JP2000159720A - Production of aldehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aldehyde in a high yield, while inhibiting the deactivation of a catalyst, by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of the rhodium complex catalyst containing an organic phosphite and then separating the produced aldehyde from a catalyst liquid containing the catalyst in a separation zone wherein a liquid contact portion is made from a metal material containing nickel. SOLUTION: This method for producing an aldehyde comprises reacting an olefinic compound (for example, propylene or 1-butene) with hydrogen and carbon monoxide in a solution containing a rhodium complex catalyst having an organic phosphite [for example, diphenyl(2,4-ditertiary butylphenyl)phosphite] as a ligand, separating the produced aldehyde from the reaction solution in a separation zone having a liquid contact portion, for example, by a distillation method, and then circulating the obtained catalyst liquid containing the rhodium complex catalyst to the reaction zone. Therein, the liquid contact portion is formed from a metal material containing nickel (for example, an austenite-based stainless steel containing >=>=8 wt.% of nickel).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an aldehyde by reacting an olefinic compound with hydrogen and carbon monoxide using a rhodium complex catalyst containing an organic phosphite as a ligand. In particular, the present invention relates to a method for reducing the decomposition of an organic phosphite and preventing a decrease in the activity of the catalyst when the rhodium complex catalyst is recycled.

[0002]

2. Description of the Related Art Rhodium is widely used as a catalyst for a hydroformylation reaction, and the activity and selectivity of the hydroformylation reaction can be improved by modification with a ligand such as a trivalent phosphorus compound. Is well known to those skilled in the art. Therefore, various studies have been made on trivalent phosphorus compounds used as ligands. In particular, many studies have been made in recent years on hydroformylation catalysts using an organic phosphite having high reactivity and selectivity as a ligand.

For example, JP-A-57-123134 discloses that
A method using a triaryl phosphite having a substituent at a specific position of a phenyl ring as a ligand is disclosed. JP-A-59-51228 and JP-A-59-5123
No. 0 discloses a method using a cyclic phosphite containing a phosphorus atom at a bridgehead as a ligand. Tokio Sho 6
1-501268 discloses a method using diorganophosphite having a cyclic structure as a ligand.
JP-A-62-116587 discloses a bidentate phosphite in which one of the two phosphite groups has a cyclic structure, and JP-A-62-116535 discloses that both phosphite groups are cyclic. Bidentate phosphates having the structure are disclosed. JP-A-4-290551 discloses a method using bisphosphite having a cyclic structure as a ligand. Further, Japanese Patent Application Laid-Open No.
39207 discloses a method using bisphosphite or polyphosphite having a substituent at a specific site as a ligand.

However, in order to use an organic phosphite as a ligand industrially, it is desired to improve its stability. That is, as disclosed in JP-A-59-51229, when an open type organic phosphite such as triphenyl phosphite is used as a ligand, the organic phosphite is depleted in a hydroformylation reaction system, and It is known that the catalyst activity is extremely low, and continuous replenishment of the organic phosphite is necessary.

Further, Japanese Patent Application Laid-Open No. 61-501268 discloses that triphenyl phosphite reacts quickly with aldehyde at room temperature even in the absence of rhodium. The reaction product of an organic phosphite and an aldehyde has been shown to readily hydrolyze to the corresponding hydroxyalkyl phosphonic acid. It is disclosed that this hydroxyalkylphosphonic acid promotes the decomposition of organic phosphite, and that it is possible to suppress the decomposition of organic phosphite by removing these acidic components with a weakly basic ion exchange resin. ing. JP-A-6-199728 describes that a new phosphite compound is generated by decomposition of an organic bisphosphite, and this combines with rhodium as a catalyst metal, resulting in a decrease in the activity of the catalyst. A method is disclosed in which a phosphite compound that poisons the catalyst is selectively decomposed by adding a weakly acidic compound to maintain the activity. Further, JP-A-6-199729 discloses that by adding an epoxide compound, a phosphoric acid compound generated by further decomposition of a phosphite compound poisoning a catalyst can be captured. Japanese Patent Application Laid-Open No. 9-59200 describes that Group VIII metals such as ruthenium, cobalt, palladium and platinum have an effect of suppressing decomposition of organic phosphite and insolubilization of rhodium.

[0006]

As described above, rhodium complex catalysts having an organic phosphite as a ligand, as the organic phosphite is decomposed and the catalytic activity tends to decrease, various measures have been studied. But none of them are yet satisfactory. Since rhodium is extremely expensive, when performing a hydroformylation reaction using a rhodium complex catalyst, it is extremely desirable to recover and reuse the rhodium complex catalyst from the reaction mixture without minimizing its activity. Therefore, the present invention provides a hydroformylation reaction,
It is an object of the present invention to provide a method for recycling a rhodium complex catalyst without reducing its activity as much as possible.

