WO2023112762A1 - アルデヒドの製造方法及びアルコールの製造方法、並びに触媒組成物 - Google Patents

アルデヒドの製造方法及びアルコールの製造方法、並びに触媒組成物 Download PDF

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WO2023112762A1
WO2023112762A1 PCT/JP2022/044805 JP2022044805W WO2023112762A1 WO 2023112762 A1 WO2023112762 A1 WO 2023112762A1 JP 2022044805 W JP2022044805 W JP 2022044805W WO 2023112762 A1 WO2023112762 A1 WO 2023112762A1
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catalyst
aldehyde
producing
group
mass
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French (fr)
Japanese (ja)
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将士 三宅
崇 佐藤
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to CN202280082661.6A priority Critical patent/CN118414322A/zh
Priority to EP22907290.5A priority patent/EP4450484A4/en
Priority to JP2022575409A priority patent/JP7639833B2/ja
Publication of WO2023112762A1 publication Critical patent/WO2023112762A1/ja
Priority to US18/743,198 priority patent/US20240327325A1/en
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
    • B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4092—Regeneration or reactivation of catalysts containing metals involving a stripping step, with stripping gas or solvent
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • 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
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • 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
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

Definitions

  • the present invention relates to an aldehyde production method, an alcohol production method, and a catalyst composition.
  • a method for producing an aldehyde by hydroformylating an olefinically unsaturated organic compound with carbon monoxide and hydrogen in the presence of a metal-phosphine complex catalyst of groups 8 to 10 of the long period periodic table is often used as an aldehyde production method.
  • This hydroformylation reaction is also referred to as the "oxo reaction”.
  • a mixed gas of hydrogen (H 2 ) and carbon monoxide (CO) used in the reaction is called "oxogas”.
  • the catalyst used for the hydroformylation reaction of olefins contains expensive metals such as rhodium and other long-period Group 8-10 metals of the periodic table, so it is ideal to use the catalyst semipermanently. Therefore, usually, the reaction product is separated from the reaction liquid, and the reaction liquid containing the catalyst, which is the distillation residue, is recycled to the reaction zone for reuse, or the reaction product is distilled off from the reaction zone by gas stripping. A method is used in which the reaction liquid containing the catalyst remains in the reaction zone and the reaction is continued continuously.
  • reaction zone In the hydroformylation reaction, high-boiling-point by-products such as aldehyde condensation by-products are produced and accumulate, so part of the reaction solution is continuously or intermittently expelled outside the reaction zone (the reaction zone is sometimes referred to as the reaction system). ). Since the extracted reaction liquid contains high-boiling-point by-products as well as catalysts, especially expensive metals of Groups 8 to 10 of the periodic table, efficient recovery is economically feasible. It is also extremely important in preventing environmental pollution.
  • Patent Document 1 discloses that a hydroformylation reaction solution in which high-boiling by-products are accumulated and extracted from a reaction zone is mixed with alcohol and water, brought into contact with hydrogen gas at 30°C, cooled to 0°C, and hydrogen A method for crystallizing and recovering an atom-coordinated rhodium-phosphine complex catalyst is disclosed.
  • Patent Document 2 alcohol, water and hydrogen are mixed with a hydroformylation reaction liquid in which high-boiling by-products are accumulated and extracted from the reaction zone, and maintained at 10 to 30 ° C. to form hydrogen-coordinated rhodium-
  • a method for depositing and recovering a phosphine-based complex catalyst is disclosed.
  • an alkylphosphine produced by partially substituting a ligand such as a triarylphosphine with an alkyl group of an ⁇ -olefin is treated with a sufficient amount of oxygen or an oxygen-containing gas at about 20 to 80°C.
  • a method for reactivating a deactivated catalyst by converting it to the corresponding phosphine oxide is disclosed.
  • Patent Document 4 discloses that a hydroformylation reaction liquid in which high-boiling by-products are accumulated and extracted from a reaction zone is mixed with alcohol and water, brought into contact with hydrogen gas at 30°C, cooled to 0°C, and hydrogen A method for crystallizing and recovering an atom-coordinated rhodium-phosphine complex catalyst is disclosed.
  • Patent Documents 1 to 4 In the methods disclosed in Patent Documents 1 to 4, first, a rhodium-phosphine-based complex catalyst is crystallized in a state in which high-boiling-point by-products are removed as much as possible, and then recovered as non-sticky crystals, Then, it is necessary to filter the collected crystals to separate the rhodium-phosphine complex catalyst crystals from the crystallization mother liquor. In Patent Documents 1 to 4, the amount of the rhodium-phosphine complex catalyst lost in this filtration process is large, so the rhodium-phosphine complex catalyst cannot be sufficiently recovered.
  • An object of the present invention is to solve these problems.
  • An object of the present invention is to produce an aldehyde capable of recovering an expensive complex catalyst, especially an expensive long-period periodic table group 8 to 10 metal in a complex catalyst at a high yield from a hydroformylation reaction solution. It is to provide a method.
  • Another object of the present invention is to provide a method for producing an alcohol, which produces an aldehyde by the method for producing an aldehyde and produces an alcohol from the aldehyde.
  • the present invention is capable of recovering expensive complex catalysts, especially expensive metals of groups 8 to 10 of the long period periodic table in complex catalysts, which are used in reactions such as hydroformylation reactions, at high yields. , to provide a catalyst composition.
  • the present inventors mixed a poor solvent for the catalyst in the reaction solution after the hydroformylation reaction, subjected to aggregation treatment in a state containing the catalyst and high boiling point by-products, and recovered as adhesive aggregates, It was found that the complex catalyst can be recovered in a higher yield than the conventional method.
  • the invention was achieved based on such knowledge, and the gist is as follows.
  • a method for producing an aldehyde comprising subjecting an olefin to a hydroformylation reaction with a gas containing hydrogen and carbon monoxide in the presence of a catalyst
  • a method for producing an aldehyde comprising mixing a poor solvent for the catalyst with a part or the whole of the reaction liquid extracted from the reaction zone, and precipitating aggregates containing the catalyst and having adhesiveness.
  • a method for producing an aldehyde comprising subjecting an olefin to a hydroformylation reaction with a gas containing hydrogen and carbon monoxide in the presence of a catalyst, Mixing a poor solvent for the catalyst with a part or all of the reaction liquid extracted from the reaction zone to precipitate aggregates containing the catalyst, Production of an aldehyde, wherein the proportion of high boiling point by-products distributed in the aggregate is 4.0% by mass or more when the total mass of the high boiling point by-products contained in the reaction solution is 100% by mass.
