JP2012046429A - Method of producing aldehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an economically useful method of producing an aldehyde according to a hydroformylation reaction, capable of easily enhancing the selectivity of a straight chain aldehyde and of preventing adverse influence on the product quality.SOLUTION: The method of producing an aldehyde comprising feeding a 3C or higher raw material olefin, hydrogen, carbon monoxide, and an inert gas into a reactor; subjecting the mixture to a hydroformylation reaction in the presence of a complex comprising a ligand derived from an organophosphorus compound and at least one species of transition metal, to obtain a reaction mixture comprising an aldehyde produced thereby; and separating a gas comprising hydrogen and carbon monoxide from the reaction mixture to recycle and feed the gas to the reactor, is characterized by keeping the partial pressure of the inert gas in the reactor in a range of 0.10 to 10.00 MPa.

Description

  The present invention relates to a method for producing an aldehyde by a hydroformylation reaction by reacting an olefin with hydrogen and carbon monoxide in the presence of a complex containing at least one transition metal having a ligand derived from an organophosphorus compound.

A method for producing aldehydes by reacting a raw material olefin with hydrogen and carbon monoxide in the presence of a catalyst comprising a group 8-10 transition metal and an organophosphorus ligand in the periodic table is widely known as a hydroformylation reaction. It has been. In the reaction with an olefin having 3 or more carbon atoms, a linear aldehyde and a branched aldehyde are produced as shown in the formula (A).
Since linear aldehydes are more industrially useful, various techniques for increasing linear selectivity have been developed so far (in the formula (A), R is an alkyl group or the like). Represents an aliphatic hydrocarbon group).

In the old days, linear selectivity was increased by reacting rhodium with a system in which a monodentate phosphine ligand such as triphenylphosphine was added in large excess. To improve linear selectivity more efficiently, Various organophosphorus ligands have been developed (for example, Patent Document 1 and Patent Document 2).
Moreover, as a method for improving the linear selectivity of aldehydes other than the ligand, as described in Non-Patent Document 1, the reaction is performed in a highly polar solvent such as a water-acetone mixed solvent. However, it has not been described that the linearity selectivity is increased by increasing the pressure of the inert gas in the reactor.

  On the other hand, Patent Document 3 discloses a hydroformylation reaction method using an inexpensive raw gas containing hydrogen, carbon monoxide, ethylene, acetylene and the above inert gas. It is not described that the reactivity (linear selectivity) can be controlled by circulating gas to the reactor and manipulating the pressure of the inert gas in the reactor.

Japanese Patent Laid-Open No. 10-045776 JP-A-6-199728 Japanese National Patent Publication No. 11-501903

J. et al. AM. Chem. Soc. , 2003, 1990, 125, p11180

  As described above, as a method for increasing the yield of industrially useful linear aldehydes, methods such as changing ligands and solvents are known. In the process of industrial hydroformylation, these methods are known. The change takes a lot of time and costs, and there is a concern that the quality of the product may be adversely affected. Therefore, there has been a demand for an economically and industrially useful method that can increase the high selectivity of the linear aldehyde by a simple method and that does not adversely affect the quality of the product.

  This invention is made | formed in view of the said subject, Comprising: Raw material olefin of 3 or more carbon atoms, hydrogen, carbon monoxide, and an inert gas are supplied to a reactor, and it has a ligand derived from an organophosphorus compound. Providing an industrially advantageous method that can easily improve and control the linear selectivity of the aldehyde in the production of the corresponding aldehyde by carrying out the hydroformylation reaction in the presence of a complex containing one or more transition metals. There is to do.

While the present inventor has eagerly studied a method for improving the basic linear selectivity achieved under normal reaction conditions while utilizing an existing hydroformylation reaction catalyst, the hydroformylation reaction It has been found that when a gas inert to a certain amount of reaction is allowed to coexist in the system, the linear selectivity of the target product aldehyde is enhanced. Further, the present inventors have found that the linear selectivity of the target product aldehyde can be controlled by recirculating the coexisting inert gas to the reactor again and controlling the partial pressure thereof, thereby reaching the present invention. That is, the gist of the present invention resides in the following [1] to [7].
[1] Hydroformyl in the presence of a complex containing at least one transition metal having a ligand derived from an organophosphorus compound, supplying raw material olefin having 3 or more carbon atoms, hydrogen, carbon monoxide, and inert gas to the reactor In the method for producing an aldehyde, a reaction mixture containing an aldehyde produced by carrying out the conversion reaction is obtained, a gas containing hydrogen and carbon monoxide is separated from the reaction mixture, and the gas is circulated to the reactor. A method for producing an aldehyde, wherein the partial pressure of the inert gas in the vessel is 0.10 to 10.00 MPa.
[2] The method for producing an aldehyde according to [1], wherein the transition metal is a transition metal of Groups 8 to 10 of the periodic table.
[3] The inert gas includes one or more selected from the group consisting of nitrogen, helium, argon, carbon dioxide, methane, ethane, propane, and butane [1] or [2] A method for producing an aldehyde as described in 1. above.
[4] The method for producing an aldehyde according to any one of claims 1 to 3, wherein the inert gas is nitrogen.
[5] The method for producing an aldehyde according to any one of [1] to [4], wherein the partial pressure of the inert gas in the reactor is 0.5 MPa or more.
[6] The method for producing an aldehyde according to any one of [1] to [5], wherein the partial pressure of the inert gas in the reactor is 1.0 MPa or more.
[7] Hydrogen, carbon monoxide, and an inert gas are obtained by a coal gasification reaction gas obtained by a reaction between coal and an oxygen-containing gas or air, or by a partial oxidation reaction between a natural gas and an oxygen-containing gas or air. The method for producing an aldehyde according to any one of [1] to [6], which is obtained from the obtained multicomponent synthesis gas.

  According to the present invention, in a method for producing an aldehyde by reacting a raw material olefin with hydrogen and carbon monoxide in the presence of a catalyst, the linear selectivity of the aldehyde of the catalyst itself is further increased, and the linear selectivity Can be easily controlled.

It is the graph which plotted the value of n / i ratio (ratio of normal butyraldehyde and isobutyraldehyde) of butyraldehyde which is a target product to the value of nitrogen partial pressure in a reactor in Examples 1-3 of the present invention. . It is the graph which plotted the value of n / i (ratio of normal butyraldehyde and isobutyraldehyde) of butyraldehyde which is a target product to the value of nitrogen partial pressure in a reactor in Examples 4-6 of the present invention. It is the graph which plotted the value of n / i (ratio of normal butyraldehyde and isobutyraldehyde) of butyraldehyde which is a target product to the value of nitrogen partial pressure in a reactor in Examples 7-9 of the present invention.

Hereinafter, the present invention will be described in detail. The following description is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents.
In the method for producing an aldehyde of the present invention, a hydroformylation reaction is performed by reacting a raw material olefin with hydrogen and carbon monoxide in the presence of a complex containing at least one transition metal having a ligand derived from an organophosphorus compound. Generate.

  In the present invention, the transition metal is not particularly limited, but a transition metal of Groups 8 to 10 (according to IUPAC Inorganic Chemical Nomenclature Revision (1998)) is preferable. Specifically, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and the like are mentioned, and because of high reaction activity, preferably ruthenium, rhodium, cobalt, palladium, platinum, More preferred is rhodium. The transition metal may be used alone or in combination of two or more.

  When these metals are used as the complex of the hydroformylation reaction of the present invention, usually, a compound containing the metal (hereinafter sometimes abbreviated as a metal compound) is used. Specific examples of the metal compound include iron compounds. , Ruthenium compounds, osmium compounds, cobalt compounds, rhodium compounds, iridium compounds, nickel compounds, palladium compounds, and platinum compounds. Among them, a ruthenium compound, a rhodium compound, a cobalt compound, a palladium compound, and a platinum compound are preferable because of high reaction activity, and a rhodium compound is more preferable.