[0007]

According to the present invention, an olefinic compound and hydrogen and carbon monoxide are reacted in a reaction zone in the presence of a liquid phase containing at least a rhodium complex catalyst comprising rhodium and an organic phosphite. In the separation zone to separate the aldehyde from the reaction mixture removed from the reaction zone to obtain a catalyst solution containing a rhodium complex catalyst, and circulate the catalyst solution to the reaction zone. In the method for producing an aldehyde including each step of the circulation step, at least a part of the liquid contact portion of the separation zone is made of a metal material containing nickel, thereby significantly decomposing the organic phosphite constituting the rhodium complex catalyst. Thus, it is possible to prevent the catalytic activity of the rhodium complex catalyst from decreasing.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail. The hydroformylation reaction itself in the method of the present invention can be carried out according to a conventional method using a rhodium complex catalyst containing an organic phosphite as a ligand. The rhodium complex catalyst used for the reaction can be prepared according to a known method for preparing a rhodium-organophosphite complex catalyst. The rhodium complex catalyst may be prepared in advance and used in the reaction, or may be formed from a rhodium compound and an organic phosphite in the reaction system. Examples of the rhodium compound used for catalyst preparation include, for example, rhodium chloride, rhodium nitrate, rhodium acetate, rhodium formate, sodium rhodate, inorganic or organic acid salts of rhodium such as potassium rhodate, alumina, silica, activated carbon, and the like. Rhodium metal supported on a carrier, rhodium dicarbonyl acetylacetonate, a chelating compound of rhodium such as rhodium (1,5-cyclooctadiene) acetylacetonate, tetrarhodium dodecacarbonyl, hexarhodium hexadecacarbonyl, μ, μ'-dichlororhodium tetracarbonyl, [Rh (OAc) (CO
D)] ₂ (COD represents 1,5-cyclooctadiene), and a rhodium carbonyl complex compound such as [Rh (μ-St-Bu) (CO) ₂ ] ₂ .

As the organic phosphite of the ligand, any organic phosphite such as triaryl phosphite, trialkyl phosphite, and alkylaryl phosphite can be used. Bisphosphite having a plurality of these phosphato structures in the same molecule,
Polyphosphites such as tris phosphite can also be used. Among these organic phosphites, monophosphites can be broadly classified into those having no phosphorus atom-containing cyclic structure and those having such a structure. The former is represented by the following general formula (1).

[0010]

Embedded image P (OR ¹ ) (OR ² ) (OR ³ ) (1)

Wherein R ^{1 to} R ³ are each independently
A hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group,
Represents a heteroaromatic hydrocarbon group of 0, to which a substituent which does not inhibit the hydroformylation reaction may be bonded. Examples of such a substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group,
Examples include an aryl group, an alkoxy group, an alkylamino group, an acyl group, an acyloxy group, and an alkoxycarbonyl group.

In the organic phosphite represented by the general formula (1), at least ^one of R ^{1 to} R ³ is preferably a substituted aryl group represented by the following general formula (2).

[0013]

Embedded image

In the formula, R ⁴ represents an aryl group which may have a substituent which does not inhibit a hydroformylation reaction;
Or -CR ⁹ R ¹⁰ R ¹¹ . Here, R ^{9 to} R ¹¹ each independently represent a hydrogen atom or an optionally fluorinated hydrocarbon group. R ⁴ is preferably a compound having a branch at the 1-position and having a large steric hindrance, such as an isopropyl group and a t-butyl group. R ^{5 to} R ⁸ each independently represent a hydrogen atom or an organic group that does not inhibit the hydroformylation reaction. Adjacent ones of R ^{5 to} R ⁸ may be bonded to each other to form a condensed aromatic ring or condensed heterocyclic ring.

Examples of such organic phosphites include diphenyl (2,4-di-tert-butylphenyl) phosphite, diphenyl (2-isopropylphenyl) phosphite, and bis (2-tert-butyl).
Butyl-4-methylphenyl) phenyl phosphite,
Diphenyl (3,6-di-tert-butyl-2-naphthyl) phosphite, bis (2-naphthyl) (3,6-
Di-tert-butyl-2-naphthyl) phosphite,
Bis (3,6,8-tri-s-butyl-2-naphthyl) phenyl phosphite, bis (3,6,8-tri-s-butyl-2-naphthyl) (2-naphthyl)
Phosphite and the like.

Organic phosphite represented by the general formula (1)
Is particularly preferred as R¹~ R ^ThreeIs a general formula
It is a substituted aryl group represented by (2). This
Some examples of organic phosphites such as
Lis (2,4-di-tert-butylphenyl) phosph
Aite, tris (2-tert-butyl-4-methyl)
Phenyl) phosphite, tris (2-tert-butyl)
Tyl-4-methoxyphenyl) phosphite, tris
(O-phenylphenyl) phosphite, tris (o-
Methylphenyl) phosphite, bis (3,6-dita-
Shari-butyl-2-naphthyl) (2,4-ditacia)
L-butylphenyl) phosphite, bis (3,6-di
Tert-butyl-2-naphthyl) (2-tert-butyl)
-Butylphenyl) phosphite, tris (3,6-di
Tert-butyl-2-naphthyl) phosphite, g
Squirrel (3,6-dita-shary-amyl-2-naphthyl)
Phosphite and the like. Out of monophosphite
Those having a cyclic structure containing a phosphorus atom are represented by the following general formula
It is represented by (3).