  • a method for producing an aldehyde comprising hydroformylating an olefin with a gas containing hydrogen and carbon monoxide in the presence of a catalyst, withdrawing part or all of the reaction liquid in which the high boiling point by-products have accumulated from the reaction zone; The extracted reaction solution is mixed with a poor solvent for the catalyst in a mixing tank to precipitate aggregates containing the catalyst and the high-boiling-point by-product, A method for producing an aldehyde, comprising attaching the precipitated aggregates to the inner surface of the mixing tank and recovering them.
  • [18] A method for producing alcohol, comprising producing an aldehyde by the method according to any one of [1] to [17] and producing an alcohol from the aldehyde.
  • a catalyst composition comprising a catalyst and a high-boiling by-product,
  • the catalyst is a long period periodic table group 8-10 metal-organophosphorus complex catalyst,
  • the catalyst composition wherein the content of the high boiling point by-product is 30% by mass or more based on 100% of the total mass of the catalyst composition.
  • a complex catalyst particularly an expensive long period periodic table group 8 to 10 metal in the complex catalyst, can be recovered at a high yield.
  • a method for producing an aldehyde. can be provided.
  • a method for producing alcohol using the aldehyde produced by this method for producing aldehyde is also provided.
  • FIG. 1 is a graph showing the relationship between the distribution ratio of high-boiling-point by-products into aggregates or crystallized substances and the rhodium recovery rate in Examples 1 to 10 and Comparative Example 1.
  • FIG. FIG. 2(a) is a photograph of the appearance of the mixing vessel after aggregation obtained in Example 2. Aggregates adhered to the inner surface of the mixing vessel, and the reaction liquid after the reaction was solid-liquid separated. This is an example of a state.
  • FIG. 2(b) is a photograph of the external appearance of the mixing tank after crystallization obtained in Comparative Example 1. The crystallized product did not adhere to the inner surface of the mixing tank, and the reaction solution after the reaction was solid-liquid. This is an example of a state in which uniform slurry is formed without separation.
  • a first embodiment of the aldehyde production method of the present invention is to hydroformylate an olefin with a gas containing hydrogen and carbon monoxide in the presence of a catalyst (hereinafter, this step is referred to as “hydroformylation reaction A method for producing an aldehyde, including a part of the reaction solution extracted from the reaction zone (hereinafter, this step may be referred to as a "reaction solution withdrawal step"), or A poor solvent for the catalyst is mixed with the whole, and an aggregate containing the catalyst and having adhesiveness is precipitated (hereinafter, this step may be referred to as an “aggregation step”). manufacturing method.
  • a poor solvent for the catalyst is mixed with part or all of the reaction solution in a mixing tank, and the precipitated aggregates are mixed in the mixing tank. or deposited in agglomerated state within the mixing vessel.
  • a second embodiment of the method for producing an aldehyde of the present invention is to hydroformylate an olefin with a gas containing hydrogen and carbon monoxide in the presence of a catalyst (hereinafter, this step is referred to as a "hydroformylation reaction step").
  • this step is referred to as a "hydroformylation reaction step”
  • the above-mentioned mixing a poor solvent for the catalyst to precipitate an aggregate containing the catalyst hereinafter, this step may be referred to as an “aggregation step”
  • the proportion of high-boiling by-products distributed in the aggregate is 4.0% by mass or more when the total mass of the organisms is 100% by mass.
  • a poor solvent for the catalyst is mixed with part or all of the reaction solution in a mixing tank, and the precipitated aggregates are mixed in the mixing tank. or deposited in agglomerated state within the mixing vessel.
  • a third embodiment of the method for producing an aldehyde of the present invention is to hydroformylate an olefin with a gas containing hydrogen and carbon monoxide in the presence of a catalyst (hereinafter, this step is referred to as a “hydroformylation reaction step”. ), in which part or all of the reaction liquid in which the high boiling point by-product has accumulated is withdrawn from the reaction zone (hereinafter, this step is sometimes referred to as the "reaction liquid withdrawal step”). ), the extracted reaction solution is mixed with a poor solvent for the catalyst in a mixing tank to precipitate an aggregate containing the catalyst and the high-boiling-point by-product (hereinafter, this step is referred to as an “aggregation step”.
  • a method for producing an aldehyde, including attaching the precipitated aggregates to the inner surface of the mixing vessel and recovering them hereinafter, this step may be referred to as a “recovery step”). is.
  • the tank in which the reaction solution and the poor solvent for the catalyst are mixed is called a “mixing tank”, and the process of "precipitating” the “aggregates” in this "mixing tank” is called “aggregation treatment”. This step is called the “aggregation step”.
  • “precipitating” the "crystallized product” as in the conventional method and the comparative example described later is called “crystallization treatment”.
  • the “inner surface of the mixing tank” refers to a portion where the reaction solution flows slowly in the mixing tank, a portion where the reaction solution aggregates are pressed during stirring, or a shape of protrusions in the mixing tank. Specific examples include the bottom surface and inner wall of the mixing tank, baffles, stirring blades, stirring shafts, and side tube surfaces. Also, as used herein, the terms “reaction zone” and “hydroformylation reaction zone” include a reactor for performing a hydroformylation reaction, and reactor peripheral equipment such as a gas-liquid separator attached to the reactor. It refers to bandwidth.
  • the catalyst composition of the present invention is a catalyst composition containing a catalyst and a high boiling point by-product, wherein the catalyst is a long period periodic table group 8 to 10 metal-organophosphorus complex catalyst, and the high boiling point The catalyst composition, wherein the content of by-products is 30% by mass or more based on 100% of the total mass of the catalyst composition.
  • the catalyst used for the hydroformylation reaction is not particularly limited as long as it has a catalytic action on the hydroformylation reaction of olefins. Because of its excellent reaction activity, the long-period periodic table Groups 8 to 10 metal (hereinafter referred to as “group 8 to 10 metal”)-organophosphorus complex catalyst is used as the catalyst used in the hydroformylation reaction. is preferred.
  • Group 8-10 metals are metals belonging to Groups 8-10 in the long period periodic table.
  • ruthenium, cobalt, rhodium, palladium, and platinum are preferred because of their high activity when used as a catalyst, and rhodium is particularly preferred because of its high activity.
  • organophosphorus ligand compound for forming the Group 8-10 metal-organophosphorus complex catalyst commonly used monodentate ligands or polydentate ligands for the Group 8-10 metals Any trivalent organophosphorus compound can be used.
  • organophosphorus compounds that serve as monodentate ligands include tertiary triorganophosphines represented by the following formula (I).
  • each R independently represents a substituted or unsubstituted monovalent hydrocarbon group.
  • the monovalent hydrocarbon group represented by R is generally an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 3 to 12 carbon atoms, and an alkylaryl group having 6 to 24 carbon atoms. groups, arylalkyl groups having 6 to 24 carbon atoms, and the like. That is, the above triorganophosphines are, for example, trialkylphosphine, triarylphosphine, tricycloalkylphosphine, alkylarylphosphine, cycloalkylarylphosphine, alkylcycloalkylphosphine and the like.