Specific examples of these metal compounds include inorganic salts such as halogen compounds, sulfates, nitrates, acetates, acetylsetonate compounds, alkene coordination compounds, amine coordination compounds, pyridines. Examples include coordination compounds, carbon monoxide coordination compounds, phosphine coordination compounds, and phosphite coordination compounds.
Specific examples of the iron compound include Fe (OAc) ₂ , Fe (acac) ₃ , FeCl ₂ , F
e (NO ₃ ) _{3 and the} like. Examples of the ruthenium compound include RuCl ₃ , Ru (OAc) ₃ , Ru (acac) ₃ , RuCl ₂ (PPh ₃ ) _{3 and the} like. Examples of the osmium compound include OsCl ₃ and Os (OAc) ₃ . Examples of the cobalt compound include Co (OAc) ₂ , Co (acac) ₂ , CoBr ₂ , and Co (NO ₃ ) ₂ . Rhodium compounds include RhCl ₃ , RhI ₃ , Rh (NO ₃ ) ₃ , Rh (OAc) ₃ , RhCl (CO
) (PPh ₃ ) ₂ , RhH (CO) (PPh ₃ ) ₃ , RhCl (PPh ₃ ) ₃ , Rh (acac) ₃ , Rh (acac) (CO) ₂ , Rh (acac) (cod), [Rh ( OAc) ₂ ] ₂ , [Rh (OAc) ₂ ] ₂ , [Rh (OAc) (cod)] ₂ , [RhCl (CO)] ₂ , [RhCl (cod)] ₂ , Rh ₄ (CO) _12, etc. Can be mentioned. Examples of the iridium compound include IrCl ₃ , Ir (OAc) ₃ , and [IrCl (cod)] ₂ . Examples of the nickel compound include NiCl ₂ , NiBr ₂ , Ni (NO ₃ ) ₂ , NiSO ₄ , Ni (cod) ₂ , NiCl ₂ (PPh ₃ ) _{3 and the} like. Examples of palladium compounds include PdCl ₂ and PdCl _2.
(Cod), PdCl ₂ (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ , Pd ₂ (dba) ₃ , K ₂ PdC
Examples include l ₄ , PdCl ₂ (CH ₃ CN) ₂ , Pd (NO ₃ ) ₂ , Pd (OAc) ₂ , PdSO ₄ , Pd (acac) _{2 and the} like. Platinum compounds include Pt (acac) ₂ , PtCl ₂ (c
od), PtCl ₂ (CH ₃ CN) ₂ , PtCl ₂ (PhCN) ₂ , Pt (PPh ₃ ) ₄ , K ₂ PtCl ₄ , Na ₂ PtCl ₆ , H ₂ PtCl ₆ (wherein the above examples) In
cod represents 1,5-cyclooctadiene, dba represents dibenzylideneacetone, acac represents an acetylacetonato group, Ac represents an acetyl group, and Ph group represents a phenyl group. ).

  In the present invention, the form of the metal compound described above is not particularly limited, and the active metal complex species may be a monomer, a dimer and / or a multimer. In addition, when using these metal compounds, one kind of specific metal compound may be used, the same metal species may be used in combination with a plurality of compounds, or compounds of two or more different metal species May be used together.

  The amount of the metal compound used is not particularly limited, but from the viewpoint of catalyst activity and economy, the transition metal compound concentration in the reaction liquid in the reactor is usually 0.1 wtppm or more, preferably 1 wtppm or more. Preferably it is 10 wtppm or more. On the other hand, it is usually 10000 wtppm or less, preferably 1000 wtppm or less, more preferably 500 wtppm or less.

  The organophosphorus compound that can be used in the present invention is not particularly limited as long as it is stable under the hydroformylation reaction conditions and coordinates to a transition metal with a phosphorus atom in the reaction system. Usually, a phosphine compound, a phosphinite compound, Trivalent organic phosphorus compounds such as phosphonite compounds and phosphite compounds can be used. In addition, for these compounds, bidentate or multidentate organophosphorus compounds coordinated with two or more phosphorus atoms to the transition metal can be equally used, as well as PN type, P Bidentate organophosphorus compounds such as -S type and PO type can also be used equally. The molecular weight of the organophosphorus compound is preferably dissolved in the reaction system in order to increase the catalytic activity, and is usually 3000 or less, preferably 2000 or less, more preferably 1500 or less, usually 50 or more, preferably 100 or more, More preferably, it is 150 or more.

Specific examples of the organic phosphorus compound include phosphine compounds such as trimethylphosphine, triphenylphosphine, 1,4-bis (diphenylphosphino) butane, P (OEt) Me ₂ , P (OPh) Ph ₂ , Ph ₂ POCH _2. Phosphinite compounds such as CH ₂ OPPh ₂ , phosphonite compounds such as P (t-Bu) (On-Bu) ₂ and PMe (OPh) ₂ , P (OEt) ₃ , P (OMe) (OPh) ₂ , P Phosphite compounds such as (OMe) (Ot-Bu) (Oi-Pr), aminophosphines such as PPh ₂ (NEt ₂ ), P (NMe ₂ ) ₃ and P (OPh) (NPh ₂ ) ₂ compound, P as others _{(SPh) 3, P (SMe} ) (NEt 2) (OPh), P (OCOMe) 3, P (SiMe 3) 2 (OPh), other such P (SeMe) _3, the following (M-1) can be exemplified ~ compound of structure represented by (M-12), etc., various bidentate chelate ligand having a trivalent phosphorus compound. In this specification, Ph is a phenyl group, Me is a methyl group, Et is an ethyl group, i-Pr is an i-propyl group, t-Bu is a t-butyl group, and n-Bu is n. Each represents a butyl group;

Among the above organic phosphorus compounds, phosphite compounds or phosphine compounds are preferable.
Although the kind in particular of a phosphite compound is not restrict | limited, As a preferable thing, the compound of the structure represented by the following general formula (I)-(VI) is mentioned.

In the general formulas (I) to (IV), R ^{10 to} R ²¹ each independently represent a chain or cyclic alkyl group or aryl group. Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, hexyl, octyl, decyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like. Examples of aryl groups include phenyl, tolyl, xylyl, di-t-butylphenyl, naphthyl, di-t-butylnaphthyl, pyridyl, pyrrolyl, pyrazolyl, imidazolyl, quinolyl, Examples thereof include an isoquinolyl group, an indolyl group, a furanyl group, a thiophenyl group, an oxazolyl group, and a thiazolyl group.

Note that the above-described alkyl group and aryl group may further have a substituent. The substituent is not particularly limited as long as it does not adversely affect the reaction system. Specifically, a hydroxy group, a halogen atom, a cyano group, a nitro group, a formyl group, an alkyl group, an alkoxy group, An aryl group, aryloxy group, amino group, amide group, perfluoroalkyl group, trialkylsilyl group, ester group and the like are preferable.

The number of carbon atoms of R ¹⁰ to R ²¹ is usually 1 to 40, preferably 1 to 30, more preferably 1 to 20. When the above-described alkyl group or aryl group further has a substituent, the total number of carbon atoms including the substituent is set in the above range.
Among the above exemplified groups, in view of the stability of the phosphite described above, R ^{10 to} R ²¹ are preferably unsubstituted or substituted aryl groups. Specific examples of the unsubstituted or substituted aryl group include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group, 2-isopropylphenyl group, 2-t-butylphenyl group, 2,4-di-t-butylphenyl group, 2- Chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 4- Trifluoromethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-di Toxiphenyl group, 4-cyanophenyl group, 4-nitrophenyl group, pentafluorophenyl group, 1-naphthyl group, 2-naphthyl group, 2-methyl-1-naphthyl group, 3-t-butyl-2-naphthyl group 3-methyloxycarbonyl-2-naphthyl group, 3,6-di-t-butyl-2-naphthyl group, 5,6,7,8-tetrahydronaphthalen-2-yl group, 5,6,7,8 -Tetrahydronaphthalen-1-yl group etc. are mentioned.