[0017]

Embedded image

In the formula, Z represents a divalent hydrocarbon group which may contain a hetero atom in the carbon chain and may have a substituent which does not inhibit the hydroformylation reaction, and Y represents a hydroformylation group. It represents a hydrocarbon group or a heteroaromatic hydrocarbon group which may have a substituent which does not inhibit the reaction.
In the general formula (3), Y is preferably a substituted aryl group represented by the general formula (2). Further, Z is preferably an alkylene group, an arylene group or a hybrid group of both, which may contain a hetero atom such as an oxygen, nitrogen or sulfur atom in the carbon chain. Examples of such a divalent hydrocarbon group include an alkylene group, an alkyleneoxyalkylene group, an alkyleneaminoalkylene group in which an alkyl group may be bonded to a nitrogen atom, an alkylenethioalkylene group, a cycloalkylene group, an arylene group, and a biarylene. Group, alkylene arylene group, arylene alkylene arylene group, arylene oxyarylene group, arylene oxyalkylene group, arylene thioarylene group, arylene thioalkylene group, or an arylene aminoarylene group or an arylene which may have an alkyl group bonded to a nitrogen atom And an aminoalkylene group. One preferred example of the organic phosphite represented by the general formula (3) is one represented by the following general formula (4).

[0019]

Embedded image

In the formula, R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group, a cycloalkyl group or an aryl group which may have a substituent which does not inhibit the hydroformylation reaction, and n is Represents an integer of 0 to 4; Y has the same meaning as in general formula (3), and preferably represents a substituted aryl group represented by general formula (2) described above. In the general formula (4), typical examples of R ¹² and R ¹³ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a hydroxymethyl group, a hydroxyethyl group, and a trifluoromethyl group. And the like. Another preferred example of the organic phosphite represented by the general formula (3) is one represented by the following general formula (5).

[0021]

Embedded image

In the formula, R ¹⁴ is an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, or an aryl group which may have a substituent which does not inhibit a hydroformylation reaction. o-, m-, p-
Any of the positions. R ¹⁴ may be condensed with the benzene ring to which it is bonded to form a condensed aromatic ring such as a naphthalene ring. Y has the same meaning as in general formula (3), and preferably represents a substituted aryl group represented by general formula (2) described above. Another preferable example of the organic phosphite represented by the general formula (3) is represented by the following general formula (6).

[0023]

Embedded image

Wherein Ar inhibits the hydroformylation reaction
Aryl groups which may have unsubstituted substituents,
They may be different. Q is -CR¹⁵R¹⁶-, -O
-, -S-, -NR¹⁷-, -SiR¹⁸R¹⁹-, -CO-
And a divalent cross-linking group. In these crosslinking groups,
R¹⁵And R¹⁶Are each independently a hydrogen atom or carbon number
1 to 12 alkyl groups, phenyl groups, tolyl groups or ani groups
Represents a sil group;¹⁷~ R ¹⁹Is, independently of each other, hydrogen
Represents an atom or a methyl group. n is independently 0
Or represents 1. Y has the same meaning as in general formula (3)
You. Preferred examples of Y include a methyl group, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, sec
-Butyl group, t-butyl group, n-pentyl group, isopene
Tyl group, t-pentyl group, neopentyl group, n-hexyl
Group, t-hexyl group, cyclohexyl group, isooctyl
Group, 2-ethylhexyl group, decyl group, octadecyl
A C1-20 alkyl group such as a group or cycloalkyl
Group and a substituent that does not inhibit the hydroformylation reaction.
Phenyl group, α-naphthyl group, β-naph
And an aryl group such as a tyl group. Aryl group placement
Examples of the substituent include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group.
Alkyl group, alkoxy group, acyl group, acyloxy group,
Alkoxycarbonyl group, alkylamino group, etc. and halo
Gen atom. Organic phosphite of general formula (6)
Particularly preferred among the compounds are the following general formula (7) or
Is represented by (8).

[0025]

Embedded image

In these formulas, Q, Y and n are the same as in the formula (6), and R ^{20 to} R ²⁵ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group,
Represents an alkoxy group, an alkylamino group, an acyl group, an acyloxy group or an alkoxycarbonyl group, or a halogen atom. Some of the above-mentioned organic phosphites having a cyclic structure containing a phosphorus atom are shown in Table 1 below.

[0027]

[Table 1]

[0028]

[Table 2]

The ligand used in the present invention has two
The polyphosphite having at least two phosphite structures is represented by the following general formula (9).