  • substituents that the monovalent hydrocarbon group may have include, but are not limited to, alkyl groups, alkoxy groups, and the like.
  • triorganophosphines include tributylphosphine, trioctylphosphine, triphenylphosphine, tritolylphosphine, tricycloalkylphosphine, monobutyldiphenylphosphine, dipropylphenylphosphine, and cyclohexyldiphenylphosphine.
  • triphenylphosphine is preferred because it is chemically stable due to its low activity and is easily available.
  • trivalent organophosphorus compounds for example, trivalent phosphite compounds represented by the following formulas (1) to (10) can be used.
  • R 1 to R 3 each independently represent a monovalent hydrocarbon group which may have a substituent.
  • the optionally substituted monovalent hydrocarbon groups represented by R 1 to R 3 include alkyl groups, aryl groups and cycloalkyl groups.
  • the compound represented by formula (1) include trimethylphosphite, triethylphosphite, n-butyldiethylphosphite, tri-n-butylphosphite, tri-n-propylphosphite, tri-n - trialkyl phosphites such as octyl phosphite and tri-n-dodecyl phosphite; triaryl phosphites such as triphenyl phosphite and trinaphthyl phosphite; and alkylaryl phosphites of.
  • bis(3,6,8-tri-t-butyl-2-naphthyl)phenyl phosphite bis(3,6,8-tri-t-butyl- 2-naphthyl)(4-biphenyl)phenyl phosphite and the like may also be used. Most preferred of these is triphenyl phosphite.
  • R 4 represents a divalent hydrocarbon group which may have a substituent.
  • R 5 represents a monovalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group optionally having a substituent for R 4 includes an alkylene group optionally containing an oxygen, nitrogen, sulfur atom, etc. in the middle of the carbon chain; A cycloalkylene group that may contain a sulfur atom, etc.; a divalent aromatic group such as phenylene and naphthylene; Bonded divalent aromatic group; those in which a divalent aromatic group and an alkylene group are bonded directly or via an atom such as oxygen, nitrogen, or sulfur in the middle.
  • Examples of monovalent hydrocarbon groups for R 5 include alkyl groups, aryl groups, and cycloalkyl groups.
  • Examples of the compound represented by formula (2) include neopentyl (2,4,6-t-butyl-phenyl) phosphite, ethylene (2,4,6-t-butyl-phenyl) phosphite and the like. Examples thereof include compounds described in Japanese Patent No. 3415906.
  • R 10 has the same definition as R 5 in formula (2) above.
  • Ar 1 and Ar 2 each independently represent an aryl group which may have a substituent.
  • x and y each independently represents 0 or 1.
  • Q is selected from the group consisting of -CR 11 R 12 -, -O-, -S-, -NR 13 -, -SiR 14 R 15 and -CO-
  • R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group or an anisyl group
  • R 13 , R 14 and R 15 each independently represent represents a hydrogen atom or a methyl group
  • n represents 0 or 1.
  • trivalent phosphite compounds represented by formula (3) include 1,1′-biphenyl-2,2′-diyl-(2,6-di-t-butyl-4-methylphenyl ) Phosphite et al., a compound described in US Pat. -Butyl-4-methoxyphenyl)phosphite and other compounds described in US Pat. No. 4,717,775.
  • R6 represents a trivalent hydrocarbon group which may have a cyclic or non-cyclic substituent.
  • Compounds represented by formula (4) include, for example, 4-ethyl-2,6,7-trioxa-1-phosphabicyclo-[2,2,2]-octane and the like described in US Pat. No. 4,567,306. and the like.
  • R 7 has the same definition as R 4 in formula (3) above.
  • R 8 and R 9 each independently represent a hydrocarbon group that may have a substituent.
  • a and b each represents an integer of 0 to 6. The sum of a and b is 2 to 6.
  • X represents a (a+b)-valent hydrocarbon group.
  • X represents a divalent group selected from the group consisting of alkylene, arylene and —Ar 1 —(CH 2 )x—Qn—(CH 2 )y—Ar 2 —.
  • Ar 1 , Ar 2 , Q, x, y, and n have the same meanings as Ar 1 , Ar 2 , Q, x, y, and n in formula (3) above.
  • X, Ar 1 , Ar 2 , Q, x, y, and n are synonymous with X, Ar 1 , Ar 2 , Q, x, y, and n in formula (3) above.
  • R 18 has the same definition as R 4 in the above formula (2).
  • R 19 and R 20 each independently represent an aromatic hydrocarbon group, and at least one of the aromatic hydrocarbon groups is carbonized to the carbon atom adjacent to the carbon atom to which the oxygen atom is bonded. has a hydrogen group, m represents an integer of 2 to 4, each —OP(OR 19 )(OR 20 ) group may be different from each other, and X may have a substituent represents an m-valent hydrocarbon group.
  • R 21 to R 24 each independently represent a hydrocarbon group which may have a substituent.
  • R 21 and R 22 , R 23 and R 24 are bonded to W represents an optionally substituted divalent aromatic hydrocarbon group,
  • L represents an optionally substituted saturated or unsaturated divalent aliphatic represents a hydrocarbon group.
  • R 25 to R 28 each represent a monovalent hydrocarbon group which may have a substituent.
  • R 25 and R 26 and R 27 and R 28 are bonded to form a ring.
  • a and B each independently represent a divalent hydrocarbon group which may have a substituent.
  • n represents an integer of 0 or 1.
  • the optionally substituted monovalent hydrocarbon groups represented by R 25 to R 28 include alkyl groups, aryl groups and cycloalkyl groups.
  • the divalent hydrocarbon groups A and B which may have substituents may be aromatic, aliphatic or alicyclic.
  • R 31 and R 41 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms. represent things.
  • Alkyl groups having 1 to 20 carbon atoms include, for example, methyl, ethyl, n-propyl, i-propyl, s-butyl, t-butyl, isopentyl, neopentyl, t-pentyl. t-hexyl group, 1,1,2-trimethylpropyl group and other linear or branched alkyl groups. Among them, those having 3 to 20 carbon atoms are preferred, those having 4 to 20 carbon atoms are more preferred, and those having 4 to 10 carbon atoms are particularly preferred. Furthermore, the carbon atom bonded to the aromatic ring is preferably tertiary, and examples thereof include t-butyl group, t-pentyl group and t-hexyl group.
  • Cycloalkyl groups having 3 to 20 carbon atoms include, for example, a cyclohexyl group, a cyclooctyl group, and an adamantyl group. Among them, cycloalkyl groups having 6 to 14 carbon atoms are preferred, and cycloalkyl groups having 6 to 10 carbon atoms are more preferred.