Z ^{1 to} Z ⁴ and A ^{1 to} A ³ each independently represent a divalent organic group. The type is not particularly limited as long as it does not adversely affect the reaction system, but an unsubstituted or substituted alkylene group, arylene group, alkylene-arylene group, or diarylene group is preferable. Z ¹ to Z ⁴ and the number of carbon atoms of each of A ¹ to A ³ is usually 1 to 60. Among them, in the case of an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group, or an unsubstituted or substituted alkylene-arylene group, the carbon number is usually 40 or less, preferably 30 or less, more preferably 20 or less. It is. On the other hand, in the case of an unsubstituted or substituted diarylene group, the carbon number is usually 60 or less, preferably 50 or less, and more preferably 40 or less.

  The alkylene group may be linear or cyclic. Preferred examples of the substituent that the alkylene group may have include a hydroxy group, a halogen atom, a cyano group, a nitro group, a formyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, an amide group, Examples include a perfluoroalkyl group, a trialkylsilyl group, and an ester group. Specific examples of the unsubstituted or substituted alkylene group include an ethylene group, a tetramethylethylene group, a 1,3-propylene group, a 2,2-dimethyl-1,3-propylene group, and a 1,4-butylene group. It is done.

  Preferable examples of the substituent that the arylene group may have include the same groups as the preferable examples of the substituent that the alkylene group may have. Specific examples of the unsubstituted or substituted arylene group include 1,2-phenylene group, 1,3-phenylene group, 3,5-di-t-butyl-1,2-phenylene group, and 2,3-naphthylene group. 1,4-di-t-butyl-2,3-naphthylene group, 1,8-naphthylene group and the like.

  Preferable examples of the substituent that the alkylene-arylene group may have include the same groups as the preferable examples of the substituent that the alkylene group may have. Specific examples of the unsubstituted or substituted alkylene-arylene group include substituents having structures represented by the following formulas (D-1) to (D-12).

A diarylene group is a group in which two arylene groups are linked directly or via a divalent organic group, and is specifically represented by —Ar ¹ — (Q ¹ ) _n —Ar ² —. A group having a structure. Here, Ar ¹ and Ar ² each independently represent an arylene group which may have a substituent. Q ¹ represents a divalent organic group. Specific examples thereof include -O- and -S-.
, -CO-, or -CR ¹⁸ R ¹⁹ - group represented by the like. Here, R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. n represents 0 or 1. Preferable specific examples of the substituent that each of the arylene group of Ar ¹ and Ar ² and the alkyl group and aryl group of R ¹⁸ and R ¹⁹ may have may include the above-described alkylene group. Examples thereof include the same groups as the preferable examples of good substituents. Specific examples of such diarylene groups include groups having structures represented by the following formulas (A-1) to (A-48).

As described above, phosphites having various structures can be used depending on the combination of substituents constituting the phosphite compounds represented by the general formulas (I) to (IV). Among them, specific examples are preferable. Trimethyl phosphite, triethyl phosphite, tri-i-propyl phosphite, triallyl phosphite, trioctadecyl phosphite, ethyl di-t-butyl phosphite, 2-ethylhexyl diethyl phosphite, dibenzyl-i-propyl phosphite Phyto, diisodecyl allyl phosphite, tris (3-methoxypropyl) phosphite, tri (2-butenyl) phosphite, tris (2,2,2-trifluoroethyl) phosphite, tris (3-chloropropyl) phosphite , Tricyclohexyl phosphite Diisooctyl-2,3-dibromo-1-propyl phosphite, trimethylolpropane phosphite, dimethylphenyl phosphite, ethylphenyl (n-propyl) phosphite, benzyldiphenyl phosphite, triphenyl phosphite, tris (2,4 -Di-t-butylphenyl) phosphite, tris (3,6-di-t-butyl-2-naphthyl) phosphite, 2-t-butylphenyl-1-naphthyl-4-methoxyphenylphosphite, Mention may be made of monodentate phosphites having structures represented by the formulas (P-1) to (P-20) and bidentate phosphites having structures represented by the following formulas (L-1) to (L-56). Can do.

Among the phosphite compounds exemplified above, bidentate phosphite compounds having a structure represented by the above general formulas (IV) to (VI) are preferable. As specific examples, the above formulas (L-6) to ( The phosphite compound of L-56) is preferred. Furthermore, in order to improve the stability of the phosphite compound, R ^{10 to} R ²¹ are each independently an unsubstituted or substituted aryl group, and Z ^{1 to} Z ⁴ and A ^{1 to} A ³ are each independently A substituted or substituted diarylene group is preferred, and specific examples of such a bidentate phosphite are the above formulas (L-24) to (L-30), (L-45), (L -46) and (L-52) to (L-56). Among them, the phosphite compound of the above general formula (IV) is most preferable, and specific examples thereof include the compounds of the above formulas (L-24) to (L-30).

  On the other hand, the type of the phosphine compound is not particularly limited, and preferred examples include compounds having a structure represented by the following general formula (VII) or general formula (VIII).

In the general formula (VII) and the general formula (VIII), R ^{31 to} R ³⁷ are each independently
A chain or cyclic alkyl group or an aryl group is represented. Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, hexyl, octyl, decyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like. Examples of aryl groups include phenyl, tolyl, xylyl, di-t-butylphenyl, naphthyl, di-t-butylnaphthyl, pyridyl, pyrrolyl, pyrazolyl, imidazolyl, quinolyl, Examples thereof include an isoquinolyl group, an indolyl group, a furanyl group, a thiophenyl group, an oxazolyl group, and a thiazolyl group.

  Note that the above-described alkyl group and aryl group may further have a substituent. The substituent is not particularly limited as long as it does not adversely affect the reaction system. Specifically, a hydroxy group, a halogen atom, a cyano group, a nitro group, a formyl group, an alkyl group, an alkoxy group, An aryl group, aryloxy group, amino group, amide group, perfluoroalkyl group, trialkylsilyl group, ester group and the like are preferable.

The number of carbon atoms of R ³¹ to R ³⁷ is usually 1 to 40, preferably 1 to 30, more preferably 1 to 20. When the above-described alkyl group or aryl group further has a substituent, the total number of carbon atoms including the substituent is set in the above range.
In view of the stability of the above-mentioned phosphine among the above exemplified groups, R ^{31 to} R ³⁷ are preferably unsubstituted or substituted aryl groups. Specific examples of the unsubstituted or substituted aryl group include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group,
2,6-dimethylphenyl group, 2-ethylphenyl group, 2-isopropylphenyl group, 2-t-butylphenyl group, 2,4-di-t-butylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 4-trifluoromethylphenyl group, 2- Methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group, 4-cyanophenyl group, 4-nitrophenyl group, pentafluorophenyl group, 1-naphthyl group, 2-naphthyl group 2-methyl-1-naphthyl group, 3-t-butyl-2-naphthyl group, 3-methyloxycarbonyl 2-naphthyl group, 3,6-di-t-butyl-2-naphthyl group, 5,6,7,8-tetrahydronaphthalen-2-yl group, 5,6,7,8-tetrahydronaphthalen-1-yl Groups and the like.