[0030]

Embedded image

In the formula, Z has the same meaning as in the formula (3), and R ²⁶ and R ²⁷ each independently represent an alkyl group,
Represents a hydrocarbon group having 1 to 30 carbon atoms such as a cycloalkyl group, an aryl group, or an aralkyl group or a heteroaromatic hydrocarbon group having 5 to 30 carbon atoms, to which a substituent that does not inhibit a hydroformylation reaction is bonded. May be. Examples of such a substituent include a halogen atom and a carbon atom having 1 to 20 carbon atoms.
And alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, alkylamino groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, and the like.

Some specific examples of R ²⁶ and R ²⁷ are as follows: methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl and n-butyl.
-Pentyl group, isopentyl group, neopentyl group, t-
A linear or branched alkyl group having 1 to 20 carbon atoms such as a pentyl group and a t-hexyl group; a cycloalkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclohexyl group, a cyclooctyl group and an adamantyl group; A phenyl group, α
-Naphthyl group, β-naphthyl group, methoxyphenyl group,
Dimethoxyphenyl, cyanophenyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, methylphenyl, ethylphenyl, dimethylphenyl, trifluoromethylphenyl, methylnaphthyl, methoxynaphthyl, chloro An aryl group which may have a substituent such as a naphthyl group, a nitronaphthyl group and a tetrahydronaphthyl group; an aralkyl group such as a benzyl group; a pyridyl group, a methylpyridyl group, a nitropyridyl group, a pyrazyl group, a pyrimidyl group, and a benzofuryl group And heteroaromatic groups such as quinolyl group, isoquinolyl group, benzimidazolyl group and indolyl group.

W represents an m-valent hydrocarbon group which may contain a hetero atom such as an oxygen, nitrogen or sulfur atom in the carbon chain and may have a substituent which does not inhibit the hydroformylation reaction. Represent. m ₁ and m ₂ each represent a number of 0 to 6, and m ₁ + m ₂ represents an integer of ₂ to 6. Note that m
_{When 1} or m ₂ represents a number of 2 or more, a plurality of Z, R
²⁶ and R ²⁷ may each be different.

Preferably, Z is the above formula (4) to (8)
R is represented by²⁶And R ²⁷Is hydroformyl
That may be substituted with a substituent that does not inhibit the
A group. Some examples of such aryl groups
Then, a phenyl group, a 2-methylphenyl group, a 3-methyl
Ruphenyl group, 4-methylphenyl group, 2,4-dimethyl
Phenyl group, 2,5-dimethylphenyl group, 2,6-
Dimethylphenyl group, 2-methoxyphenyl group,
Toxiphenyl group, 4-methoxyphenyl group, 2,4-
Dimethoxyphenyl group, 2,5-dimethoxyphenyl
Group, 2,6-dimethoxyphenyl group, α-naphthyl group,
3-methyl-α-naphthyl group, 3,6-dimethyl-α-
Naphthyl group, β-naphthyl group, 1-methyl-β-naphthyl
And a 3-methyl-β-naphthyl group.

W is preferably an alkylene group, or a general formula
-Ar- (CH in (6)_Two) _n-(Q)_n− (C
H_Two)_nIt is a divalent group represented by -Ar-. like this
Examples of such a divalent group include a 1,2-ethylene group and a 1,3-propylene group.
Ropylene group, 1,3-dimethyl-1,3-propylene
Group, 1,4-butylene group, 1,5-pentylene, 1,6
-Hexylene group, 1,8-octylene group, 1,2-fe
Nylene group, 1,3-phenylene group, 2,3-naphthylene
Group, 1,8-naphthylene group, 1,1′-biphenyl-
2,2'-diyl group, 1,1'-binaphthyl-7,7 '
-Diyl group, 1,1'-binaphthyl-2,2'-diyl
Group, 2,2'-binaphthyl-1,1'-diyl group, 2,
2'-binaphthyl-3,3'-diyl group and the like.
You.

A more preferred example of the polyorganophosphite represented by the general formula (9) is that Z is -Ar- (CH ₂ ) _n -Q _n- (CH ₂ ) _n -Ar- in the general formula (6).
And m ₁ is at least 1;
And W is represented by the following general formula (10).

[0037]

Embedded image

In the formula, Q and n are as follows in the general formula (6).
Synonymous with R³²And R³³Are each independently carbon
Number 1 to 12 alkyl groups, cycloalkyl groups, alcohols
A xy, silyl or siloxy group, or a halogen atom
Represents a hydrogen atom or a hydrogen atom. Some examples
And methyl, ethyl, n-propyl, isopropyl
Group, n-butyl group, methoxy group, ethoxy group, n-propyl
Loxy group, hydrogen atom, fluorine atom, chlorine atom, bromine atom
And an iodine atom. Also, R²⁸~ R ³¹Is
Each independently represents an alkyl group having 1 to 20 carbon atoms,
Chloroalkyl, alkoxy, silyl or silo
A xy group, a halogen atom or a hydrogen atom,
Examples of these include methyl, ethyl, n-propyl
Group, isopropyl group, n-butyl group, t-butyl group,
An opentyl group, a 2,2-dimethylbutyl group, a nonyl group,
Decyl group, methoxy group, ethoxy group, t-butoxy group, etc.
Is mentioned. Also, R³⁰And R³²Or R³¹And R³³And
1,1'-binaphthyl-2,2'-diyl
And a condensed ring such as a phenyl group may be formed.