  • R 31 and R 41 a tertiary alkyl group having 4 to 20 carbon atoms is preferred, a tertiary alkyl group having 4 to 7 carbon atoms is more preferred, and a t-butyl group is particularly preferred. .
  • R 31 and R 41 may be the same or different.
  • R 31 and R 41 are t-butyl groups
  • the bulkiness of the t-butyl groups provides a sufficient stabilizing effect against hydrolysis of the compound represented by formula (11).
  • R 31 and R 41 are particularly preferably t-butyl groups.
  • R 32 and R 42 each independently represent a hydrogen atom, an alkyl or alkoxy group having 1 to 20 carbon atoms, a cycloalkyl or cycloalkoxy group having 3 to 20 carbon atoms, 2 to 20 , aryl and aryloxy groups having 6 to 20 carbon atoms, alkylaryl, alkylaryloxy, arylalkyl and arylalkoxy groups having 7 to 20 carbon atoms.
  • Alkyl groups having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group and n-pentyl group. , an isopentyl group, a neopentyl group, a t-pentyl group, a t-hexyl group, and other linear or branched alkyl groups.
  • Cycloalkyl groups having 3 to 20 carbon atoms include, for example, cyclohexyl, cyclooctyl, and adamantyl groups.
  • Alkoxy groups having 1 to 20 carbon atoms include, for example, methoxy, ethoxy, isopropoxy, t-butoxy and the like. Among them, alkoxy groups having 1 to 12 carbon atoms are preferred.
  • a cycloalkoxy group having 3 to 20 carbon atoms includes, for example, a cyclopentyloxy group.
  • Dialkylamino groups having 2 to 20 carbon atoms include, for example, dimethylamino group and diethylamino group.
  • Aryl groups having 6 to 20 carbon atoms include, for example, phenyl and naphthyl groups.
  • Aryloxy groups having 6 to 20 carbon atoms include, for example, phenoxy groups, naphthoxy groups and the like.
  • Alkylaryl groups having 7 to 20 carbon atoms include, for example, p-tolyl group, o-tolyl group and the like.
  • Alkylaryloxy groups having 7 to 20 carbon atoms include, for example, 2,3-xylenoxy and the like.
  • Arylalkyl groups having 7 to 20 carbon atoms include, for example, benzyl groups and the like.
  • Arylalkoxy groups having 7 to 20 carbon atoms include, for example, 2-(2-naphthyl)ethoxy groups and the like.
  • Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
  • R 32 and R 42 are preferably hydrogen atoms.
  • the substituent at this position contributes little to the effect of improving the reactivity to hydroformylation reaction and the effect of stabilizing the compound represented by formula (11) itself. Therefore, from the viewpoint of suppressing the manufacturing cost of the compound, it is preferably a hydrogen atom, which is the simplest substituent.
  • R 33 and R 43 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an alkylaryl group and an arylalkyl group having 7 to 20 carbon atoms.
  • Alkyl groups having 1 to 20 carbon atoms include, for example, methyl, ethyl, n-propyl, i-propyl, s-butyl, t-butyl, isopentyl, neopentyl, t-pentyl. linear or branched alkyl groups such as t-hexyl group. Among them, those having 4 to 20 carbon atoms are preferred, and those having 4 to 10 carbon atoms are particularly preferred. Furthermore, the carbon atom bonded to the aromatic ring is preferably tertiary, and examples thereof include t-butyl group, t-pentyl group and t-hexyl group.
  • Cycloalkyl groups having 3 to 20 carbon atoms include, for example, cyclohexyl, cyclooctyl, and adamantyl groups. Among them, cycloalkyl groups having 6 to 14 carbon atoms are preferred, and cycloalkyl groups having 6 to 10 carbon atoms are more preferred.
  • Examples of aryl groups having 6 to 20 carbon atoms include phenyl groups and naphthyl groups.
  • alkylaryl groups having 7 to 20 carbon atoms include p-tolyl group and o-tolyl group.
  • An arylalkyl group having 7 to 20 carbon atoms includes, for example, a benzyl group.
  • R 33 and R 43 are each independently preferably a tertiary alkyl group having 4 to 20 carbon atoms, more preferably a tertiary alkyl group having 4 to 7 carbon atoms.
  • a t-butyl group is particularly preferred.
  • R 34 and R 44 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms , a silyl group, a siloxy group and a halogen atom.
  • alkyl groups having 1 to 12 carbon atoms include linear or branched alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group and decyl group. be done.
  • Cycloalkyl groups having 3 to 12 carbon atoms include, for example, cyclopropyl and cyclohexyl groups.
  • Alkoxy groups having 1 to 12 carbon atoms include, for example, methoxy, ethoxy, t-butoxy and the like.
  • Silyl groups include, for example, a trimethylsilyl group.
  • the siloxy group includes, for example, a silyl group and a trimethylsiloxy group.
  • Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
  • R 34 and R 44 are each independently an alkyl group having 1 to 3 carbon atoms such as methyl group or ethyl group, or 1 to 3 carbon atoms such as methoxy group or ethoxy group.
  • Alkoxy groups having a, halogen atoms are preferred, alkyl groups having 1 to 3 carbon atoms are more preferred, and R 34 and R 44 are particularly preferably methyl groups.
  • R 34 and R 44 Small groups such as alkyl groups having 1 to 3 carbon atoms, especially methyl groups, are preferred as R 34 and R 44 .
  • the reason for this is that the hydroformylation reaction can proceed smoothly and the stability of the compound represented by formula (11) can be improved.
  • Z 1 to Z 4 are each independently an aryl group having 6 to 20 carbon atoms.
  • the aryl group may have a substituent. None of Z 1 and Z 2 and Z 3 and Z 4 are bonded to each other.
  • Z 1 to Z 4 each independently have no substituent on the aromatic ring carbon atom adjacent to the carbon atom bonded to the oxygen atom, or have a substituent on the aromatic ring carbon atom.
  • the substituent has 0 to 2 carbon atoms.
  • the substituent has 1 to 2 carbon atoms such as a methyl group and an ethyl group, respectively. is preferably selected from the group consisting of groups, trifluoromethyl groups, cyano groups and nitro groups, halogen atoms such as chlorine atoms and fluorine atoms, and the like.
  • the substituents include methyl group, ethyl group, n-propyl group, i-propyl group and n-butyl group.
  • substituents include halogen atoms, cyano groups, nitro groups, trifluoromethyl groups, hydroxyl groups, amino groups, acyl groups, carbonyloxy groups, oxycarbonyl groups, amide groups, sulfonyl groups, sulfinyl groups, and silyl groups. groups, thionyl groups, and the like.
  • Each of Z 1 to Z 4 may have 1 to 5 of these substituents.