A ¹¹ represents a divalent organic group. The type is not particularly limited as long as it does not adversely affect the reaction system, but an unsubstituted or substituted alkylene group, arylene group, alkylene-arylene group, or diarylene group is preferable. Z ¹ to Z ³ and the number of carbon atoms of each of A ¹ to A ³ is usually 1 to 60. Among them, in the case of an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group, or an unsubstituted or substituted alkylene-arylene group, the carbon number is usually 40 or less, preferably 30 or less, more preferably 20 or less. It is. On the other hand, in the case of an unsubstituted or substituted diarylene group, the carbon number is usually 60 or less, preferably 50 or less, and more preferably 40 or less.

  The alkylene group may be linear or cyclic. Preferred examples of the substituent that the alkylene group may have include a hydroxy group, a halogen atom, a cyano group, a nitro group, a formyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, an amide group, Examples include a perfluoroalkyl group, a trialkylsilyl group, and an ester group. Specific examples of the unsubstituted or substituted alkylene group include an ethylene group, a tetramethylethylene group, a 1,3-propylene group, a 2,2-dimethyl-1,3-propylene group, and a 1,4-butylene group. It is done.

  Preferable examples of the substituent that the arylene group may have include the same groups as the preferable examples of the substituent that the alkylene group may have. Specific examples of the unsubstituted or substituted arylene group include 1,2-phenylene group, 1,3-phenylene group, 3,5-di-t-butyl-1,2-phenylene group, and 2,3-naphthylene group. 1,4-di-t-butyl-2,3-naphthylene group, 1,8-naphthylene group and the like.

Preferable examples of the substituent that the alkylene-arylene group may have include the same groups as the preferable examples of the substituent that the alkylene group may have. Specific examples of the unsubstituted or substituted alkylene-arylene group include (D-1) to (D-12) described above.
As the diarylene group, a diarylene group which may have a divalent linking group between two arylene groups and at both ends, specifically, — (Q ¹¹ ) _a —Ar ¹¹ — (Q ²⁰ ) _c —Ar ¹² - (Q ¹²⁾ _b - group having the structure represented by may be mentioned as a ^11. Here, Ar ¹¹ and Ar ¹² each independently represent an arylene group which may have a substituent. Q ¹¹ and Q ¹²
Each independently represents a methylene group which may have a substituent. Q ²⁰ represents a divalent organic group. Specific examples thereof include —O—, —S—, —CO—, and —CR ⁴¹ R ⁴² —. Here, R ⁴¹ and R ⁴² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. a, b, and c each independently represents 0 or 1; Preferable specific examples of the substituent that each of the arylene group of Ar ¹¹ and Ar ¹² and the alkyl group and aryl group of R ⁴¹ and R ⁴² may have may include the above-described alkylene group. Examples thereof include the same groups as the preferable examples of good substituents. Among them, specific examples of the group preferable as A ¹¹ include the compounds of the formulas (A-1) to (A-48) described above when a = b = 0, and in the other cases, the following formula ( And groups having the structures represented by B-1) to (B-20).

As described above, phosphines having various structures can be used depending on the combination of substituents constituting the phosphine compounds represented by the general formulas (VII) and (VIII).
Among them, preferred examples include trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-nonylphosphine, methyldiphenylphosphine, di-n-octyl-2-naphthylphosphine, bis (4-fluorophenyl) isopropylphosphine, tri Phenylphosphine, tris (2,4,6-trimethylphenyl) phosphine, 2-chlorophenyl-4-methoxyphenyl-3,6-di-t-butyl-2-naphthylphosphine, the following (P-21) to (P Monodentate phosphines such as -36) and 1,2-bis (di-t-butylphosphino) ethane, 1,3-bis (diethylphosphino) propane, 1,4-bis (dimethylphosphino) -1 , 1,4,4-tetramethylbutane, 1,2-bis (diphenyl) Phosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,5-bis (diphenylphosphino) pentane, 1,6-bis (diphenylphosphino) Examples thereof include bidentate phosphines such as hexane and (L-57) to (L-80).

Among the phosphines exemplified above, triphenylphosphine is particularly preferable among the monodentate phosphines having the structure represented by the general formula (VII), and among the bidentate phosphines having the structure represented by the general formula (VIII). Compounds of the above formulas (L-57) to (L-80) are preferred. These organic phosphorus compounds may be reacted using only one type of organic phosphorus compound or may be reacted using any combination of two or more types of organic phosphorus compounds.

The amount of the organophosphorus compound used is usually 0.1 or more, preferably 0.5 or more, particularly preferably 1.0 or more, and usually 10,000 or less, preferably as a ratio (molar ratio) to the transition metal compound. Is in the range of 500 or less, particularly preferably 100 or less.
In the present invention, a complex containing at least one transition metal having a ligand derived from an organophosphorus compound is present in the reactor to carry out the hydroformylation reaction. The metal compound and organophosphorus compound described above are independent of each other. Even if the complex is formed in the reactor by supplying it to the reactor, the complex may be formed in advance before the hydroformylation reaction, and the complex may be supplied to the reactor. Alternatively, an organic phosphorus compound bonded to an insoluble resin carrier may be supplied to the reactor as an insoluble solid catalyst in which the above metal compound is supported.

  The raw material olefin applied to the method for producing an aldehyde of the present invention is not particularly limited as long as it is an olefin having 3 or more carbon atoms and having at least one olefinic double bond in the molecule. Any olefin such as an olefin substituted only by a saturated hydrocarbon group, an olefin substituted by a hydrocarbon group containing an unsaturated hydrocarbon group, or an olefin substituted by a functional group containing a hetero atom It can also be applied to.

  Specific examples include olefins substituted only with saturated hydrocarbon groups: propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene. Linear terminal olefins such as 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and 1-docosene, branched terminal olefinic hydrocarbons such as isobutene and 2-methyl-1-butene, cis and trans Linear internals such as 2-butene, cis and trans-2-hexene, cis and trans-3-hexene, cis and trans-2-octene, cis and trans-3-octene, cis and trans-4-octene Octene obtained by dimerization of olefins and butenes, lower olefins such as propylene, 1-butene and isobutene Mer ~ terminal olefinic hydrocarbon-internal olefinic hydrocarbon mixtures olefin oligomer isomer mixtures, such as tetramers, and the like.

  Examples of olefins substituted with hydrocarbon groups containing unsaturated hydrocarbon groups include olefins having aromatic groups such as styrene, α-methylstyrene, allylbenzene, 1,3-butadiene, 1,5-hexadiene. And diene compounds such as 1,7-octadiene. Other examples of the olefin substituted with a functional group containing a hetero atom include ethers having an olefinic double bond such as vinyl ethyl ether, allyl-n-propyl ether, 1-methoxy-2,7-octadiene, Olefinic double bonds such as allyl alcohol, 1-hexen-4-ol, 3-methyl-3-buten-1-ol, 3-hydroxy-1,7-octadiene, 1-hydroxy-2,7-octadiene In addition to esters having an olefinic double bond such as alcohols having vinyl acetate, methyl acrylate, methyl methacrylate, 1-acetoxy-2,7-octadiene, 3,4-diacetoxy-1-butene, Examples include octen-1-al and acrylonitrile.

  The aldehyde produced by the aldehyde production method of the present invention is an aldehyde having 4 or more carbon atoms, and a hydrogen atom and a formyl group (aldehyde group: —CHO group) with respect to the olefinic double bond of the raw material olefin described above. The structure is not particularly limited as long as it is an aldehyde having a structure added thereto. However, since there are two types of bonds as described in the above formula (A) in the method of adding a hydrogen atom and a formyl group to an olefinic double bond, a linear aldehyde and a branched aldehyde Produces.