In the general formula (10), R ²⁸ and R ²⁹ are preferably an alkyl group having 3 to 20 carbon atoms and branched at the 1-position. R ³⁰ and R ³¹ are an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or R ³⁰ and R ³² , or R ³¹ and R ³³ are bonded to form an alkyl group or an alkoxy group as a substituent; It preferably forms part of a naphthalene ring that may be present. Some examples of W represented by the general formula (10) include: 3,3′-di-t
-Butyl-1,1'-binaphthyl-2,2'-diyl group, 3,3 ', 6,6'-tetra-t-butyl-1,
1'-binaphthyl-2,2'-diyl group, 3,3'-di-t-butyl-6,6'-di-t-butoxy-1,1 '
-Binaphthyl-2,2'-diyl group, 3,3'-di-t
-Pentyl-1,1-binaphthyl-2,2'-diyl group, 3,3 ', 6,6'-tetra-t-pentyl-1,
1'-binaphthyl-2,2'-diyl group, 3,3'-di-t-butyl-5,5'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ' , 5,5'-Tetra-t-butyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra-t-pentyl-
1,1'-biphenyl-2,2'-diyl group, 3,3 '
-Di-t-butyl-5,5'-dimethoxy-1,1'-
Biphenyl-2,2'-diyl group, 3,3'-di-t-
Butyl-5,5 ', 6,6'-tetramethyl-1,1'
-Biphenyl-2,2'-diyl group, 3,3 ', 5
5'-tetra-t-butyl-6,6'-dimethyl-1,
1'-biphenyl-2,2'-diyl group, 3,3 ',
5,5'-tetra-t-pentyl-6,6'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,
3'-di-t-butyl-5,5'-dimethoxy-6
6'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra-t-butyl-
6,6'-dichloro-1,1'-biphenyl-2,2 '
-Diyl group and the like.

Of the W represented by the general formula (10),
One of the preferred is R³²And R ³³But independent
A methyl group, an ethyl group, an n-propyl group,
Pill group, methoxy group, ethoxy group, n-propoxy group,
Isopropoxy group, fluorine atom, chlorine atom, bromine atom,
Alkyl groups having 1 to 3 carbon atoms, such as iodine atom, alkoxy
It is a group or a halogen atom. Such a W
Examples of 3,3'-di-t-butyl-5,5 ',
6,6'-tetramethyl-1,1'-biphenyl-2,
2'-diyl group, 3,3 ', 5,5'-tetra-t-butyl
Tyl-6,6'-dimethyl-1,1'-biphenyl-
2,2'-diyl group, 3,3 ', 5,5'-tetra-t
-Butyl-6,6'-diethyl-1,1'-biphenyl
-2,2'-diyl group, 3,3 ', 5,5'-tetra-
t-butyl-6,6'-dimethoxy-1,1'-biphe
Nyl-2,2'-diyl group, 3,3'-di-t-butyl
-5,5'-dimethoxy-6,6'-dichloro-1,
1'-biphenyl-2,2'-diyl group, 3,3 ',
5,5'-tetra-t-butyl-6,6'-difluoro
-1,1'-biphenyl-2,2'-diyl group and the like.
Can be Polyphosphite represented by the general formula (9)
Some are illustrated in Table-2.

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

[Table 6]

[0045]

[Table 7]

[0046]

[Table 8]

[0047]

[Table 9]

[0048]

[Table 10]

[0049]

[Table 11]

[0050]

[Table 12]

[0051]

[Table 13]

[0052]

[Table 14]

[0053]

[Table 15]

[0054]

[Table 16]

[0055]

[Table 17]

[0056]

[Table 18]

[0057]

[Table 19]

[0058]

[Table 20]

[0059]

[Table 21]

[0060]

[Table 22]

[0061]

[Table 23]

The hydroformylation reaction can be carried out using the starting olefinic compound itself as a main solvent, but it is usually preferable to use a solvent inert to the reaction.
Examples of such a solvent include aromatic hydrocarbons such as toluene, xylene and dodecylbenzene; ketones such as acetone, diethyl ketone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; ethyl acetate;
Esters such as n-octyl phthalate; and high-boiling component mixtures which are by-produced during the hydroformylation reaction of aldehyde condensates and the like. Among them, it is preferable to use an aromatic hydrocarbon such as toluene or xylene, a high-boiling component mixture by-produced in the reaction, or a combination of these.