  • Z 1 to Z 4 include phenyl, 1-naphthyl, 2-naphthyl, p-trifluoromethylphenyl, 2-ethylphenyl, 2-methylphenyl and 3-methylphenyl groups.
  • a 1-naphthyl group or a 2-naphthyl group is preferable from the viewpoint of improving the thermal stability of the ligand and improving the selectivity of linear aldehyde production when producing aldehydes by hydroformylation reaction.
  • R 31 and R 41 are each independently a tertiary alkyl group having 4 to 20 carbon atoms
  • R 32 and R 42 are hydrogen
  • R 33 and R 43 are each independently a tertiary alkyl group having from 4 to 20 carbon atoms
  • R 34 and R 44 are each independently from 1 to 3 carbon atoms
  • Bisphosphite compounds are preferred which are selected from the group consisting of alkyl groups containing atoms, alkoxy groups containing 1 to 3 carbon atoms and halogen atoms.
  • Z 1 to Z 4 each independently have no substituent on the aromatic ring carbon atom adjacent to the carbon atom bonded to the oxygen atom, or the aromatic ring carbon atom has 1 to 2 carbon atoms
  • Bisphosphite compounds having substituents with atoms and none of Z 1 to Z 4 being bonded to each other are preferred.
  • R 31 , R 41 , R 33 and R 43 are each independently a tertiary alkyl group having 4 to 7 carbon atoms
  • More preferred are bisphosphite compounds in which R 32 and R 42 are hydrogen atoms and R 34 and R 44 are each independently alkyl groups having 1 to 3 carbon atoms.
  • more preferred are bisphosphite compounds in which Z 1 to Z 4 are each independently a 1-naphthyl group or a 2-naphthyl group, and R 31 , R 41 , R 33 and R 43 are t-butyl groups.
  • bisphosphite compounds in which R 34 and R 44 are methyl groups are particularly preferred.
  • the bisphosphite compound represented by formula (11) can be produced by the method described in International Publication No. 2019/039565.
  • organophosphorus ligand compounds Only one kind of these organophosphorus ligand compounds may be used, or two or more kinds may be mixed and used, but usually only one kind is used.
  • the organic phosphorus-based ligand compound is not particularly limited, but from the viewpoint of excellent catalytic activity and thermal decomposition resistance in the hydroformylation reaction, the phosphite compound represented by the above formula (10) or the above A bisphosphite compound represented by formula (11) is preferred, and a bisphosphite compound represented by formula (11) is particularly preferred. That is, the Group 8-10 metal-organophosphorus complex catalyst used in the present invention is preferably a Group 8-10 metal-phosphite complex catalyst.
  • Groups 8 to 10 metal-organophosphorus complex catalyst is a long period periodic table Groups 8 to 10 metal compound (hereinafter referred to as "Group 8 to 10 metal compound") and an organophosphorus ligand compound can be easily prepared by a known complex forming method from A Group 8-10 metal compound and an organophosphorus ligand compound may be supplied to the reaction zone to form a complex within the reaction zone.
  • the organophosphorus ligand compound may be introduced into the reaction zone as it is, but it is preferable to dissolve it in the reaction medium and introduce it in consideration of ease of handling.
  • Group 8 to 10 metal compounds include aqueous solutions of rhodium chloride, palladium chloride, ruthenium chloride, platinum chloride, rhodium bromide, rhodium iodide, rhodium sulfate, rhodium nitrate, palladium nitrate, rhodium ammonium chloride, rhodium sodium chloride, and the like.
  • organic inorganic salts or inorganic complex compounds water-soluble organic acid salts such as rhodium formate, rhodium acetate, palladium acetate, rhodium propionate, palladium propionate and rhodium octanoate; Moreover, you may use the complex seed
  • the hydroformylation reaction is carried out by reacting the olefin with hydrogen and carbon monoxide in the presence of a catalyst such as a Group 8-10 metal-organophosphorus complex catalyst.
  • a catalyst such as a Group 8-10 metal-organophosphorus complex catalyst.
  • the olefin is not particularly limited, but includes, for example, olefins having 2 to 20 carbon atoms. Examples of olefins having 2 to 20 carbon atoms include ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene, 2-butene, 2-pentene, 3-hexene, Internal olefins such as 4-octene are included.
  • a solvent that dissolves the raw material olefin and a catalyst such as a group 8-10 metal-organophosphorus complex catalyst has a higher boiling point than the resulting aldehyde, and has no reaction-inhibiting action.
  • solvents that can be used in the hydroformylation reaction include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and octane; esters such as butyl acetate and butyl butyrate; mentioned.
  • the concentration of the catalyst in the reaction medium is usually 1 ppm by mass to 10% by mass in terms of metal atoms such as Group 8 to 10 metals, and organic phosphorus ligands such as phosphite compounds used as ligands.
  • the compound is usually present in the reaction medium in excess for purposes such as increasing the stability of the complex catalyst.
  • the hydroformylation reaction can be performed under known conditions.
  • the reaction conditions are usually appropriately selected within the following range.
  • Hydrogen partial pressure 0.01 to 20 MPaG Carbon monoxide partial pressure: 0.01 to 20 MPaG Total pressure: 0.02 MPaG to 30 MPaG
  • Hydrogen partial pressure/carbon monoxide partial pressure 0.1 to 10
  • Reaction temperature 60-200°C Rh (rhodium) concentration: several ppm by mass to several percent by mass P (free organic phosphorus ligand) / Rh: 2 to 10000 (molar ratio)
  • Reaction time several minutes to ten hours
  • an aldehyde with n+1 carbon atoms can be obtained from a raw material olefin with n carbon atoms (n is an integer of 2 to 20, for example).
  • aldehydes include propionaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde and decylaldehyde.
  • Aldehydes are usually obtained as a mixture of linear and branched chains.
  • the hydroformylation reaction is usually carried out under the above reaction conditions using a flow reactor, but a batch reactor can also be used.
  • the main methods of the flow reaction are the stripping method and the liquid circulation method.
  • the stripping method is a method in which a reaction liquid containing a catalyst is held in a reactor, olefin and oxo gas are continuously supplied, and aldehyde produced by the reaction is vaporized in the reactor and taken out of the system.
  • the liquid circulation system is a method in which a reaction medium containing olefin, oxogas, and catalyst is continuously supplied to the reactor, and the reaction liquid containing the produced aldehyde, catalyst, reaction medium, etc. is continuously drawn out of the reactor.
  • the reaction solution withdrawn from the reactor is separated into a product aldehyde and a reaction solution containing a catalyst by a separation operation such as stripping with unreacted gas or distillation.
  • the produced aldehyde obtained is withdrawn out of the system, and the catalyst-containing reaction liquid (in the present invention, this reaction liquid corresponds to the reaction liquid withdrawn in the reaction liquid withdrawing step.