Specifically, an aldehyde produced from an olefin substituted only by a saturated hydrocarbon group, an aldehyde produced from an olefin substituted by a hydrocarbon group containing an unsaturated hydrocarbon group, or a functional group containing a hetero atom Examples thereof include aldehydes produced from the produced olefins.
As specific examples for each, aldehydes generated from olefins substituted only with saturated hydrocarbon groups include n-butyraldehyde, n-pentylaldehyde, n-hexylaldehyde, n-heptylaldehyde, n Nonyl aldehyde, n-decyl aldehyde, n-undecyl aldehyde, n-tridecyl aldehyde, n-pentadecyl aldehyde, n-heptadecyl aldehyde, n-nonadecyl aldehyde, n-heneicosyl aldehyde, n-tricosyl Linear aldehydes such as aldehyde, i-butyraldehyde, 2-methylbutyraldehyde, 2-methylpentylaldehyde, 2-methylhexylaldehyde, 2-methyloctylaldehyde, 2-methylnonylaldehyde, 2-methyldecylaldehyde, 2-me Ludodecylaldehyde, 2-methyltetradecylaldehyde, 2-methylhexadecylaldehyde, 2-methyloctadecylaldehyde, 2-methyleicosylaldehyde, 2-methyldocosylaldehyde, 3-methylbutyraldehyde, 3-methylpentylaldehyde, In addition to branched aldehydes such as 2-ethylpentylaldehyde, 2-ethylheptylaldehyde, and 2-propylhexylaldehyde, dimerization of butenes such as 2,3-dimethylheptylaldehyde and 2,5-dimethylheptylaldehyde From olefins obtained from terminal olefinic hydrocarbons such as olefin oligomer isomer mixtures such as dimers to tetramers of lower olefins such as octene, propylene, 1-butene and isobutene obtained Aldehyde or the like for growth, and the like.

  Examples of aldehydes generated from olefins substituted with hydrocarbon groups containing unsaturated hydrocarbon groups include 2-phenylpropylaldehyde, 3-phenylpropylaldehyde, 3-phenylbutyraldehyde, 4-phenylbutyraldehyde, Aldehyde having an aromatic group such as 3-phenyl-2-methylpropylaldehyde, 2-pentenylaldehyde, 3-pentenylaldehyde, 4-pentenylaldehyde, 2-methyl-2-butenylaldehyde, 2-methyl-3- Examples thereof include aldehydes having an unsaturated aliphatic group such as butenyl aldehyde, 6-heptenyl aldehyde, 2-methyl-5-hexenyl aldehyde, 8-nonenyl aldehyde, and 2-methyl-7-octenyl aldehyde.

Other examples of aldehydes generated from olefins substituted with functional groups containing heteroatoms include 2-ethoxypropyl aldehyde, 3-ethoxypropyl aldehyde, 2- (n-propoxymethyl) propyl aldehyde, 4- (n- Propoxy) butyraldehyde, 2-methoxymethyl-7-octenylaldehyde, 2- (2′-methoxyethyl) -6-heptenylaldehyde, 8-methoxy-2-methyl-6-heptenylaldehyde, 9-methoxy- Aldehydes containing ether groups such as 7-nonenylaldehyde, 4-hydroxybutyraldehyde, 3-hydroxy-2-methylpropylaldehyde, 5-hydroxyheptylaldehyde, 4-hydroxy-2-methylhexylaldehyde, 5-hydroxy -3-methylpentylal Dehydr, 4-hydroxy-8-nonenyl aldehyde, 3-hydroxy-2-methyl-7-octenyl aldehyde, 9-hydroxy-7-nonenyl aldehyde, 8-hydroxy-2-methyl-6-octenyl aldehyde, etc. Aldehydes containing 2-hydroxyl group, 2-acetoxypropylaldehyde, 3-acetoxypropylaldehyde, 3-methoxycarbonylbutyraldehyde, 2-methoxycarbonylpropylaldehyde, 3-methoxycarbonylpropylaldehyde, 2-acetoxymethyl-7-octenyl In addition to aldehydes containing 2- (2′-acetoxyethyl) -6-heptenylaldehyde, 4,5-diacetoxypentylaldehyde, 3,4-diacetoxy-2-methylbutyraldehyde ester groups, nonane -1, Examples include aldehydes containing other formyl groups such as 9-diar, aldehydes containing cyano groups such as 2-cyanopropyl aldehyde, and the like.

In the present invention, the reaction can be carried out in the presence or absence of a solvent. When using a solvent, the above-described metal compound, organophosphorus compound, and raw material olefin are dissolved at least partly, and any solvent that does not adversely affect the reaction activity or selectivity of the hydroformylation reaction is used. There is no particular limitation.
Specific examples in the case of using a solvent include, in addition to water, ethers such as diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), diphenyl ether, dibenzyl ether, diallyl ether, tetrahydrofuran (THF), dioxane and the like. Amides such as N-methyl-2-pyrrolidone, dimethylformamide, N, N-dimethylacetamide, esters such as ethyl acetate, butyl acetate, ethyl butyrate, butyl butyrate, γ-butyrolactone, di (n-octyl) phthalate , Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and dodecylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and dodecane, halogens such as chloroform, dichloromethane and carbon tetrachloride Nitriles such as hydrogenated hydrocarbon, acetonitrile, propionitrile, benzonitrile, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butyl alcohol, n-pentanol, neopentyl alcohol, Examples include alcohols such as n-hexanol, 2-ethylhexanol, n-octanol, n-nonanol, and n-decanol.

In addition, it has a higher boiling point than aldehydes which are target products such as alcohols which are hydrogenated aldehydes produced as by-products of the hydroformylation reaction of the present invention, acetal reactants of aldehydes, esters and aldol condensates. The compound which has is also mentioned.
The amount of the solvent when using the solvent is usually 5% by weight or more, preferably 10% by weight or more, and usually 95% by weight or less, preferably 90% by weight with respect to the total weight of the reaction liquid in the reactor. % Or less. The solvent may be a single compound or a mixture of a plurality of compounds.

  Next, reaction conditions for carrying out the hydroformylation reaction for producing the aldehyde of the present invention will be described. It is generated by carrying out the reaction pressure in the reactor, that is, the partial pressure of hydrogen, the partial pressure of carbon monoxide, the partial pressure of inert gas, the partial pressure of raw material olefin, and the hydroformylation reaction in the reactor. The sum of the vapor pressures of the reaction mixture containing aldehyde (and, when a solvent is used if necessary, the value obtained by adding the vapor pressure of the solvent to the reaction pressure) is not particularly limited, but is usually 0.01 MPa or more The pressure is preferably 0.10 MPa or more, more preferably 0.50 MPa or more, and usually 30.00 MPa or less, preferably 20.00 MPa or less, more preferably 10.00 MPa or less. If the reaction pressure is too low, the transition metal of the complex containing one or more transition metals used in the reaction may be metallized and deactivated, and the activity of the hydroformylation reaction may not be sufficiently expressed, and aldehyde Yield may be reduced. On the other hand, if the reaction pressure, particularly hydrogen partial pressure and carbon monoxide partial pressure are too high, the loss of raw olefins due to hydrogenation of raw olefins increases, or the linear selection of the target product aldehyde obtained. There is a risk that the sex will decline. In particular, the partial pressure of hydrogen is preferably 0.005 MPa or more, more preferably 0.01 MPa or more, and preferably 20 MPa or less, more preferably 10 MPa or less. If the partial pressure of hydrogen is too low, the reaction activity may be lowered, and if the partial pressure of hydrogen is too high, the raw material olefin may be wasted due to the progress of the hydrogenation reaction of the raw material olefin. The partial pressure of carbon monoxide is preferably 0.005 MPa or more, more preferably 0.01 MPa or more, while it is preferably 15 MPa or less, more preferably 8 MPa or less. If the partial pressure of carbon monoxide is too low, there is a concern about reduction in reaction activity, particularly metalation of transition metals in the complex, and if it is too high, reduction in linear selectivity of the resulting alcohol is expected.

