temperature exceeding the reaction temperature (T 1 ) (hereinafter also referred to as "catalyst holding temperature (T 2 )”) in the presence of an olefin. )
  • T 1 reaction temperature
  • T 2 catalyst holding temperature
  • FIG. 2 is a diagram showing changes in catalyst activity over time in the continuous reaction of Step 1 of Example 1.
  • the present invention relates to a method for producing an internal olefin and a method for regenerating the activity of a catalyst, which can regenerate the activity of a catalyst that has decreased due to the isomerization reaction of a raw material olefin.
  • the present inventors have discovered that the above problem can be solved by maintaining a catalyst subjected to an olefin isomerization reaction under specific temperature conditions in the presence of an olefin. More specifically, in the presence of the raw material olefin and/or the isomerism of the raw material olefin, there are concerns about catalyst deactivation due to an increase in the amount of raw material olefin and coking, and further catalyst deactivation due to poisonous substances in the raw material. We have found that it is possible to regenerate the activity of the catalyst by controlling the temperature in the presence of the internal olefin obtained by the chemical reaction.
  • the present invention relates to a method for producing an internal olefin, which includes a step of subjecting a raw material olefin to an isomerization reaction in the presence of the catalyst R described below.
  • Catalyst R A catalyst subjected to an olefin isomerization reaction at a reaction temperature (T 1 ) is heated at a temperature exceeding the reaction temperature (T 1 ) (hereinafter also referred to as "catalyst holding temperature (T 2 )”) in the presence of an olefin.
  • the present invention also relates to a method for regenerating the activity of a catalyst, which includes the following steps. A step of maintaining a catalyst subjected to an olefin isomerization reaction at a reaction temperature (T 1 ) at a catalyst holding temperature (T 2 ) exceeding the reaction temperature (T 1 ) in the presence of an olefin.
  • a method for producing an internal olefin and a method for regenerating the activity of a catalyst which can regenerate the activity of a catalyst that has decreased due to the isomerization reaction of a raw material olefin.
  • the method for producing an internal olefin of the present invention is a method for producing an internal olefin, which includes a step of isomerizing a raw material olefin in the presence of a catalyst R described below.
  • Catalyst R A catalyst subjected to an olefin isomerization reaction at a reaction temperature (T 1 ) is heated at a temperature exceeding the reaction temperature (T 1 ) (hereinafter also referred to as "catalyst holding temperature (T 2 )”) in the presence of an olefin.
  • an olefin means the presence of a raw material olefin and/or the presence of an internal olefin obtained by an isomerization reaction of the raw material olefin.
  • Catalyst R maintains the catalyst subjected to the isomerization reaction of the raw material olefin at the reaction temperature (T 1 ) at a catalyst holding temperature (T 2 ) exceeding the reaction temperature (T 1 ) in the presence of the raw material olefin. It may be the obtained catalyst.
  • Step 1 is a step of obtaining a catalyst subjected to an olefin isomerization reaction at a reaction temperature (T 1 ), and the catalyst obtained in Step 1 is held in the presence of an olefin at a temperature exceeding the reaction temperature (T 1 ).
  • the step of maintaining the temperature (T 2 ) to obtain catalyst R is called step 2, and the step of isomerizing the raw material olefin in the presence of catalyst R is called step 3.
  • the production method of the present invention it is possible to regenerate the activity of the catalyst that has decreased due to the isomerization reaction of the raw material olefin.
  • the reason for this is not necessarily certain, it is thought to be as follows. It is thought that as the isomerization reaction of the raw material olefin progresses, poisoning components accumulate on the surface of the catalyst and the activity of the catalyst decreases over time. However, by holding the catalyst subjected to the isomerization reaction of the raw material olefin under specific temperature conditions, the poisoning components accumulated on the surface of the catalyst are removed for some reason, and the activity of the catalyst is thought to be regenerated. Note that the above mechanism regarding the effects of the present invention is a conjecture, and is not limited thereto.
  • Step 1 obtaining a catalyst used in the isomerization reaction
  • Step 2 catalyst regeneration step
  • Step 3 isomerization reaction step
  • the raw material olefin is preferably an olefin having 8 or more and 36 or less carbon atoms.
  • the number of carbon atoms in the raw material olefin is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 24 or less, more preferably 22 or less, More preferably, it is 18 or less.
  • raw olefins examples include octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, hene-eicosene, docosene, tricosene, tetracosene, etc. From the viewpoint of availability, , hexadecene, and octadecene.
  • the double bond position of the raw material olefin is not particularly limited, but from the viewpoint of availability, it is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2. That is, the raw material olefin is preferably a 1-olefin, 2-olefin, 3-olefin, or 4-olefin, more preferably a 1-olefin, 2-olefin, or 3-olefin, and still more preferably a 1-olefin or 2-olefin. It is an olefin. Note that the raw material olefin may be a mixture of two or more types of olefins having different double bond positions.
  • the average double bond position of the raw material olefin is preferably 3.0 or less, more preferably 2.0 or less, even more preferably 1.8 or less, and preferably 1.0 or more.
  • the raw material olefin preferably contains at least 1-olefin, and the 1-olefin is preferably a linear 1-olefin.
  • the raw material olefin may be obtained by any method, and a commercially available olefin having 8 or more carbon atoms and 36 or less carbon atoms, preferably a 1-olefin having 8 or more carbon atoms and 36 or less carbon atoms, may be used as the raw material olefin. It may be produced by dehydration reaction using an aliphatic primary alcohol having 8 or more and 36 or less (straight chain aliphatic primary alcohol having 8 or more and 36 or less carbon atoms) as a raw material (raw material alcohol). The reaction is expressed by the following reaction formula.
  • R represents an alkyl group having 4 or more carbon atoms, and from the viewpoint of usefulness, it is preferably a linear alkyl group having 4 or more carbon atoms.