  • the stickiness of the resulting aggregate can be controlled by adjusting the content of the high boiling point by-product in the reaction solution in the aggregation step described later.
  • reaction liquid containing the high-boiling by-product and the catalyst in the present invention, this reaction liquid corresponds to the reaction liquid extracted in the reaction liquid extraction step
  • the amount of the reaction liquid withdrawn from the reaction zone, ie, the reactor may be appropriately determined according to the amount of high-boiling by-products produced.
  • the reaction liquid when the reaction liquid is drawn out of the reaction zone, an amount of catalyst corresponding to the catalyst contained in the drawn out reaction liquid is newly supplied to the reaction zone.
  • the amount of newly supplied catalyst can be reduced by subjecting the extracted reaction liquid to the aggregation step and returning it to the reaction zone.
  • the reaction can be maintained with almost no replenishment.
  • the components of the high-boiling by-products are diverse and complex, but they are mainly aldehyde condensates produced by condensation of aldehydes, which are the target products of the hydroformylation reaction, and have higher boiling points than the produced aldehydes. It is a high-boiling substance that cannot be removed by a simple aldehyde distillation process.
  • Specific examples of such high-boiling-point by-products include aldol, which is a dimer of the produced aldehyde, an ester-based compound, which is a dimer of the produced aldehyde and produced by the Tishchenko reaction of the produced aldehyde, and dehydration of the aldol.
  • Examples include saturated ethers, acetals obtained by reacting the hemiacetal with the produced aldehyde, trimers of the produced aldehyde, and the like.
  • the reaction liquid in which the high-boiling-point by-products have accumulated contains phosphites, phosphonates generated by the decomposition of phosphites, phosphorous acids, etc. exists.
  • rhodium complexes such as the following (a) to (b) are present in the reaction liquid in which the high-boiling-point by-products have accumulated.
  • reaction solution withdrawal step is a step of withdrawing part or all of the reaction solution in which high-boiling-point by-products have accumulated from the hydroformylation reaction zone. It is a step of withdrawing the reaction liquid containing the aldehyde produced by the above, the catalyst, the reaction medium, etc., out of the reactor.
  • the reaction liquid in the hydroformylation reaction zone contains about 40 to 80% by mass of high boiling point by-products.
  • a poor solvent for the catalyst is added and mixed with the reaction solution containing the high boiling point by-products to crystallize aggregates containing the catalyst and the high boiling point by-products.
  • crystallization is performed in a state in which high-boiling-point by-products are removed as much as possible, and the precipitated crystals are filtered to crystallize catalyst crystals.
  • the loss of the catalyst in the filtration process can be eliminated, and the catalyst can be recovered at a high recovery rate.
  • the hydroformylation reaction liquid extracted from the hydroformylation reaction zone may be supplied to the agglomeration step after removing low-boiling components in the reaction liquid.
  • a known separation operation such as distillation can be used to remove the low-boiling components from the reaction solution.
  • the reaction liquid extracted in the reaction liquid extraction step that is, the reaction liquid before the aggregation treatment usually has the following composition. to perform the next agglomeration step.
  • Rhodium atom in complex catalyst 50 to 2000 mass ppm
  • Phosphite compound 1000 ppm by mass to 3% by mass
  • n-aldehyde 1 to 30 mass%
  • Other components 40 to 80% by mass
  • variable complexes contained in “other components” refer to various rhodium complexes contained in the reaction solution in which the high-boiling-point by-products have accumulated, as mentioned in the above section [Hydroformylation reaction step].
  • a poor solvent for the catalyst (hereinafter sometimes simply referred to as “poor solvent”) is added to and mixed with the reaction solution extracted in the reaction solution extraction step to precipitate aggregates containing the catalyst and high boiling point by-products.
  • the extracted reaction solution and poor solvent are put into a mixing tank to precipitate the aggregates.
  • a poor solvent is one in which the Group 8-10 metal compound has a lower solubility than the reaction solution.
  • the poor solvent preferably maintains a homogeneous phase with the reaction solution and does not participate in the reaction in the reaction zone.
  • poor solvents include methanol, ethanol, propanol (n-, i-), butanol (n-, i-, t-), acetone, and mixtures thereof with water.
  • a mixture of water and an alcohol is preferred, and a mixture of water and an alcohol having 1 to 3 carbon atoms is particularly preferred, from the viewpoint of recovery of the group 8-10 metal-phosphite complex catalyst.
  • the content of water in this mixture is preferably 12 to 40% by mass, more preferably 13 to 25% by mass, and further preferably 15 to 22% by mass with respect to 100% by mass of the mixture. preferable.
  • the recovery rate of the complex catalyst increases due to the solubility of the complex.
  • the reaction solution tends to become a homogeneous phase, and the recovery rate of the complex catalyst can be maintained satisfactorily.
  • the mixing ratio (mass ratio) of the poor solvent and the reaction solution depends on the type of the poor solvent and the composition of the reaction solution, but the ratio of the poor solvent to the reaction solution is preferably 5:1 to 15:1, and 6:1 to 10:1. 1 is more preferred, and 7:1 to 9:1 is even more preferred.
  • the ratio of the poor solvent is below the upper limit, the amount of the complex catalyst dissolved in the poor solvent decreases, the recovery rate of the catalyst increases, and the aggregate recovery apparatus can be made smaller.
  • the ratio of the poor solvent is at least the lower limit, the reaction solution tends to become a homogeneous phase, and the recovery rate of the complex catalyst can be maintained satisfactorily.
  • the extracted reaction solution may be mixed with the poor solvent as it is, or may be mixed with the poor solvent after removing at least part of the reaction medium by distillation or the like.
  • reaction solution It is preferable to mix the reaction solution and the poor solvent while stirring.
  • the temperature of the aggregation step is preferably 0 to 70°C, more preferably 0 to 40°C, even more preferably 5 to 20°C. If the temperature at the time of aggregation is equal to or lower than the above upper limit, the recovery rate of the catalyst is excellent. If the temperature at the time of aggregation is equal to or higher than the above lower limit, the poor solvent can be kept in a liquid state, and the cooling energy can be reduced.
  • the aggregation time is not particularly limited. It is usually 10 minutes to 10 hours, more preferably 30 minutes to 5 hours.
  • the aggregation step is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
  • the aggregation step is carried out by stirring the reaction solution and the poor solvent under neutral to acidic conditions. It is preferable because there is no need to perform operations such as processing.
  • the reaction solution withdrawn from the hydroformylation reaction zone is weakly acidic, and the solution obtained by mixing this reaction solution with a poor solvent consisting of a mixture of water and alcohol has a pH of about 4-7. Therefore, the flocculation operation can be performed as it is without any particular pH adjustment.