In the present invention, the molar ratio of hydrogen to carbon monoxide supplied to the reactor is 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and still more preferably 1: 2 to 2. 2: 1.
The reaction temperature in the reactor is usually 25 ° C. or higher, preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and is usually 200 ° C. or lower, preferably 170 ° C. or lower, more preferably 150 ° C. or lower. It is. If the reaction temperature is too low, the reaction activity itself may not be sufficiently obtained, and if the reaction temperature is too high, the linear selectivity of the target product aldehyde obtained may be reduced, or the resulting aldehyde may be subjected to aldol condensation. The yield of the product may decrease due to the progress, and the organophosphorus compound may be lost by thermal decomposition, or may be deactivated due to decomposition of the complex.

  In the present invention, the hydroformylation reaction is carried out in an atmosphere where an inert gas is present in the reactor, and the inert gas comprises nitrogen, helium, argon, carbon dioxide, methane, ethane, propane, and butane. It is 1 or more types chosen from a group, and may be used independently or may be used in mixture of 2 or more types. More preferred inert gases are nitrogen, helium, and argon, more preferred inert gases are nitrogen and argon, and the most preferred inert gas is nitrogen. In the present invention, when two or more kinds of inert gases are mixed and used, the sum of the partial pressures of the respective gases becomes the partial pressure of the inert gas.

  In the present invention, the partial pressure of the inert gas in the reactor is 0.1 MPa or more, preferably 0.5 MPa or more, more preferably 1.0 MPa or more, most preferably 1.5 MPa or more, It is 10.0 MPa or less, preferably 8.0 MPa or less, more preferably 6.0 MPa or less. By setting the partial pressure of the inert gas in the reactor within the above range, the linear selectivity of the target product aldehyde is improved. The reason is not clear, but the following is presumed. That is, in the hydroformylation reaction with a transition metal complex having a ligand derived from an organophosphorus compound, the linear selectivity of the aldehyde is mainly determined by the stereocontrol effect of the ligand, but the inert gas partial pressure is When the pressure is increased and the reaction solution is under pressure, the complex itself is considered to be in a compressed state due to pressure from the surrounding solvent / solute. In this case, the ligand derived from the organophosphorus compound is more strongly coordinated to the transition metal (closed state), and the steric control effect of the ligand is further enhanced, so that the linear selectivity of the aldehyde is increased. It is guessed. If the partial pressure of the inert gas is too low, the effect of improving the linear selectivity of the aldehyde which is a sufficient target product may not be obtained. Conversely, if it is too high, the total pressure in the reactor will increase. For this reason, it is necessary to use a reactor with high pressure resistance, which may increase the construction cost, and may increase the utility cost of the compressor for maintaining the pressure in the reactor.

In the present invention, a reaction mixture containing an aldehyde produced by performing a hydroformylation reaction is obtained. The reaction mixture means the sum of all the compositions formed in the hydroformylation reactor, and a gas composition and It can be divided roughly into liquid compositions. The gas composition will be specifically described. When hydrogen, carbon monoxide, inert gas, raw material olefin, etc. have a vapor pressure, the gas component, and further, the aldehyde produced by the hydroformylation reaction is vapor pressure. If the gas component and solvent are used, and the solvent has a vapor pressure, the gas component, the product aldehyde, the ligand derived from the organophosphorus compound, and the decomposition product of the transition metal compound If they have vapor pressure, they are gas components. Further, the liquid composition will be specifically described. When a solvent is used, the solvent, the raw material olefin, the generated aldehyde, alcohols that are by-products of the hydroformylation reaction of the present invention, an acetal reactant of the aldehyde, Compounds having a boiling point higher than the aldehyde, which is the target product, such as esters and aldol condensates, and transition metal compounds, organophosphorus compounds, transition metal compounds and organophosphorus compounds dissolved in the above liquid composition Decomposition product, dissolved gas component (the gas composition described above and dissolved in the liquid composition). The amount and ratio of the components contained in these reaction mixtures are appropriately determined depending on the reaction conditions and the yield of the target product aldehyde.

  In the present invention, the gas containing unreacted hydrogen and carbon monoxide is separated from the reaction mixture, and this gas is circulated again to the reactor. Even if separation is performed by providing a line for extracting gas at the top of the reactor, the reaction mixture is extracted from the reactor and then introduced into a gas-liquid separation device, gas stripping device, gas absorption device or extraction device. A gas containing unreacted hydrogen and carbon monoxide may be separated from the reaction mixture.

  In addition, it is preferable to separate the inert gas together with unreacted hydrogen and carbon monoxide from the reaction mixture. At this time, the inert gas may be separated alone or separated so that the inert gas is contained in the gas containing hydrogen and carbon monoxide. And it is preferable to isolate | separate from a reaction mixture so that an inert gas may be contained in the gas containing carbon monoxide.

  The gas containing unreacted hydrogen and carbon monoxide separated from the reaction mixture as described above is circulated and supplied to the reactor, but when the inert gas is separated from the reaction mixture, the inert gas is also Both are preferably circulated and fed to the reactor. The form of circulating and supplying the gas containing unreacted hydrogen and carbon monoxide to the reactor is not particularly limited, but even if a single circulation supply line is provided in the reactor and directly supplied to the reactor, The partial pressure of the inert gas in the reactor that is connected to the line for supplying the raw material olefin, hydrogen, carbon monoxide, or inert gas and may be supplied to the reactor together with these is 0.10 to 10.00 MPa. To control the inert gas in the reactor, the pressure of the inert gas supplied to the reactor is adjusted so as not to deviate from the range of 0.10 to 10.00 MPa. Good. In addition, for example, when the gas containing unreacted hydrogen and carbon monoxide is separated from the reaction mixture so as to contain an inert gas and is circulated and supplied to the reactor, the raw material newly fed to the reactor The reaction system in the latter stage of the reactor comprises the supply amount of olefin, hydrogen and carbon monoxide, the supply amount of gas containing hydrogen and carbon monoxide circulated to the reactor, and the gas components in the reaction mixture flowing out of the reactor. The amount of inert gas supplied to the reactor may be controlled in accordance with the balance of the purge amount discharged to the outside. Specifically, the partial pressure of the inert gas in the reactor can be reduced by increasing the purge amount of the gas discharged to the outside of the reaction system and decreasing the flow rate of the gas containing hydrogen and carbon monoxide supplied to the reactor. Can be kept low. Conversely, the partial pressure of the inert gas in the reactor can be kept high by reducing the purge amount of the gas discharged outside the reaction system and increasing the amount of gas containing hydrogen and carbon monoxide to be circulated and supplied to the reactor. it can.

  In the present invention, hydrogen and carbon monoxide are used as raw materials, but usually a mixed gas of hydrogen and carbon monoxide (so-called oxo gas or synthesis gas) is often used. At that time, a hydrogen and carbon monoxide mixed gas supply source and an inert gas supply source may be provided separately, but a hydrogen and carbon monoxide mixed gas containing an inert gas such as nitrogen in advance. As a specific source of such a gas, a coal gasification reaction gas obtained by a heating reaction between coal and an oxygen-containing gas or air, or a natural gas and an oxygen-containing gas or air may be used. Mention may be made of a multicomponent mixed gas obtained by a partial oxidation reaction. In these coal gasification reaction gas and natural gas partial oxidation reaction gas, air is usually used as an oxidant, and the product gas often contains several percent to several tens of percent nitrogen. Since these gases are very inexpensive compared with the hydrogen and carbon monoxide mixed gas used in a general hydroformylation reaction, this gas is used from the viewpoint of cost reduction of raw material gas and improvement of linearity selectivity. It can be suitably used in the invention.