  • Aliphatic primary alcohol (raw material alcohol) (10) produces 1-olefin (1) by intramolecular dehydration represented by (IV), and as shown in (V) and (VI), By intermolecular dehydration, 1-olefin (1) is produced via reaction intermediate dialkyl ether (11). A part of the produced 1-olefin (1) becomes an internal olefin such as a 2-olefin in which the double bond position is closer to the end by an isomerization reaction.
  • the raw alcohol may be either petroleum-derived alcohol or natural raw material-derived alcohol.
  • naturally occurring aliphatic primary alcohols include those made from coconut oil, palm oil, palm kernel oil, soybean oil, rapeseed oil, beef tallow, lard, tall oil, fish oil, and the like.
  • aliphatic primary alcohols include n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n- Tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol, n-nonadecanol, n-eicosanol, n-heneicosanol, n-docosanol , n-tricosanol, n-tetracosanol, etc.
  • n-hexadecanol and n-octadecanol are preferred.
  • the method for producing the raw material olefin from the raw material alcohol is not particularly limited and may be produced by any known method, but it is preferable to produce it by liquid phase dehydration reaction in the presence of a solid catalyst, preferably in the presence of a solid acid catalyst.
  • a solid catalyst metal oxides containing aluminum are preferred.
  • the reaction temperature of the liquid phase dehydration reaction is preferably 255°C or more and 300°C or less.
  • the reaction pressure is preferably normal pressure.
  • the catalyst provided in the olefin isomerization reaction step (step 1) at the reaction temperature (T 1 ) is heated at a temperature exceeding the reaction temperature (T 1 ) (catalyst retention temperature (T 2 )) in the presence of the olefin. ) and subjected to the catalyst regeneration step (step 2). Further, the catalyst (catalyst R) obtained by the catalyst regeneration step (step 2) is subjected to the raw material olefin isomerization reaction step (step 3).
  • the catalyst used in step 1 preferably contains elements of the 3rd to 5th period, more preferably aluminum (Al), silicon (Si), titanium (Ti), iron (Fe).
  • the catalyst is preferably a solid catalyst, more preferably a solid acid catalyst, and even more preferably a solid Lewis acid catalyst.
  • the catalyst is preferably at least one selected from an aluminum oxide catalyst (hereinafter also simply referred to as "aluminum oxide”), an aluminum phosphate catalyst, and a zeolite (aluminosilicate) catalyst, and more preferably an aluminum oxide catalyst. It is a catalyst.
  • Examples of crystal forms of aluminum oxide include ⁇ , ⁇ , ⁇ , etc.
  • aluminum oxide is preferably ⁇ -alumina.
  • the purity of aluminum oxide in the aluminum oxide catalyst is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 98% by mass or more, from the viewpoint of reactivity.
  • the upper limit is not particularly limited and is 100% by mass.
  • the reaction system in the olefin isomerization reaction is not particularly limited, and may be either a heterogeneous system or a homogeneous system. From the viewpoint of recovery, a heterogeneous system is preferable.
  • the homogeneous system here refers to a system in which the catalyst and olefin are compatible, and the heterogeneous system refers to a system in which the catalyst and olefin are incompatible.
  • the catalyst in the present invention is preferably a solid catalyst.
  • the solid catalyst may be used as a powdered solid catalyst as it is, or may be used as a granulated product or a molded product.
  • the shape of the solid catalyst include powder, granules, beads, noodles, and pellets.
  • the shape of the solid catalyst is preferably shaped into granules, beads, noodles, pellets, etc. from the viewpoint of solid-liquid separation in suspended bed batch reactions and from the viewpoint of reducing pressure loss in fixed bed continuous reactions. It is preferably bead-shaped or noodle-shaped, and still more preferably bead-shaped.
  • the average particle diameter of the solid catalyst is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, even more preferably 5 ⁇ m or more, and preferably 300 ⁇ m or less, from the viewpoint of reactivity. , more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, even more preferably 30 ⁇ m or less.
  • the average particle diameter of the powdered solid catalyst can be determined by a method such as a laser diffraction/scattering method.
  • the average particle diameter of the solid catalyst is preferably 0.2 mm or more, more preferably 0.4 mm or more, and even more preferably 0.6 mm or more, from the viewpoint of reactivity. And preferably it is 2.0 mm or less, more preferably 1.3 mm or less, and still more preferably 0.8 mm or less.
  • the average particle diameter of the granular solid catalyst can be determined by the following method. That is, 2000, 1400, 1000, 710, 500, 355, 250, 180, 125, 90, 63, 45 ⁇ m sieves as specified in JIS Z8801-1 (established on May 20, 2000, last revised on November 20, 2006).
  • the 50% average diameter is calculated for the under-sieve mass distribution by the sieving method, and this is taken as the average particle diameter.
  • 2000, 1400, 1000, 710, 500, 355, 250, 180, 125, 90, 63 Using a 45 ⁇ m sieve, stack the sieves with the smallest opening on a saucer, add 100 g of granules from the top of the top 2000 ⁇ m sieve, cover with a lid, and use a low-tap type sieve shaker (manufactured by HEIKO Seisakusho, tapping).
  • the mass of the granules remaining on each sieve and saucer was measured, and the mass percentage of the granules on each sieve (%) was measured. ) is calculated.
  • the mass percentages of the granules on the sieves with smaller openings are integrated in order from the receiving tray, and the particle diameter that makes the total 50% is defined as the average particle diameter.
  • the diameter of the solid catalyst is preferably 1 mm or more, more preferably 1.5 mm or more, and even more preferably 2 mm or more, from the viewpoint of reactivity and ease of recovery of the catalyst.
  • the length is preferably 5 mm or less, more preferably 4 mm or less, and still more preferably 3 mm or less.
  • the diameter of the solid catalyst may be an average value measured arbitrarily three times.
  • the diameter of the bead-shaped solid catalyst can be measured using a vernier caliper.
  • the diameter of the solid catalyst is preferably 0.3 mm or more, more preferably 0.5 mm or more, and even more preferably 0.7 mm or more, from the viewpoint of reactivity and catalyst strength. and is preferably 2.5 mm or less, more preferably 2.3 mm or less, and even more preferably 2.0 mm or less.