The concentration of the rhodium complex catalyst in the reaction zone is usually about 0.0 as rhodium metal per liter of liquid phase.
5 to 5000 mg. It is preferably from 0.5 to 1000 mg, particularly preferably from 10 to 500 mg. The organic phosphite is usually used in an amount of about 0.1 to 500 moles relative to rhodium. It is preferably used in an amount of 0.1 to 100 times, particularly 1 to 30 times the mole of rhodium. In addition, several types of organic phosphites may be used as a mixture.

As the starting olefinic compound, any compound having at least one olefinic double bond in the molecule can be used. The olefinic double bond may be at the terminal or inside the molecular chain. The carbon chain constituting the molecule may be linear, branched or cyclic. Further, in the molecule, a carbonyl group which is substantially inert to the hydroformylation reaction in the reaction,
It may contain a hydroxy group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a halogen atom and the like. Representative olefinically unsaturated compounds are α-olefins, internal olefins, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers, alkenols and the like. Some examples of olefinically unsaturated compounds include ethylene, propylene, butene, butadiene, pentene, hexene, hexadiene, octene, octadiene, nonene, decene,
Hexadecene, octadecene, eicosene, docosene,
Styrene, α-methylstyrene, cyclohexene, and lower olefin mixtures such as propylene-butene mixture, 1-butene-2-butene-isobutylene mixture, 1-butene-2-butene-isobutylene-butadiene mixture, propylene, n-butene Olefins such as a mixture of olefin oligomer isomers such as dimer to tetramer of lower olefin such as isobutylene, 3-phenyl-1-
Hydrocarbon olefins such as propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, acrylonitrile, allyl alcohol, 1-hydroxy-2,7-octadiene, 3-hydroxy-
1,7-octadiene, oleyl alcohol, 1-methoxy-2,7-octadiene, methyl acrylate, methyl methacrylate, methyl oleate, oct-1-en-4-ol, vinyl acetate, allyl acetate, acetic acid 3 -Butenyl, allyl propionate, vinyl ethyl ether,
Vinyl methyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenenitrile, 5
And olefins substituted with a polar group such as -hexenamide. Preferably, a monoolefinic unsaturated compound having only one olefinic double bond in the molecule is used. Particularly preferred are olefins having 2 to 20 carbon atoms, especially propylene, or 1-butene, 2-butene, isobutene, and mixtures thereof, 1-octene, and mixed octene.

The reaction temperature of the hydroformylation reaction is usually 1
5 to 150C, but 30 to 130C, especially 50 to 1C.
A range of 10 ° C. is preferred. The reaction pressure is from normal atmospheric pressure to 20
0 kg / cm ² G, but 1-100 kg / cm
² G, especially 3 to 50 kg / cm ² G, is preferred. The molar ratio of hydrogen to carbon monoxide (H ₂ / CO) of the oxo gas supplied to the reaction zone is usually 10/1 to 1/10,
/ 1 to 6/1 are preferred.

The reaction can be carried out in either a continuous mode or a batch mode. Usually, the reaction is carried out in a continuous mode, in particular, in a reaction zone containing a liquid phase containing a rhodium complex catalyst, a reaction solvent containing a catalyst and an olefinic compound as a raw material. And an oxo gas is continuously supplied, a reaction product liquid containing the aldehyde generated from the reaction zone is continuously withdrawn, and at least the generated aldehyde is separated therefrom, and a reaction solvent containing the remaining catalyst is circulated to the reaction zone. It is performed in a cyclic manner. Separation of the produced aldehyde in the liquid circulation system may be performed by any method, and is usually performed by distillation. When the aldehyde is separated from the reaction product solution by distillation, the rhodium complex catalyst is generally easily deactivated. In particular, since the rhodium complex catalyst having an organic phosphite as a ligand as in the present invention has high activity, the hydroformylation reaction is often performed at a relatively low temperature as described above, and the aldehyde is separated from the reaction product by distillation. In some cases, the distillation temperature may be higher. In this case, it is considered that the deactivation of the rhodium complex catalyst mainly occurs in the distillation step. The deactivation of the rhodium complex catalyst during distillation is because carbon monoxide and hydrogen that are easily coordinated with rhodium are not present in the system during distillation, and the rhodium complex is easily decomposed in a coordinatively unsaturated form. As a result, it is considered that the rhodium complex catalyst is deactivated. However, when the liquid contact part of the distillation column is constituted by a material containing nickel according to the method of the present invention,
The deactivation of the catalyst in this distillation step can be reduced.

Although the details of the reason are unknown, it is conceived that nickel elutes from the metal material containing nickel, and this nickel may trap or detoxify the compound which promotes the decomposition generated by the decomposition of the phosphite compound. Conceivable. This is because the amount of nickel powder charged in Example 2 to be described later was reduced to 1/5 of Example 1,
This is supported by the increased decomposition rate of organic phosphite.