Moreover, as a reaction system, any of continuous type, semi-continuous type, or batch type operation can be easily implemented in a stirring type reaction vessel or a bubble column type reaction vessel. Separation of a complex containing a transition metal having a ligand derived from an unreacted raw material olefin, products, and an organophosphorus compound from a reaction mixture extracted from the reactor is usually simple distillation, vacuum distillation, thin film distillation, In addition to distillation operations such as steam distillation, it can be carried out by known methods such as gas-liquid separation, evaporation (evaporation), gas stripping, gas absorption and extraction. Distillation conditions are not particularly limited, and are arbitrarily set so as to obtain desirable results in consideration of the volatility of the product, thermal stability, etc. Usually, a temperature of 50 to 300 ° C., 760 to It is selected from a range of pressure conditions of 0.01 mmHg. In performing the distillation, the use of a solvent is not essential, but if necessary, an inert solvent can be present in the products and catalyst components. From the remaining liquid containing the complex containing the transition metal having the ligand derived from the separated organophosphorus compound, the transition metal can be recovered by a known method, or the entire amount or a part of the remaining liquid is used in the reaction step. It can be recycled and reused.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.
<Example 1>
To a glass container for catalyst preparation, RhH (CO) (PPh ₃ ) ₃ (158.2 mg, 0.1722 mmol) and triphenylphosphine (PPh ₃ ) (13.25 g, 51.03 mmol, 296 of Rh under a nitrogen atmosphere. Equivalent amount), toluene (50.0 ml) and n-dodecane (5.0 ml), which is an internal standard for gas chromatography analysis, are added and dissolved, and the solution is separately prepared, and the magnetic induction up and down stirring with an internal volume of 200 ml is prepared. A stainless steel autoclave of the type was charged in a nitrogen atmosphere. Further, after propylene (4.64 g, 110.27 mmol) was injected, the autoclave was sealed, and the autoclave was heated to 100 ° C. At this time, the internal pressure of the reactor was 0.60 MPa in terms of gauge pressure, but the atmospheric pressure nitrogen gas contained at about 20 ° C. when the catalyst solution was charged was heated to 100 ° C. The nitrogen partial pressure was 0.13 MPa (however, this value is a value ignoring dissolution of nitrogen in a toluene solvent, etc.). Thereafter, the reaction was started by feeding a mixed gas of hydrogen and carbon monoxide (mixing ratio: hydrogen / carbon monoxide = 1/1) so that the internal pressure (gauge pressure) was 1.33 MPa. The partial pressure of the mixed gas of hydrogen and carbon monoxide at the initial stage of the reaction was 0.73 MPa. In addition, the mixed gas of hydrogen and carbon monoxide is changed from a constant capacity accumulator to a secondary pressure regulator so that the internal pressure can be kept at the initial reaction pressure when the gas is consumed in the reactor and the internal pressure decreases. To be automatically fed through. It is assumed that this automatic supply separates the gas containing unreacted hydrogen and carbon monoxide from the reaction mixture flowing out of the reactor and circulates it to the reactor. It becomes possible to hold | maintain to the pressure of. The reaction was carried out for 2 hours while maintaining the nitrogen partial pressure in the reactor during the hydroformylation reaction at 0.13 MPa.

After completion of the reaction, the autoclave was cooled to room temperature, the reaction solution was taken out and analyzed by gas chromatography to estimate the butyraldehyde yield. As a result, the n-butyraldehyde yield was 83.62%, the i-butyraldehyde yield was 14.75%, and the n / i ratio was 5.67. The results are shown in Table-1.
<Example 2>
In Example 1, before feeding the mixed gas of hydrogen and carbon monoxide, nitrogen gas of 1.00 MPa was introduced into the autoclave at 100 ° C., and then the mixed gas of hydrogen and carbon monoxide was fed in the same manner. Reaction was performed. However, the partial pressure in the initial reaction of the mixed gas of hydrogen and carbon monoxide was adjusted to be the same as in Example 1. The nitrogen partial pressure in the reactor in this reaction was 1.13 MPa.

As a result of the same analysis after completion of the reaction, the yield of n-butyraldehyde was 85.08%, the yield of i-butyraldehyde was 13.06%, and the n / i ratio was 6.52. Table 1 shows the results.
Shown in
<Example 3>
In Example 1, before feeding the mixed gas of hydrogen and carbon monoxide, 2.00 MPa of nitrogen gas was introduced into the autoclave at 100 ° C., and then the mixed gas of hydrogen and carbon monoxide was fed in the same manner. Reaction was performed. However, the partial pressure in the initial reaction of the mixed gas of hydrogen and carbon monoxide was adjusted to be the same as in Example 1. The partial pressure of nitrogen in the reactor in this reaction was 2.13 MPa.

As a result of the same analysis after completion of the reaction, the n-butyraldehyde yield was 85.12%, the i-butyraldehyde yield was 11.98%, and the n / i ratio was 7.11. The results are shown in Table-1.
From the results of Examples 1 to 3, the horizontal axis represents the nitrogen partial pressure in the reactor and the n / i ratio in the reaction is plotted on the vertical axis. FIG. 1 shows the nitrogen partial pressure in the reactor. As it is gradually increased, the n / i ratio is improved, and it can be seen that the selectivity for the target n-butyraldehyde increases. In addition, when the partial pressure of nitrogen in the reactor is set to an appropriate value, it is possible to achieve the desired linear selectivity of the aldehyde, so that the linear selectivity of the aldehyde can be controlled by the partial pressure of nitrogen in the reactor. .

<Example 4>
[Rh (cod) (OAc)] ₂ (19.8 mg, 0.0733 mmol as Rh) and bidentate phosphite (compound of formula L-26 in the specification) (0) in a glass vessel for catalyst preparation under nitrogen atmosphere. 3126 mg, 0.2918 mmol, 4 equivalents of Rh), toluene (50.0 ml) and n-dodecane (5.0 ml) which is an internal standard for gas chromatography analysis are added and dissolved, and the solution is separately added. The prepared magnetic induction top and bottom stirring type stainless steel autoclave with an internal volume of 200 ml was charged in a nitrogen atmosphere. Further, after propylene (4.66 g, 110.74 mmol) was injected, the autoclave was sealed and the autoclave was heated to 70 ° C. At this time, the internal pressure of the reactor showed a gauge pressure of 0.42 MPa. However, when the atmospheric nitrogen gas contained at about 20 ° C. was heated to 70 ° C. when the catalyst solution was charged, The nitrogen partial pressure was 0.12 MPa (however, this value is a value ignoring dissolution of nitrogen in a toluene solvent, etc.). Thereafter, the reaction was started by feeding a mixed gas of hydrogen and carbon monoxide (mixing ratio: hydrogen / carbon monoxide = 1/1) so that the internal pressure (gauge pressure) was 0.98 MPa. That is, the partial pressure of the mixed gas of hydrogen and carbon monoxide at the beginning of the reaction was 0.56 MPa. In addition, the mixed gas of hydrogen and carbon monoxide is changed from a constant capacity accumulator to a secondary pressure regulator so that the internal pressure can be kept at the initial reaction pressure when the gas is consumed in the reactor and the internal pressure decreases. To be automatically fed through. It is assumed that this automatic supply separates the gas containing unreacted hydrogen and carbon monoxide from the reaction mixture flowing out of the reactor and circulates it to the reactor. It becomes possible to hold | maintain to the pressure of. The reaction was carried out for 2.5 hours while maintaining the nitrogen partial pressure in the reactor during the hydroformylation reaction at 0.12 MPa.

After completion of the reaction, after completion of the reaction, the autoclave was cooled to room temperature, and the reaction solution was taken out and analyzed by gas chromatography. The n-butyraldehyde yield was 94.89% and the i-butyraldehyde yield was 1.15%. And the n / i ratio was 82.71. The results are shown in Table-1.
<Example 5>
In Example 4, 1.01 MPa of nitrogen gas was introduced into the autoclave at 70 ° C. before feeding the mixed gas of hydrogen and carbon monoxide, and then the mixed gas of hydrogen and carbon monoxide was fed in the same manner. Reaction was performed. However, the partial pressure in the initial reaction of the mixed gas of hydrogen and carbon monoxide was adjusted to be the same as in Example 4. The nitrogen partial pressure in the reactor in this reaction was 1.13 MPa.