  • Aggregates are precipitated by stirring the reaction solution and the poor solvent for a predetermined time in the above suitable temperature range in an inert gas atmosphere. For this reason, it is preferable to use a sealable glass container with a stirrer, a stainless steel container, a SUS container, or the like as the mixing tank used in the aggregation step.
  • Aggregates precipitated by mixing a poor solvent with the reaction solution extracted from the hydroformylation reaction zone have stickiness under aggregation conditions.
  • the term “having stickiness” means that the precipitated aggregates in the aggregation step of the present invention have sufficient adhesive strength to adhere to the inner surface of the mixing vessel. Since the aggregates have stickiness in this way, the precipitated aggregates are separated from the liquid in the mixing tank, and the stickiness causes the inner surface of the mixing tank, that is, the bottom and inner walls of the mixing tank. , and become attached to the stirring blades and the like.
  • the reaction solution containing the high boiling point by-product is withdrawn from the hydroformylation reaction zone and coagulated, the aggregate precipitated by the coagulation contains the high boiling point by-product together with the complex catalyst.
  • the presence of boiling by-products makes the agglomerates sticky.
  • the complex catalyst can be recovered at a high recovery rate.
  • the adhesive aggregates are precipitated, and the precipitated aggregates are adhered to the inner surface of the mixing tank and recovered to increase the recovery rate of the complex catalyst.
  • Aggregation is preferably carried out under conditions such that high-boiling by-products migrate into the aggregate at a certain distribution ratio. Specifically, when the total mass of the high boiling point by-products contained in the reaction liquid extracted from the hydroformylation reaction zone is 100% by mass, the lower limit of the distribution ratio of the high boiling point by-products into the aggregates is Aggregation is preferably carried out so that the concentration is preferably 4.0% by mass or more, more preferably 5.0% by mass or more, and still more preferably 6.0% by mass or more.
  • the distribution ratio of the high boiling point by-products in the agglomerates is excessively large, the yield of the agglomerates will decrease. % or less, more preferably 20 mass % or less, and still more preferably 10 mass % or less.
  • the above upper and lower limits can be combined arbitrarily. That is, the distribution ratio of the high-boiling by-products in the agglomerate is 4.0% by mass when the total mass of the high-boiling by-products contained in the reaction liquid extracted from the hydroformylation reaction zone is 100% by mass. It is preferably 30 mass % or less, more preferably 5.0 mass % or more and 20 mass % or less, and even more preferably 6.0 mass % or more and 10 mass % or less.
  • This distribution ratio can be controlled by adjusting aggregation conditions such as the composition of the poor solvent, the ratio of the poor solvent and the reaction solution, and the aggregation temperature.
  • aggregation conditions such as the composition of the poor solvent, the ratio of the poor solvent and the reaction solution, and the aggregation temperature. The details of the method for measuring the "distribution ratio" will be described later in the Examples section.
  • the aggregates deposited in the aggregation step and adhering to the inner surface of the mixing vessel are recovered.
  • the recovered agglomerate is preferably fed to the hydroformylation reaction zone.
  • the method for collecting the aggregates is not particularly limited, but it is easy to operate and collect the aggregates by dissolving the aggregates in a good solvent for the complex catalyst in the aggregates, and the recovery rate of the complex catalyst is also high. It is preferable because Specifically, the liquid in the mixing tank is extracted to leave only the aggregates, and a good solvent for the complex catalyst is added to dissolve the aggregates.
  • the good solvent for the complex catalyst used in this case there are no particular restrictions on the good solvent for the complex catalyst used in this case.
  • the good solvent those mentioned above as the reaction medium used in the hydroformylation reaction, or aldehyde, which is the product obtained in the hydroformylation reaction, are preferable because the aggregate solution can be supplied as it is to the hydroformylation reaction zone.
  • the good solvent examples include aldehydes such as n-butyraldehyde and i-butyraldehyde, and aromatic hydrocarbons such as benzene, toluene and xylene when the raw olefin is propylene. be done.
  • aldehydes such as n-butyraldehyde and i-butyraldehyde
  • aromatic hydrocarbons such as benzene, toluene and xylene when the raw olefin is propylene.
  • the amount of the good solvent used for dissolving the aggregates is not particularly limited, and the smaller the amount for dissolving the aggregates, the better from the viewpoint of reducing the capacity of the mixing tank.
  • the amount of the good solvent varies depending on the solubility of the catalyst in the good solvent to be used and the content of the high-boiling point compound in the aggregates, it is usually preferably about 5 to 100 times the weight of the aggregates.
  • the temperature condition for dissolving the aggregates in the good solvent is preferably about 5 to 60°C.
  • the aggregate solution can be supplied as it is to the hydroformylation reaction zone, but if necessary, it may be subjected to a known separation operation such as distillation to remove unnecessary components, or to a solvent or a complex catalyst with high catalytic activity. After addition, it may be fed to the hydroformylation reaction zone.
  • the reaction solution containing the complex catalyst and high boiling point by-products is withdrawn from the hydroformylation reaction zone, and a poor solvent is added and mixed in the mixing tank to obtain a sticky liquid containing the complex catalyst and high boiling point by-products.
  • the precipitated aggregates are adhered to the inner surface of the mixing tank and recovered.
  • the production method of the present invention eliminates the loss of the complex catalyst due to the filtration operation of the slurry, etc., and can recover and reuse the complex catalyst at a high recovery rate. Therefore, in the production method of the present invention, it is possible to improve productivity without wasting the expensive Group 8 to 10 metals such as rhodium in the complex catalyst.
  • the alcohol production method of the present invention uses an aldehyde produced by the aldehyde production method of the present invention.
  • An alcohol can be produced by reacting an aldehyde as it is with hydrogen, that is, by subjecting it to a hydrogenation reaction, or by subjecting it to a hydrogenation reaction after dimerization.
  • a known solid catalyst in which a metal such as nickel, chromium, or copper is supported on a carrier can be used for the hydrogenation reaction.
  • the reaction conditions are usually a temperature of 60 to 200° C. and a hydrogen pressure of about 0.1 to 20 MPaG.
  • the catalyst composition of the present invention is a catalyst composition containing a catalyst and a high boiling point by-product, wherein the catalyst is a long period periodic table group 8 to 10 metal-organophosphorus complex catalyst,
  • the content of the high boiling point by-product is 30% by mass or more with respect to 100% of the total mass of the catalyst composition.
  • the catalyst composition of the present invention satisfies the above conditions, it becomes sticky. A good recovery rate is obtained.
  • the method for obtaining the catalyst composition of the present invention is not particularly limited. There is a method of obtaining it as a product.
  • the same catalyst as the catalyst used in the first, second and third embodiments of the method for producing aldehyde of the present invention can be employed.