  • the diameter of the solid catalyst may be an average value measured at positions 1/4, 1/2, and 3/4 of the length from one end in the longitudinal direction.
  • the length of the solid catalyst is preferably 2 mm or more, more preferably 2.5 mm or more, from the viewpoint of uniformly filling the catalyst in the reaction system and from the viewpoint of catalyst strength. , more preferably 3 mm or more, and preferably 8 mm or less, more preferably 6 mm or less, even more preferably 5.5 mm or less.
  • the diameter and length of the noodle-shaped solid catalyst can be measured using calipers.
  • the diameter and length of the solid catalyst are preferably 1.5 mm or more, more preferably 2.0 mm or more, and still more preferably 2.0 mm or more, from the viewpoint of reactivity and catalyst strength. .5 mm or more, and preferably 5.0 mm or less, more preferably 4.0 mm or less, still more preferably 3.0 mm or less.
  • the diameter and length of the pelletized solid catalyst can be measured using calipers.
  • the specific surface area of the solid catalyst is preferably 80 m 2 /g or more, more preferably 100 m 2 /g or more, even more preferably 120 m 2 /g or more, and preferably is 300 m 2 /g or less, more preferably 280 m 2 /g or less, even more preferably 250 m 2 /g or less.
  • the specific surface area of the solid catalyst can be measured by a method that generally determines a specific surface area, such as the BET method. For example, it can be measured by a nitrogen adsorption method using a specific surface area measuring device.
  • the average pore diameter of the solid catalyst is preferably 4 nm or more, more preferably 5 nm or more, even more preferably 6 nm or more, and preferably 20 nm or less, more preferably 17 nm.
  • the thickness is preferably 15 nm or less.
  • the average pore diameter of the solid catalyst is calculated by the BJH method (Barrett-Joyner-Halenda method) after preheating the sample at 250°C for 5 hours using a specific surface area/pore distribution measuring device, for example.
  • the peak top pore diameter (pore diameter) of the pore diameter distribution can be taken as the average pore diameter.
  • the BJH method is calculated using a cylindrical pore that is not connected to other pores as a model, and is a method for determining pore distribution from capillary aggregation of nitrogen gas and multilayer adsorption. The details are described in "Shimadzu Review” (Vol. 48, No. 1, pp. 35-44, published in 1991).
  • the pore volume of the solid catalyst is preferably 0.1 mL/g or more, more preferably 0.15 mL/g or more, and even more preferably 0.2 mL/g or more. , and is preferably 0.8 mL/g or less, more preferably 0.75 mL/g or less, even more preferably 0.7 mL/g or less.
  • the pore volume of the solid catalyst can be measured by a method that generally determines pore volume, such as mercury porosimetry, and can be measured, for example, by mercury porosimetry using a mercury porosimeter.
  • the acid amount of the solid catalyst is preferably 0.1 mmol/g or more, more preferably 0.15 mmol/g or more, and even more preferably 0.2 mmol/g or more, from the viewpoint of reactivity and reaction selectivity. And preferably 1.5 mmol/g or less, more preferably 1.0 mmol/g or less, even more preferably 0.9 mmol/g or less, even more preferably 0.85 mmol/g or less, even more preferably 0.8 mmol/g or less. It is.
  • the amount of acid in the solid catalyst can be measured by a method that generally determines the amount of acid, such as ammonia temperature program desorption (NH 3 -TPD).
  • the crushing strength of the solid catalyst is preferably 1 daN or more, more preferably 1.5 daN or more, even more preferably 2 daN or more, and preferably 11 daN or less, more preferably 10 daN or less, even more preferably It is 9 daN or less.
  • the crushing strength of a solid catalyst can be measured, for example, by applying a compressive force to a granulated or molded catalyst using a destructive testing device or the like.
  • the crushing pressure in this specification is indicated by the magnitude of the force when cracks begin to appear in the catalyst when a force is applied to compress the granulated or molded catalyst.
  • the amount of catalyst used is preferably adjusted appropriately depending on the reaction method.
  • the amount of catalyst used is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass, based on 100 parts by mass of the raw material olefin.
  • the amount is at least 50 parts by weight, more preferably 40 parts by weight, and even more preferably 35 parts by weight.
  • the amount of the catalyst used can be adjusted as appropriate depending on the amount of raw material olefin supplied (the amount of liquid fed).
  • Step 1 is a step of obtaining a catalyst that is subjected to an olefin isomerization reaction at a reaction temperature (T 1 ).
  • the olefin may be the raw material olefin described above, and the isomerization reaction in step 1 may be an internal isomerization reaction, and may include an isomerization reaction in which a 2-olefin becomes a 1-olefin. You can stay there.
  • the reaction system in Step 1 is not particularly limited and may be either a heterogeneous system or a homogeneous system, and a heterogeneous system is preferable from the viewpoint of efficiently providing the catalyst used in Step 1 to Step 2 and from the viewpoint of ease of operation.
  • the reaction format of the isomerization reaction in Step 1 is not particularly limited, and a batch type or a continuous type can be selected as appropriate, but from the viewpoint of ease of operation, a continuous type is preferably selected.
  • the reaction format is continuous, either a fixed bed method or a suspended bed method may be employed. Among these, the fixed bed method is preferred from the viewpoint of ease of operation. That is, the reaction format of the isomerization reaction in Step 1 is preferably a continuous fixed bed method.
  • reaction temperature T 1 is preferably 120°C or higher, more preferably 140°C or higher, from the viewpoint of reactivity and reaction selectivity.
  • the temperature is more preferably 160°C or higher, more preferably 340°C or lower, more preferably 320°C or lower, even more preferably 300°C or lower.
  • reaction pressure The pressure in the reaction vessel during the reaction is not particularly limited, and from the viewpoint of safety and ease of operation, the absolute pressure is preferably 1 MPa or less, more preferably 0.5 MPa or less, still more preferably 0.2 MPa or less, and even more preferably 0.2 MPa or less. Preferably it is 0.1 MPa, ie atmospheric pressure.
  • an inert gas can be introduced into the reaction vessel.