As a result of the same analysis after completion of the reaction, the n-butyraldehyde yield was 96.41%, the i-butyraldehyde yield was 1.11%, and the n / i ratio was 86.56. The results are shown in Table-1.
<Example 6>
In Example 4, 2.05 MPa nitrogen gas was introduced into the autoclave at 70 ° C. before feeding the mixed gas of hydrogen and carbon monoxide, and then the mixed gas of hydrogen and carbon monoxide was fed in the same manner. Reaction was performed. However, the partial pressure in the initial reaction of the mixed gas of hydrogen and carbon monoxide was adjusted to be the same as in Example 4. The nitrogen partial pressure in the reactor in this reaction was 2.17 MPa.

As a result of the same analysis after completion of the reaction, the n-butyraldehyde yield was 96.46%, the i-butyraldehyde yield was 1.07%, and the n / i ratio was 89.98.
From the results of Examples 4 to 6, the nitrogen partial pressure in the reactor is plotted on the horizontal axis, and the n / i ratio in the reaction is plotted on the vertical axis. FIG. 2 shows the nitrogen partial pressure in the reactor gradually. It can be seen that the n / i ratio improves as the value increases, and the selectivity for the target product n-butyraldehyde increases. In addition, when the partial pressure of nitrogen in the reactor is set to an appropriate value, it is possible to achieve the desired linear selectivity of the aldehyde, so that the linear selectivity of the aldehyde can be controlled by the partial pressure of nitrogen in the reactor. .

<Example 7>
[Rh (cod) (OAc)] ₂ (4.95 mg, 0.0183 mmol as Rh) and bidentate phosphite (compound of formula L-56 in the specification) (0) in a glass vessel for catalyst preparation under nitrogen atmosphere. 0.0612 mg, 0.0729 mmol, 4 equivalents of Rh), toluene (50.0 ml) and n-dodecane (5.0 ml) which is an internal standard for gas chromatography analysis are added and dissolved, and the solution is separately added. The prepared magnetic induction top and bottom stirring type stainless steel autoclave with an internal volume of 200 ml was charged in a nitrogen atmosphere. Further, after propylene (4.70 g, 111.69 mmol) was injected, the autoclave was sealed and the autoclave was heated to 70 ° C. At this time, the internal pressure of the reactor was 0.40 MPa in terms of gauge pressure. However, when the atmospheric nitrogen gas contained at about 20 ° C. was heated to 70 ° C. when the catalyst solution was charged, The nitrogen partial pressure was 0.12 MPa (however, this value is a value ignoring dissolution of nitrogen in a toluene solvent, etc.). Thereafter, the reaction was started by feeding a mixed gas of hydrogen and carbon monoxide (mixing ratio: hydrogen / carbon monoxide = 1/1) so that the internal pressure (gauge pressure) was 0.86 MPa. That is, the partial pressure of the mixed gas of hydrogen and carbon monoxide at the initial stage of the reaction was 0.46 MPa. In addition, the mixed gas of hydrogen and carbon monoxide is changed from a constant capacity accumulator to a secondary pressure regulator so that the internal pressure can be kept at the initial reaction pressure when the gas is consumed in the reactor and the internal pressure decreases. To be automatically fed through. It is assumed that this automatic supply separates the gas containing unreacted hydrogen and carbon monoxide from the reaction mixture flowing out of the reactor and circulates it to the reactor. It becomes possible to hold | maintain to the pressure of. The reaction was carried out for 2 hours while maintaining the nitrogen partial pressure in the reactor during the hydroformylation reaction at 0.12 MPa.

After completion of the reaction, after completion of the reaction, the autoclave was cooled to room temperature, and the reaction solution was taken out and analyzed by gas chromatography. The n-butyraldehyde yield was 93.98% and the i-butyraldehyde yield was 2.51%. And the n / i ratio was 37.50. The results are shown in Table-1.
<Example 8>
In Example 7, before feeding the mixed gas of hydrogen and carbon monoxide, 1.02 MPa of nitrogen gas was introduced into the autoclave at 70 ° C., and then the mixed gas of hydrogen and carbon monoxide was fed in the same manner. Reaction was performed. However, the partial pressure in the initial reaction of the mixed gas of hydrogen and carbon monoxide was adjusted to be the same as in Example 7. The nitrogen partial pressure in the reactor in this reaction was 1.14 MPa.

As a result of the same analysis after completion of the reaction, the n-butyraldehyde yield was 94.01%, the i-butyraldehyde yield was 2.42%, and the n / i ratio was 38.90. The results are shown in Table-1.
<Example 9>
In Example 7, before feeding the mixed gas of hydrogen and carbon monoxide, nitrogen gas of 2.00 MPa was introduced into the autoclave at 70 ° C., and then the mixed gas of hydrogen and carbon monoxide was fed in the same manner. Reaction was performed. However, the partial pressure in the initial reaction of the mixed gas of hydrogen and carbon monoxide was adjusted to be the same as in Example 7. The nitrogen partial pressure in the reactor in this reaction was 2.12 MPa.

As a result of the same analysis after completion of the reaction, the n-butyraldehyde yield was 92.73%, the i-butyraldehyde yield was 2.22%, and the n / i ratio was 41.80. The results are shown in Table-1.
From the results of Examples 7-9, FIG. 3 shows the nitrogen partial pressure in the reactor on the horizontal axis and the n / i ratio in the reaction on the vertical axis. The nitrogen partial pressure in the reactor is shown in FIG. As it is gradually increased, the n / i ratio is improved, and it can be seen that the selectivity for the target n-butyraldehyde increases. In addition, when the partial pressure of nitrogen in the reactor is set to an appropriate value, it is possible to achieve the desired linear selectivity of the aldehyde, so that the linear selectivity of the aldehyde can be controlled by the partial pressure of nitrogen in the reactor. .

Claims (7)

  Hydroformylation reaction is performed in the presence of a complex containing at least one transition metal having a ligand derived from an organophosphorus compound by supplying raw material olefin having 3 or more carbon atoms, hydrogen, carbon monoxide, and inert gas to the reactor. In the method for producing an aldehyde, a reaction mixture containing an aldehyde generated by performing is obtained, a gas containing hydrogen and carbon monoxide is separated from the reaction mixture, and the gas is circulated to the reactor. A method for producing an aldehyde, wherein the partial pressure of the inert gas is 0.10 to 10.00 MPa.   The method for producing an aldehyde according to claim 1, wherein the transition metal is a transition metal of Groups 8 to 10 of the periodic table.   The aldehyde according to claim 1 or 2, wherein the inert gas contains one or more selected from the group consisting of nitrogen, helium, argon, carbon dioxide, methane, ethane, propane, and butane. Production method.   The method for producing an aldehyde according to any one of claims 1 to 3, wherein the inert gas is nitrogen.   The method for producing an aldehyde according to any one of claims 1 to 4, wherein the partial pressure of the inert gas in the reactor is 0.5 MPa or more.   The partial pressure in the reactor of the said inert gas is 1.0 Mpa or more, The manufacturing method of the aldehyde of any one of Claims 1-5 characterized by the above-mentioned.   Hydrogen, carbon monoxide, and inert gas can be obtained by a coal gasification reaction gas obtained by reaction of coal with an oxygen-containing gas or air, or by a partial oxidation reaction of natural gas and oxygen-containing gas or air. The method for producing an aldehyde according to any one of claims 1 to 6, which is obtained from a component synthesis gas.

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