Examples of the metal material containing nickel include nickel-iron-chromium, nickel-iron-chromium-molybdenum, nickel-copper, nickel-molybdenum alloy, and the like, such as austenitic stainless steel, monel steel, inconel steel, and the like. Hastelloy steel or the like is used.
Preferably, an alloy containing a large amount of nickel, which is considered to be easily eluted with nickel, particularly an alloy containing 8% by weight or more of nickel is used. A typical example is an austenitic stainless steel containing nickel in an amount of 8% by weight or more, such as SUS304, SUS304L, and SUS3.
16, SUS316L or the like is preferably used. It is unclear how much nickel should be eluted from the liquid contact part of the separation zone, but it is considered that the nickel concentration in the liquid phase of the separation zone should be 1 ppm or more, preferably 10 ppm or more. When the catalyst is circulated, the eluted nickel accumulates and the nickel concentration in the liquid phase gradually increases, so it is not impossible to reach such a concentration by elution.

Even when the liquid contact portion of the distillation column is made of a metal material containing nickel, decomposition of the rhodium complex catalyst cannot be avoided at high temperatures, so that the distillation temperature is 150 ° C. or less, especially 13 ° C.
The temperature is preferably set to 0 ° C. or lower. Most preferably, it is distilled at 50 to 120 ° C. Therefore, when the boiling point of the aldehyde is high, it is preferable to perform distillation under reduced pressure. The reaction solvent containing the rhodium complex catalyst obtained by separating the aldehyde by distillation is present in the reaction solvent by an appropriate means such as extraction, washing, crystallization, or adsorption before being circulated to the reaction zone. The decomposition products of the organic phosphite may be removed.

[0070]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. Example 1 SUS-316 with a magnetic stirrer and an inner volume of 100 mL
In a stainless steel autoclave, di-μ-acetato-bis (1,5-cyclooctadiene) dirhodium ([Rh
_{(C 8 H 12) (μ} -CH 3 CO 2)] 2) complexes 65.7
mg, (0.121 mmol), 1041.5 mg (0.972 mmol) of bidentate phosphite represented by the following formula
And nickel metal powder 141.5 mg, and toluene 2
5 mL and 25 mL of n-butyraldehyde were charged under a nitrogen atmosphere. In this autoclave, oxo gas (H ₂
/ CO = 1 (molar ratio)) to 9 kg / cm ² G, and the mixture was stirred at room temperature for 15 minutes to activate the catalyst. Then, oxo gas was released, and the atmosphere was replaced with nitrogen gas again.
And heated. Decomposition products generated by decomposition of the ligand in the solution after the heat treatment were quantified by high performance liquid chromatography. As a result, the detected decomposition product was 3 mol% of the original ligand after the heat treatment for 66 hours, and was 72 mol% of the original ligand after the heat treatment for 138 hours.
Note that, by the activation treatment of the above catalyst, rhodium is coordinated with hydrogen, carbon monoxide, and phosphite to become rhodium hydride dicarbonyl (phosphite).
Confirmed separately.

[0071]

Embedded image

Example 2 A heat treatment was performed at 130 ° C. for 135.5 hours in exactly the same manner as in Example 1 except that the charged amount of the nickel metal powder was 29.2 mg. As a result, the detected decomposition product was 99 mol% of the original ligand.

Example 3 A 200-mL SUS316 stainless steel autoclave of induction rotation type was charged with di-μ-acetato-bis (1,
5-cyclooctadiene) rhodium ([Rh (C ₈ H
₁₂ ) (μ-CH ₃ CO ₂ )] ₂ ) 151.7 mg complex
(0.281 mmol), 1074.2 mg (2.33 mmol) of tri-1-naphthyl phosphite, 60 mL of toluene, and 60 mL of n-butyraldehyde were charged under a nitrogen atmosphere. The catalyst was activated by injecting oxo gas (H ₂ / CO = 1 (molar ratio)) into the autoclave up to 9 kg / cm ² G and stirring at room temperature for 15 minutes. Then, after oxo gas was released and replaced with nitrogen gas again, the autoclave was placed in a nitrogen atmosphere for 8 hours.
Heated to 0 ° C. Sampling was performed over time from when the temperature reached 80 ° C., and the amount of ligand in the solution was quantified by high performance liquid chromatography. The results were as follows. Heat treatment time (Hr) 0 3 18.8 42.8 Remaining amount of ligand (%) 65 62 47