  • the inert gas include nitrogen, argon, helium, etc. Nitrogen is preferred from the viewpoint of easy availability. It is preferable to circulate the inert gas as a carrier.
  • the flow rate of the inert gas can be adjusted as appropriate depending on the scale of the reactor and the reaction type, but is preferably 0.5 NL/hr or more, more preferably 1 NL/hr or more, and still more preferably 3 NL/hr or more. and is preferably 20 NL/hr or less, more preferably 10 NL/hr or less, even more preferably 5 NL/hr or less.
  • the reaction type is a batch type
  • the inert gas can be passed by a method such as passing above the reaction solution or bubbling it into the reaction solution.
  • reaction time The reaction time in the isomerization reaction is appropriately determined depending on the type and amount of the (raw material) olefin, the reaction temperature, and the like.
  • the reaction time is preferably 0.25 hr or more, more preferably 0.5 hr or more, and even more preferably 1.0 hr or more, from the viewpoint of reactivity and reaction selectivity. , preferably 20 hr or less, more preferably 16 hr or less, even more preferably 12 hr or less, even more preferably 8 hr or less, and still more preferably 5 hr or less.
  • the rotation speed of stirring can be appropriately set depending on the scale of the reaction apparatus, and is preferably 20 rpm or more, more preferably 100 rpm or more, still more preferably 300 rpm or more, and preferably 800 rpm.
  • the speed is more preferably 700 rpm or less, and even more preferably 600 rpm or less.
  • LHSV liquid hourly space velocity
  • LHSV liquid hourly space velocity
  • Catalyst obtained in step 1 When the reaction type is a batch type, the catalyst obtained in Step 1 is appropriately separated from the reaction system and subjected to the catalyst regeneration step in Step 2. On the other hand, when the reaction type is a continuous type, the catalyst obtained in Step 1 can be subjected to the catalyst regeneration step in Step 2 without requiring an operation to separate it from the reaction system.
  • Step 2 is a step of obtaining catalyst R by maintaining the catalyst obtained in Step 1 described above at a catalyst holding temperature (T 2 ) exceeding the reaction temperature (T 1 ). From the viewpoint of catalyst regeneration efficiency, Step 2 is preferably carried out in the presence of an olefin, and carried out while the olefin is flowing.
  • the olefin used in step 2 may be the raw material olefin described above, and does not have to be the same as the olefin used in steps 1 and 3, but from the viewpoint of producing an internal olefin with few impurities, it may be used in step 3. It is preferable that the olefin be of the same type or composition as the raw material olefin. Further, when the catalyst regeneration step is performed in the presence of the raw material olefin used in step 3, it is preferable because a special cleaning operation of the catalyst and equipment is not required after the catalyst regeneration step.
  • the catalyst holding system in Step 2 is not particularly limited, and may be either a heterogeneous system or a homogeneous system as in Step 1, and efficiently regenerates the activity of the catalyst that has decreased due to the isomerization reaction of the (raw material) olefin in Step 1. From this point of view, a heterogeneous system is preferred.
  • the catalyst holding format in Step 2 is not particularly limited, and as in Step 1, a batch type or continuous type can be selected as appropriate. The catalyst activity that has decreased due to the isomerization reaction of the (raw material) olefin in Step 1 can be efficiently regenerated.
  • the catalyst holding method is a continuous type
  • either a fixed bed method or a suspended bed method may be adopted.
  • the fixed bed method is preferred from the viewpoint of ease of operation. That is, the catalyst holding method in step 2 is preferably a continuous fixed bed method.
  • the catalyst obtained in step 1 is maintained at a temperature higher than the reaction temperature T1 in step 1, from the viewpoint of efficiently regenerating the activity of the catalyst that has decreased due to the olefin isomerization reaction in step 1.
  • the catalyst holding temperature at which the catalyst obtained in step 1 in step 2 is held at a temperature exceeding the reaction temperature T 1 in step 1 is T 2 (°C)
  • the catalyst holding temperature T 2 in step 2 is the olefin in step 1.
  • the temperature is preferably 5° C. or more higher than the reaction temperature T1 in Step 1 , more preferably 30° C. or more higher, and even more preferably 35° C. or higher.
  • the temperature is high, more preferably 40°C or more, and even more preferably 45°C or more.
  • the difference ⁇ T (T 2 - T 1 ) between the catalyst holding temperature (T 2 ) in step 2 and the reaction temperature (T 1 ) in step 1 is the difference ⁇ T (T 2 - T 1 ) between the catalyst holding temperature (T 2 ) in step 2 and the reaction temperature (T 1 ) in step 1, which is the difference between the catalyst holding temperature (T 2 ) in step 2 and the reaction temperature (T 1 ) in step 1.
  • the temperature is 150°C or lower, more preferably 130°C or lower, even more preferably 100°C or lower, even more preferably 80°C or lower.
  • the catalyst holding temperature (T 2 ) in step 2 may be appropriately selected in relation to the reaction temperature (T 1 ) in step 1 so that ⁇ T (T 2 - T 1 ) is within the above range.
  • the temperature is preferably 180°C or higher, more preferably 200°C or higher, and still more preferably 210°C or higher.
  • the temperature is 350°C or lower, more preferably 330°C or lower, even more preferably 320°C or lower.
  • the reaction temperature (T 1 ) When the reaction temperature (T 1 ) varies, the reaction temperature (T 1 ) may be an average value. Furthermore, when the catalyst holding temperature (T 2 ) varies, the catalyst holding temperature (T 2 ) may be an average value.
  • a contact measuring method using a thermocouple As a method for measuring the reaction temperature (T 1 ), a contact measuring method using a thermocouple can be mentioned. Further, as a method for measuring the catalyst retention temperature (T 2 ), a contact measurement method using a thermocouple can be mentioned.
  • the absolute pressure is preferably 1 MPa or less, more preferably 0.5 MPa or less, and still more preferably 0.2 MPa or less. , more preferably 0.1 MPa, ie, atmospheric pressure.
  • an inert gas can be introduced into the reaction vessel.