  • the high-boiling by-products may be the same high-boiling by-products listed in the first, second and third embodiments of the method for producing aldehyde of the present invention.
  • the long-period periodic table Groups 8 to 10 metal-organophosphorus complex catalyst is mentioned in the first, second and third embodiments of the above-described method for producing aldehyde of the present invention.
  • the same catalyst as the long period type periodic table Groups 8 to 10 metal-organophosphorus complex catalyst can be used.
  • the lower limit of the content of the high boiling point by-product is such that the catalyst composition becomes sticky and adheres to the inner surface of a reaction apparatus such as a mixing tank.
  • the recovery rate of the catalyst such as the complex catalyst it is 30% by mass or more, preferably 40% by mass or more, or more relative to the total mass of 100% of the catalyst composition. It is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
  • the upper limit of the content ratio of the high boiling point by-product is not particularly limited, and from the viewpoint that the catalyst composition is likely to precipitate as aggregates, It is preferably 97% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.
  • the lower limit of the content of the catalyst is not particularly limited. On the other hand, it is preferably 3% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more.
  • the upper limit of the content ratio of the catalyst is that the catalyst composition becomes sticky, and the catalyst composition is adhered to the inner surface of a reaction apparatus such as a mixing tank and recovered. from the viewpoint of being able to increase the recovery rate of the catalyst, relative to the total mass of 100% of the catalyst composition, preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, and further It is preferably 40% by mass or less, particularly preferably 30% by mass or less.
  • the reaction solvent and the target product of the hydroformylation reaction are added to 100% of the total mass of the catalyst composition. , 10% by mass or less, preferably 5% by mass or less.
  • the method for producing an aldehyde of the present invention comprises dissolving the catalyst composition of the present invention described above in a good solvent for the catalyst to obtain a catalyst solution, and in the presence of the catalyst solution, olefin is hydroformylated to obtain an aldehyde corresponding to the olefin.
  • the method for obtaining a catalyst solution by dissolving the catalyst composition of the present invention in a good solvent for the catalyst is not particularly limited.
  • the same methods and conditions can be employed as in the method of obtaining an agglomerate solution using the catalyst composition of the present invention in place of agglomerates.
  • the method of hydroformylating an olefin in the presence of the catalyst solution to obtain an aldehyde corresponding to the olefin is not particularly limited. and the same conditions as exemplified in the hydroformylation reaction step in any of the methods of the third embodiment.
  • Rhodium acetate aqueous solution (rhodium acetate concentration 28% by mass) (trade name: rhodium acetate L, manufactured by N.E. Chemcat Co., Ltd.) n-butyraldehyde (purity of 99% or more, manufactured by Mitsubishi Chemical Corporation) Methanol (trade name: reagent grade methanol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) Demineralized water (manufactured by Mitsubishi Chemical Corporation)
  • Phosphite ligand A bisphosphite ligand compound shown below, synthesized by the method described in International Publication No. 2019/039565
  • Example 1 A hydroformylation reaction of propylene was carried out using rhodium acetate as a long-period periodic table group 8-10 metal compound and phosphite ligand A as an organic phosphorus-based ligand.
  • the reaction liquid was then withdrawn from the hydroformylation reaction zone and the light boiling point components were distilled off using a distillation method.
  • the composition of the reaction liquid after distillation and before being subjected to aggregation treatment was as follows.
  • the amount of rhodium atoms in the complex catalyst in the reaction solution was quantified by fluorescent X-ray analysis.
  • the amount of n-butyraldehyde was determined by gas chromatography-internal standard method.
  • the amount of phosphite ligand A was determined by high performance liquid chromatography-external standard method.
  • a glass container with an electromagnetic induction stirrer and a capacity of 0.5 L was used as the mixing tank.
  • the mixture was stirred at 500 rpm and held at a temperature of 10° C. for 2 hours to carry out agglomeration treatment to deposit a rhodium complex together with a high-boiling by-product.
  • Other components (various complexes, high boiling point by-products, etc.) 54.4% by mass
  • Rh 2 (cod) 2 (OAc) 2 , bisphosphite ligand A, and toluene as a solvent were mixed, and 54 mL of the resulting mixture was placed in a nitrogen atmosphere in a vertically stirring autoclave with a capacity of 0.2 L. and sealed the autoclave.
  • Table 2 shows the composition of the reaction solution before the hydroformylation reaction.
  • Example 2 to 10 Aggregation treatment was performed under the same conditions as in Example 1, except that the composition of the reaction solution before the aggregation treatment or the composition of the poor solvent (water/methanol) was changed as shown in Table 1, and a rhodium complex catalyst was included. Agglomerates were obtained. Furthermore, aldehyde was produced under the same conditions as in Example 1 using the obtained aggregate. Table 1 shows the evaluation results.
  • FIG. 2(a) A photograph of the appearance of the mixing tank after aggregation obtained in Example 2 is shown in Fig. 2(a). When visually observed, aggregates adhered to the inside of the mixing tank, and the reaction liquid after the reaction was in a state of solid-liquid separation.
  • Example 1 The crystallization treatment was performed under the same conditions as the aggregation treatment in Example 1, except that the composition of the reaction solution before the crystallization treatment and the composition of the poor solvent (water/methanol) were changed as shown in Table 1. A crystallized product containing a rhodium complex catalyst was obtained.
  • FIG. 2(b) A photograph of the external appearance of the mixing tank after the crystallization treatment obtained in Comparative Example 1 is shown in FIG. 2(b). Visual observation revealed that the crystallization treatment liquid did not undergo solid-liquid separation and formed a uniform slurry. Also, no deposition of crystallized material inside the mixing tank was observed.
  • Fig. 1 shows the relationship between the distribution ratio of high boiling point by-products and the rhodium recovery rate in the aggregates of Examples 1 to 10 and the crystallized product of Comparative Example 1.
  • Example 1 the distribution ratio of the high-boiling-point by-products in the aggregate was significantly increased, and the aggregation conditions were controlled so that adhesive aggregates were precipitated. Separation proceeded, and almost the entire amount of precipitated aggregates adhered to the inside of the mixing tank, specifically to the stirring blades and introduction pipe in the glass container. Furthermore, by dissolving and recovering the deposits from the mixing tank, the rhodium complex catalyst could be recovered at a high yield. From the results shown in Table 2, the rhodium complex catalyst recovered in Example 1 had catalytic performance equivalent to that of a complex catalyst using a commercially available rhodium-based catalyst in the production of aldehyde.
  • Comparative Example 1 the high-boiling-point by-product distribution ratio in the crystallized product was low, so the obtained crystallized product crystallized as non-sticky crystals.
  • the form of the crystallization treatment liquid was in a uniform slurry state.
  • the recovery rate of the rhodium complex catalyst was low.

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EP4450484A4 (en) 2025-08-27
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