Comparative Example 1 A 300-mL glass container equipped with a stirrer made of Teflon with stirring blades and a condenser was charged with di-μ-acetato-bis (1,5-cyclooctadiene) dirhodium ([Rh (C _{8 H 12) (μ-CH} 3 CO 2)] 2) complex 132.5mg (0.245mmol), tri-1-naphthyl phosphite 895.4mg (1.94mmo
l), toluene 50 mL, and n-butyraldehyde 5
0 mL was charged under a nitrogen atmosphere. The catalyst was activated by blowing oxo gas (H ₂ / CO = 1 (molar ratio)) into the vessel for 15 minutes while stirring. Next, oxo gas was released and replaced with nitrogen gas again.
Heated. Sampling was performed over time from when the temperature reached 80 ° C., and the amount of ligand in the solution was quantified by high performance liquid chromatography. The results were as follows. Heat treatment time (Hr) 0 3 18.8 Remaining amount of ligand (%) 58 31 1

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akio Nakanishi 3-10 Ushidori, Kurashiki-shi, Okayama Pref. Mitsubishi Chemical Co., Ltd. F-term (reference) 4G069 AA06 BA27A BA27B BC71A BC71B BE29A BE29B BE32A BE33A BE37A BE37B BE38A CB51 CB52 CB72 DA02 4H006 AA02 AC45 AD11 BA24 BA35 BA48 BA83 BB11 BB15 BD40 BD36 BD20 CL45

Claims (8)

[Claims] 1. A reaction step of reacting an olefinic compound with hydrogen and carbon monoxide to form an aldehyde in a reaction zone in the presence of a liquid phase containing at least a rhodium complex catalyst comprising rhodium and an organic phosphite. Production of an aldehyde including a separation step of separating a aldehyde from a reaction mixture taken out of a reaction zone in a separation zone to obtain a catalyst solution containing a rhodium complex catalyst, and a circulation step of circulating the catalyst solution to the reaction zone A method wherein at least a portion of the wetted portion of the separation zone comprises a metallic material including nickel. 2. The method according to claim 1, wherein the metal material containing nickel is nickel.
The method according to claim 1, wherein the austenitic stainless steel is contained in an amount of at least% by weight. 3. The method according to claim 1, wherein the organic phosphite constituting the rhodium complex catalyst is represented by the general formula (1). [Image Omitted] P (OR ¹ ) (OR ² ) (OR ³ ) (1) (wherein, R ¹ to R ³ are each independently a carbon number which may have a substituent. Represents a hydrocarbon group having 1 to 30 or a heteroaromatic hydrocarbon group having 5 to 30 carbon atoms) 4. In the general formula (1), R ¹ to R ³
Are each independently a substituted aryl group represented by the general formula (2). Embedded image (Wherein R ⁴ is —CR ⁹ R ¹⁰ R ¹¹ (R ⁹ , R ¹⁰ and R ¹¹
Each independently represents a hydrogen atom or a hydrocarbon group which may be fluorinated) or an aryl group which may have a substituent. R ⁵ to R ⁸ each independently represent a hydrogen atom or an organic group. Note that adjacent ones of R ⁵ to R ⁸ may combine with each other to form a condensed aromatic ring or a condensed heterocyclic ring. 5. The method according to claim 1, wherein the organic phosphite constituting the rhodium complex catalyst is represented by the general formula (3). Embedded image (In the formula, Z represents a divalent hydrocarbon group which may contain a hetero atom in the carbon chain and may have a substituent, and Y represents a carbon atom which may have a substituent. Represents a hydrogen group or a heteroaromatic hydrocarbon group.) 6. The method according to claim 1, wherein the organic phosphite constituting the rhodium complex catalyst is represented by the general formula (9). Embedded image (In the formula, Z represents a divalent hydrocarbon group which may contain a hetero atom in the carbon chain and may have a substituent. R ²⁶ and R ²⁷ each independently represent Represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms or a heteroaromatic hydrocarbon group having 5 to 30 carbon atoms, W may include a hetero atom in the carbon chain, and Represents an m-valent hydrocarbon group which may have a substituent, m ₁ and m
₂ represents an integer of 0 to 6, and m ₁ + m ₂ =
2-6) 7. In the general formula (9), R ²⁶ and R ²⁷ are each independently an aryl group which may have a substituent, and W is represented by the general formula (10). 7. The method of claim 6, wherein the method comprises: Embedded image (Wherein, R ²⁸ and R ²⁹ each independently represent a group having 3 carbon atoms)
~ 20 branched alkyl groups. R ³⁰ and R ³¹ are each independently an alkyl group or an alkoxy group having 1 to 20 carbon atoms. R ³² and R ³³ are each independently a hydrogen atom, a halogen atom, a silyl group, siloxy group, or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or an alkoxy group. Q is -CR ¹⁵ R ^16- , -O-,-
^{S -, - NR 17 -,} - SiR 18 R 19 - is a bridging group which is, or -CO-. In this bridging group, R ¹⁵ and R
¹⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group or an anisyl group, and R ^{17 to} R ¹⁹ each independently represent a hydrogen atom or a methyl group. n represents 0 or 1. ) 8. An olefinic compound comprising propylene, 1
-Butene, 2-butene, isobutene, mixed butene, 1-
The method according to any one of claims 1 to 7, wherein the method is selected from the group consisting of octene and mixed octene.