  • the inert gas include nitrogen, argon, helium, etc. Nitrogen is preferred from the viewpoint of easy availability. It is preferable to circulate the inert gas as a carrier.
  • the flow rate of the inert gas can be adjusted as appropriate depending on the scale of the reactor and the reaction type, but is preferably 0.01 NL/hr or more, more preferably 1 NL/hr or more, and still more preferably 3 NL/hr or more. and is preferably 20 NL/hr or less, more preferably 10 NL/hr or less, even more preferably 5 NL/hr or less.
  • the reaction type is a batch type
  • the inert gas can be passed by a method such as passing above the reaction solution or bubbling it into the reaction solution.
  • the catalyst retention time in the catalyst regeneration step is appropriately determined depending on the catalyst retention temperature (T 2 ) and the like.
  • the catalyst holding time is preferably 0.25 hr or more, more preferably 0.05 hr or more, from the viewpoint of efficiently regenerating the activity of the catalyst that has decreased due to the isomerization reaction of the (raw material) olefin in Step 1. It is .5 hr or more, more preferably 1.0 hr or more, and preferably 20 hr or less, more preferably 16 hr or less, still more preferably 12 hr or less, and still more preferably 10 hr or less.
  • the rotation speed of stirring can be appropriately set depending on the scale of the reaction apparatus, and is preferably 20 rpm or more, more preferably 100 rpm or more, and still more preferably 300 rpm or more.
  • the speed is 800 rpm or less, more preferably 700 rpm or less, even more preferably 600 rpm or less.
  • LHSV Liquid Hourly Space Velocity
  • the catalyst holding type is a continuous type
  • LHSV liquid hourly space velocity
  • it is preferably 0.05/hr or more, more preferably 0.1/hr or more, even more preferably 0.15/hr or more, and preferably 20/hr or less, more preferably 15/hr or more. /hr or less, more preferably 10/hr or less.
  • Catalyst obtained in step 2 When the catalyst holding system is a batch type, the catalyst obtained in step 2 is appropriately separated from the catalyst holding system and is subjected to the isomerization reaction step of step 3. On the other hand, when the catalyst holding system is a continuous type, the catalyst obtained in step 2 can be subjected to the isomerization reaction step of step 3 without requiring an operation to separate it from the catalyst holding system.
  • Step 3 is a step in which the raw material olefin is subjected to an isomerization reaction in the presence of the catalyst obtained in Step 2 (catalyst R).
  • the isomerization reaction in step 3 may be an internal isomerization reaction as the main reaction, or may include an isomerization reaction in which a 2-olefin becomes a 1-olefin.
  • reaction format The reaction system in Step 3 is not particularly limited, and as in Steps 1 and 2, it may be a heterogeneous system or a homogeneous system, and from the viewpoint of ease of operation, a heterogeneous system is preferred.
  • the reaction format of the isomerization reaction in Step 3 is not particularly limited, and as in Steps 1 and 2, batch type or continuous type can be selected as appropriate, but from the viewpoint of ease of operation, continuous type is preferably selected. preferable.
  • the reaction format is continuous, either a fixed bed method or a suspended bed method may be employed. Among these, the fixed bed method is preferred from the viewpoint of ease of operation. That is, the reaction format of the isomerization reaction in Step 3 is preferably a continuous fixed bed method.
  • reaction temperature T3 If the isomerization reaction temperature in step 3 is T 3 (° C.), the reaction temperature T 3 in step 3 can be lower than the catalyst holding temperature T 2 in step 2 from the viewpoint of reactivity and reaction selectivity. preferable. Furthermore, from the viewpoint of reactivity and reaction selectivity, the reaction temperature T 3 in step 3 is preferably a temperature lower than the catalyst holding temperature T 2 in step 2 by 5° C. or more, more preferably 10° C. or more lower, More preferably, the temperature is lower by 15°C or more.
  • the difference ⁇ T (T 2 - T 3 ) between the catalyst holding temperature (T 2 ) in step 2 and the reaction temperature (T 3 ) in step 3 is preferably 5 from the viewpoint of reactivity and reaction selectivity.
  • the temperature is preferably 15°C or higher, more preferably 15°C or higher, and preferably 150°C or lower, more preferably 130°C or lower, and still more preferably 120°C or lower.
  • the reaction temperature (T 3 ) in Step 3 may be appropriately selected in relation to the catalyst holding temperature (T 2 ) in Step 2 so that ⁇ T (T 2 - T 3 ) is within the above range.
  • the temperature is preferably 120°C or higher, more preferably 140°C or higher, even more preferably 160°C or higher, and preferably 340°C or lower, more preferably 320°C or lower, and even more preferably is below 300°C.
  • the reaction temperature (T 3 ) in step 3 may be an average value.
  • the method for measuring the reaction temperature (T 3 ) is the same as that for the reaction temperature (T 1 ).
  • reaction pressure There is no particular restriction on the pressure inside the reaction vessel during the reaction, and from the viewpoint of safety and ease of operation, the absolute pressure is preferably 1 MPa or less, more preferably 0.5 MPa or less, still more preferably 0.2 MPa or less, and even more preferably 0.2 MPa or less. Preferably it is 0.1 MPa, ie atmospheric pressure.
  • an inert gas can be introduced into the reaction vessel.
  • the inert gas include nitrogen, argon, helium, etc. Nitrogen is preferred from the viewpoint of easy availability. It is preferable to circulate the inert gas as a carrier.
  • the flow rate of the inert gas can be adjusted as appropriate depending on the scale of the reactor and the reaction type, but is preferably 0.01 NL/hr or more, more preferably 1 NL/hr or more, and still more preferably 3 NL/hr or more. and is preferably 20 NL/hr or less, more preferably 10 NL/hr or less, even more preferably 5 NL/hr or less.
  • the inert gas can be passed by a method such as passing above the reaction solution or bubbling it into the reaction solution.
  • reaction time The reaction time in the isomerization reaction is appropriately determined depending on the type and amount of the raw material olefin, the reaction temperature, and the like.
  • the reaction time is preferably 0.25 hr or more, more preferably 0.5 hr or more, and even more preferably 1.0 hr or more, from the viewpoint of reactivity and reaction selectivity. , preferably 20 hr or less, more preferably 16 hr or less, still more preferably 12 hr or less, even more preferably 10 hr or less, still more preferably 5 hr or less.
  • the rotation speed of stirring can be appropriately set depending on the scale of the reaction apparatus, and is preferably 20 rpm or more, more preferably 100 rpm or more, still more preferably 300 rpm or more, and preferably 800 rpm.
  • the speed is more preferably 700 rpm or less, and even more preferably 600 rpm or less.
  • the LHSV liquid hourly space velocity
  • the LHSV liquid hourly space velocity
  • the reaction type is a continuous type
  • the LHSV (liquid hourly space velocity) which represents the amount of raw material olefin supplied relative to the amount of catalyst used
  • it is preferably 0.05/hr or more, from the viewpoint of reactivity and reaction selectivity.
  • it is 0.1/hr or more, more preferably 0.15/hr or more, and preferably 20/hr or less, more preferably 15/hr or less, still more preferably 10/hr or less.
  • the reaction type is a batch type
  • the internal olefin produced in step 3 is obtained by appropriately separating it from the catalyst that has passed through step 3.
  • the reaction type is continuous
  • the internal olefin produced in step 3 can be obtained without requiring an operation for separating it from the catalyst that has passed through step 3.
  • the internal olefin obtained by the internal olefin production method of the present invention is useful as a raw material or intermediate raw material for surfactants, organic solvents, softeners, sizing agents, etc., and is particularly useful as a raw material for surfactants. .
  • a method for producing an internal olefin which includes the step of subjecting a raw material olefin to an isomerization reaction in the presence of the following catalyst R.
  • Catalyst R A catalyst subjected to an olefin isomerization reaction at a reaction temperature (T 1 ) is heated at a temperature exceeding the reaction temperature (T 1 ) (hereinafter also referred to as "catalyst holding temperature (T 2 )”) in the presence of an olefin.
  • Step 1 is a step of obtaining a catalyst subjected to an olefin isomerization reaction at a reaction temperature (T 1 ).
  • the step of obtaining the catalyst R by maintaining the catalyst at a temperature (T 2 ) exceeding the above is called step 2, and the step of isomerizing the raw olefin in the presence of the catalyst R is called step 3.
  • the catalyst R is heated at a temperature exceeding the reaction temperature (T 1 ) (hereinafter referred to as "catalyst retention temperature (T 2 )”) in the presence of the raw material olefin, at a temperature exceeding the reaction temperature (T 2 ).
  • the difference ⁇ T (T 2 ⁇ T 1 ) between the catalyst holding temperature (T 2 ) in step 2 and the reaction temperature (T 1 ) in step 1 is preferably 5° C. or more, more preferably more than 30° C., and even more preferably 35° C.
  • the catalyst holding temperature (T 2 ) in step 2 is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 210°C or higher, and preferably 350°C or lower, more preferably 330°C or lower, and The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 5>, wherein the temperature is preferably 320° C. or lower.
  • the pressure inside the reaction vessel used in the catalyst holding step of Step 2 is an absolute pressure, preferably 1 MPa or less, more preferably 0.5 MPa or less, even more preferably 0.2 MPa or less, and still more preferably 0.1 MPa, that is, atmospheric pressure.
  • ⁇ 8> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 7>, wherein step 2 is carried out under inert gas flow.
  • the flow rate of the inert gas is preferably 0.01 NL/hr or more, more preferably 1 NL/hr or more, even more preferably 3 NL/hr or more, and preferably 20 NL/hr or less, more preferably 10 NL/hr or less. , more preferably 5 NL/hr or less, the method for producing an internal olefin according to ⁇ 8>.
  • the catalyst retention time in step 2 is preferably 0.25 hr or more, more preferably 0.5 hr or more, even more preferably 1.0 hr or more, and preferably 20 hr or less, more preferably 16 hr or less, and even more preferably 12 hr.
  • the method for producing an internal olefin according to ⁇ 10> which is more preferably 10 hr or less.
  • the rotational speed of stirring in step 2 is preferably 20 rpm or more, more preferably 100 rpm or more, even more preferably 300 rpm or more, and preferably 800 rpm or less, more preferably 700 rpm or less, still more preferably 600 rpm or less.
  • LHSV Liquid Hourly Space Velocity
  • the method for producing an internal olefin according to ⁇ 13> which is above and preferably 20/hr or less, more preferably 15/hr or less, and even more preferably 10/hr or less.
  • ⁇ 15> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 14>, wherein the reaction temperature (T 3 ) in Step 3 is lower than the catalyst retention temperature (T 2 ) in Step 2.
  • the difference ⁇ T (T 2 ⁇ T 3 ) between the catalyst holding temperature (T 2 ) in step 2 and the reaction temperature (T 3 ) in step 3 is preferably 5° C. or higher, more preferably 10° C. or higher, and even more preferably 15° C. °C or higher, and preferably 150°C or lower, more preferably 130°C or lower, even more preferably 120°C or lower, the method for producing an internal olefin according to ⁇ 15>.
  • ⁇ 17> As described in ⁇ 15> or ⁇ 16>, wherein the difference ⁇ T (T 2 - T 3 ) between the catalyst holding temperature (T 2 ) in Step 2 and the reaction temperature (T 3 ) in Step 3 is 10° C.
  • reaction temperature (T 3 ) in step 3 is preferably 120°C or higher, more preferably 140°C or higher, even more preferably 160°C or higher, and preferably 340°C or lower, more preferably 320°C or lower, even more preferably is 300°C or less, the method for producing an internal olefin according to any one of ⁇ 15> to ⁇ 17>.
  • the pressure in the reaction vessel in step 3 is an absolute pressure, preferably 1 MPa or less, more preferably 0.5 MPa or less, even more preferably 0.2 MPa or less, even more preferably 0.1 MPa, that is, atmospheric pressure, ⁇ 15
  • the flow rate of the inert gas is preferably 0.01 NL/hr or more, more preferably 1 NL/hr or more, even more preferably 3 NL/hr or more, and preferably 20 NL/hr or less, more preferably 10 NL/hr or less. , more preferably 5 NL/hr or less, the method for producing an internal olefin according to ⁇ 20>.
  • ⁇ 22> The method for producing an internal olefin according to any one of ⁇ 15> to ⁇ 21>, wherein the reaction type in step 3 is a batch type.
  • the reaction time in step 3 is preferably 0.25 hr or more, more preferably 0.5 hr or more, even more preferably 1.0 hr or more, and preferably 20 hr or less, more preferably 16 hr or less, even more preferably 12 hr or less. , more preferably 10 hr or less, still more preferably 5 hr or less, the method for producing an internal olefin according to ⁇ 22>.
  • the rotational speed of stirring in step 3 is preferably 20 rpm or more, more preferably 100 rpm or more, even more preferably 300 rpm or more, and preferably 800 rpm or less, more preferably 700 rpm or less, still more preferably 600 rpm or less.
  • LHSV Liquid Hourly Space Velocity
  • the method for producing an internal olefin according to ⁇ 25> which is above and preferably 20/hr or less, more preferably 15/hr or less, and even more preferably 10/hr or less.
  • the reaction temperature (T 1 ) in step 1 is preferably 120°C or higher, more preferably 140°C or higher, even more preferably 160°C or higher, and preferably 340°C or lower, more preferably 320°C or lower, even more preferably
  • the pressure in the reaction vessel in step 1 is an absolute pressure, preferably 1 MPa or less, more preferably 0.5 MPa or less, even more preferably 0.2 MPa or less, even more preferably 0.1 MPa, that is, atmospheric pressure, ⁇ 1
  • the flow rate of the inert gas in step 1 is preferably 0.5 NL/hr or more, more preferably 1 NL/hr or more, even more preferably 3 NL/hr or more, and preferably 20 NL/hr or less, more preferably 10 NL/hr. /hr or less, more preferably 5NL/hr or less, the method for producing an internal olefin according to ⁇ 30>.
  • ⁇ 32> The method for producing an internal olefin according to ⁇ 1> to ⁇ 31>, wherein the reaction format of Step 1 is a batch type.
  • the reaction time in step 1 is preferably 0.25 hr or more, more preferably 0.5 hr or more, even more preferably 1.0 hr or more, and preferably 20 hr or less, more preferably 16 hr or less, and even more preferably 12 hr or less. , more preferably 8 hr or less, still more preferably 5 hr or less, the method for producing an internal olefin according to ⁇ 32>.
  • the rotational speed of stirring in step 1 is preferably 20 rpm or more, more preferably 100 rpm or more, even more preferably 300 rpm or more, and preferably 800 rpm or less, more preferably 700 rpm or less, and still more preferably 600 rpm or less.
  • ⁇ 35> The method for producing an internal olefin according to ⁇ 1> to ⁇ 31>, wherein the reaction format of Step 1 is continuous.
  • LHSV Liquid Hourly Space Velocity
  • the method for producing an internal olefin according to ⁇ 35> is preferably 0.05/hr or more, more preferably 0.1/hr or more, and even more preferably 0.15/hr. or more, and preferably 20/hr or less, more preferably 15/hr or less, even more preferably 10/hr or less, the method for producing an internal olefin according to ⁇ 35>.
  • ⁇ 37> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 36>, wherein the catalyst is a solid Lewis acid catalyst.
  • the catalyst preferably contains elements of the third to fifth periods, more preferably aluminum (Al), silicon (Si), titanium (Ti), iron (Fe), zinc (Zn), and yttrium (Y). , zirconium (Zr), and tin (Sn), and further contains aluminum (Al).
  • the catalyst is preferably at least one selected from an aluminum oxide catalyst (hereinafter also simply referred to as "aluminum oxide”), an aluminum phosphate catalyst, and a zeolite (aluminosilicate) catalyst, and more preferably an aluminum oxide catalyst.
  • the aluminum oxide is preferably ⁇ -alumina, and the purity of the aluminum oxide in the aluminum oxide catalyst is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and The method for producing an internal olefin according to ⁇ 39>, wherein the content is preferably 98% by mass or more, and the upper limit is not particularly limited, but is 100% by mass.
  • ⁇ 42> The method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 41>, wherein the olefin preferably contains a 1-olefin, and the 1-olefin is preferably a linear 1-olefin.
  • the carbon number of the raw material olefin is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 18 or less, ⁇ 1 >> The method for producing an internal olefin according to any one of ⁇ 42>.
  • a method for regenerating the activity of a catalyst comprising the steps of: A step of maintaining a catalyst subjected to an olefin isomerization reaction at a reaction temperature (T 1 ) at a catalyst holding temperature (T 2 ) exceeding the reaction temperature (T 1 ) in the presence of an olefin ⁇ 46>
  • the step is a step in which the catalyst subjected to the isomerization reaction of the raw material olefin at the reaction temperature (T 1 ) is maintained at a catalyst holding temperature (T 2 ) exceeding the reaction temperature (T 1 ) in the presence of the raw material olefin.
  • ⁇ 47> The method for regenerating the activity of a catalyst according to ⁇ 45> or ⁇ 46>, wherein the step is preferably performed under the flow of an olefin.
  • ⁇ 48> The method for regenerating the activity of a catalyst according to any one of ⁇ 45> to ⁇ 47>, wherein the step is step 2 in the method for producing an internal olefin according to any one of ⁇ 1> to ⁇ 44>.
  • Example 1 [Step 1: Isomerization reaction step] A ⁇ -alumina catalyst (manufactured by Mizusawa Chemical Industry Co., Ltd., product name “Neobead GB-13”, ⁇ -Al 2 O 3 , bead shape, diameter 2.0 mm, specific surface area 180 m 2 /g) was used as a catalyst in the catalyst continuous evaluation device. , average pore diameter 11.1 nm, pore volume 0.50 mL/g, acid amount 0.28 mmol/g, crushing strength 2.6 daN), and 400 mL of 1-hexadecene (Fujifilm Wako Pure Chemical Industries, Ltd.) was filled as the raw material olefin.
  • ⁇ -alumina catalyst manufactured by Mizusawa Chemical Industry Co., Ltd., product name “Neobead GB-13”, ⁇ -Al 2 O 3 , bead shape, diameter 2.0 mm, specific surface area 180 m 2 /g
  • a continuous reaction was carried out under the conditions of nitrogen pressure 0.1 MPaG, reaction temperature (T 1 ) 230°C, and reaction time 3,216 h, while flowing nitrogen at 3.9 NL/h. Ta. After the reaction was completed, the catalyst layer was cooled to room temperature, the pressure was removed, and the catalyst was extracted from the continuous catalyst evaluation device and used in the next step.
  • step 1 the reaction solution was collected from the outlet of the apparatus every 12 hours, and about 1 drop of the collected reaction solution was put into a sample tube, and 1 mL of dimethyl disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 mg of iodine (manufactured by Fujifilm Co., Ltd.) were added. (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and after thorough mixing, the mixture was allowed to stand at 65° C. for 15 minutes.
  • dimethyl disulfide manufactured by Tokyo Chemical Industry Co., Ltd.
  • iodine manufactured by Fujifilm Co., Ltd.
  • the product was analyzed using a flame ion detector (FID) under the following conditions: injection temperature: 300°C, detector temperature: 350°C, He flow rate: 0.8 mL/min, and the product was quantified.
  • the average double bond position (Ave.DBP) was calculated from the olefin content at each double bond position using the following formula 1. The change over time is shown in Figure 1. From the results shown in FIG. 1, it was confirmed that the activity of the catalyst decreased over time due to the isomerization reaction of the raw material olefin in Step 1. Ave.
  • DBP (1-olefin+2 ⁇ 2-olefin+3 ⁇ 3-olefin+4 ⁇ 4-olefin+5 ⁇ 5-olefin+6 ⁇ 6-olefin+7 ⁇ 7-olefin+8 ⁇ 8-olefin)/100 (Formula 1)
  • a catalyst continuous reaction apparatus separate from Step 1 was filled with 10 mL of the catalyst that had passed through Step 1, 1-hexadecene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was fed at a rate of 80 mL/h, and nitrogen was fed at a rate of 1.9 NL/h.
  • Continuous reaction was carried out under the conditions of a reaction temperature of 260° C. and a reaction time of 6 h while flowing at a constant flow rate of 6 h.
  • the reaction solution collected at the end of the reaction was subjected to quantitative determination of the product by the method described above, and the average double bond position (Ave.DBP 1 ) was calculated.
  • Step 2 Catalyst regeneration step
  • 1-hexadecene manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • nitrogen was flowing at 1.9 NL/h
  • the catalyst holding temperature (T 2 ) Continuous reaction was carried out under the conditions of 280°C and catalyst retention time of 6 hours.
  • Step 3 Isomerization reaction step
  • Continuous reaction was performed in the catalyst continuous reaction apparatus after performing Step 2 under the same conditions as in the above-mentioned catalyst activity evaluation.
  • the reaction solution collected at the end of the reaction was subjected to quantitative determination of the product by the method described above, and the average double bond position (Ave.DBP 2 ) was calculated.
  • Examples 2 to 11 Except for changing the type and amount of feed material olefin, the amount of catalyst used, the nitrogen flow rate, the reaction temperatures T 1 and T 3 , the catalyst holding temperature T 2 , and the reaction time as shown in Table 1. Each step was carried out in the same manner as in Example 1, and the product was quantified at each step. In Examples 10 to 11, in which 1-octadecene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the raw material olefin, the average double bond position ( Ave.DBP) was calculated. Ave.
  • DBP (1-olefin+2 ⁇ 2-olefin+3 ⁇ 3-olefin+4 ⁇ 4-olefin+5 ⁇ 5-olefin+6 ⁇ 6-olefin+7 ⁇ 7-olefin+8 ⁇ 8-olefin+9 ⁇ 9-olefin)/100 (Formula 2)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JPH0751576A (ja) * 1990-03-22 1995-02-28 Exxon Res & Eng Co 改質触媒の調製法
JPH08502955A (ja) * 1992-10-19 1996-04-02 デーエスエム ナムローゼ フェンノートシャップ オレフィン又はオレフィン混合物の変換法
JP2008517062A (ja) 2004-10-19 2008-05-22 ハーキュリーズ・インコーポレーテッド アルファオレフィンを内部オレフィンに異性化するための方法
JP2016539128A (ja) 2013-11-20 2016-12-15 ルーマス テクノロジー インク． 高耐被毒性オレフィン二重結合異性化触媒
JP2018177750A (ja) * 2017-04-21 2018-11-15 Ｊｘｔｇエネルギー株式会社 不飽和炭化水素の製造方法及び脱水素触媒の再生方法
JP2022096503A (ja) * 2020-12-17 2022-06-29 花王株式会社 内部オレフィンの製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0751576A (ja) * 1990-03-22 1995-02-28 Exxon Res & Eng Co 改質触媒の調製法
JPH08502955A (ja) * 1992-10-19 1996-04-02 デーエスエム ナムローゼ フェンノートシャップ オレフィン又はオレフィン混合物の変換法
JP2008517062A (ja) 2004-10-19 2008-05-22 ハーキュリーズ・インコーポレーテッド アルファオレフィンを内部オレフィンに異性化するための方法
JP2016539128A (ja) 2013-11-20 2016-12-15 ルーマス テクノロジー インク． 高耐被毒性オレフィン二重結合異性化触媒
JP2018177750A (ja) * 2017-04-21 2018-11-15 Ｊｘｔｇエネルギー株式会社 不飽和炭化水素の製造方法及び脱水素触媒の再生方法
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Title
SHIMADZU REVIEW, vol. 48, no. 1, 1991, pages 35 - 44

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