JPS63196537A - Production of hydroformylated compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound and recover a VIII group noble metal complex from an active carbon adsorbent at the same time, by bringing a hydroformylated reaction liquid obtained by using a VIII group noble metal complex catalyst containing an organophosphorous compound as a ligand into contact with an active carbon adsorbent and then distilling the eluate. CONSTITUTION:An unsaturated compound is hydroformylated with H2/CO mixed gas in the presence of a catalyst consisting of a VIII group noble metal complex containing an organic phosphorous compound as a ligand and the resultant reaction liquid is brought into contact with an active carbon adsorbent (e.g. active carbon, oxidation treated active carbon or organophosphorous compound carried on oxidation-treated active carbon) to adsorb the VIII group noble metal complex. The reaction liquid after adsorption treatment is distilled and the organophosphorous compound is recovered and hydroformylated compound is separated. An adsorbent after separating the reaction liquid is brought into contact with an eluting agent (e.g. polar solvent, composition consisting of an organic base and organophosphorous compound) to elute the adsorbed complex. The expensive noble metal catalyst can be recovered without lowering the activity of the catalyst by the above-mentioned method.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is an improvement in a method for carrying out a hydroformylation reaction by reacting an unsaturated compound with a mixed gas of H and CO in the presence of a catalyst consisting of a Group Ⅰ noble metal complex. It is related to.

BACKGROUND OF THE INVENTION Conventionally, a soluble complex of a Group I noble metal compound and an organic phosphorus compound has been used as a catalyst in the hydroformylation or hydrocarboxylation reaction of olefins.

Since the catalyst remains uniformly dissolved in the reaction solution after the reaction, it is necessary to separate and recover the expensive catalyst and return it to the reaction system.

When the reaction product has a low boiling point, it is possible to separate the reaction product and the catalyst liquid by distillation and reuse the catalyst liquid in the next reaction.

However, in this reaction, various high-boiling by-products are produced, so in order to avoid accumulation of high-boiling by-products in the reaction system due to circulation of the catalyst liquid, high-boiling by-products are removed from the reaction system by distillation. It is necessary. Since the removed high-boiling byproducts contain expensive Group III noble metals,
It is necessary to collect this efficiently.

However, at high temperatures of 150°C or higher, the above complex undergoes thermal deterioration and its catalytic activity decreases. requires a special activation treatment to activate the separated catalyst.゛If the reaction product has a high boiling point, it can be treated by a method other than distillation, such as adsorption or extraction, in the same manner as above.
It is necessary to recover the Group noble metal complex or, in the case of distillation, to carry out a special activation treatment to activate the separated catalyst.

Conventionally, the following method has been proposed as a method for recovering a soluble complex of a group (I) noble metal compound and an organic phosphorus compound or a group (I) noble metal from a reaction solution used in the hydroformylation reaction of an olefin.

■ JP-A-49-121793 discloses that when an olefin such as butene is subjected to a hydroformylation reaction using a rhodium-tertiary phosphine complex catalyst, the low-boiling point portion is separated by distillation, and then the high-boiling point distillation residue is From rhodium
As a method for separating the tertiary phosphine complex catalyst, a mixture consisting of the catalyst and a high-boiling organic distillation residue is first brought into contact with an adsorbent typified by an alkaline earth metal silicate such as magnesium silicate, and then aromatic carbonization is performed. A method is described in which a hydrogen solvent is used to wash high-boiling organic distillation residues from an adsorbent, and a polar solvent containing a small amount of tertiary amine is used to elute the catalyst adsorbed on the adsorbent.

■ Japanese Patent Publication No. 53-3993 discloses that when a group (III) noble metal is adsorbed and separated from an organic liquid containing a group (III) metal complex using activated carbon, methanol is allowed to coexist in the organic liquid. ing.

In this method, for example, propylene is subjected to a hydroformylation reaction in the presence of a rhodium-phosphorous compound complex catalyst, and then the aldehyde product is separated by distillation, and an organic liquid containing a high-boiling by-product and a catalyst is produced. When carrying out a hydroformylation reaction by charging rhodium into a reactor repeatedly as necessary, rhodium can be recovered from an organic liquid containing high-boiling byproducts and a catalyst by adding methanol and activated carbon to the organic liquid to remove the catalyst. This is done by adsorption. It is said that Group Ⅰ noble metals can be recovered from activated carbon after adsorption treatment by conventional methods such as roasting.

■ Japanese Patent Publication No. 53-3994 discloses the use of activated carbon that has been treated with nitric acid in advance in adsorbing and separating Group III noble metals from an organic liquid containing a Group III noble metal complex using activated carbon. There is. In this method,
For example, after propylene is subjected to a hydroformylation reaction in the presence of a rhodium-phosphorus compound complex catalyst, the product aldoxide is separated by distillation, while the organic liquid containing the high-boiling by-product and the catalyst is separated by distillation. is added to the activated carbon treated with nitric acid, and methanol is further added to make the activated carbon treated with nitric acid adsorb rhodium. It is said that Group Ⅰ noble metals can be recovered from the nitric acid-treated activated carbon after adsorption treatment by conventional methods such as roasting.

■ Japanese Patent Publication No. 53-3995 describes the use of an alkane having 5 to 14 carbon atoms, an alkane having 6 to 14 carbon atoms, an alkane having 5 to 14 carbon atoms, and a method for adsorbing and separating Group Ⅰ noble metals from an organic liquid containing Group Ⅰ noble metal complexes using activated carbon. It has been shown that Group I noble metals can be recovered by coexisting a compound selected from alkenes, polyhydric alcohols having 2 to 6 carbon atoms, aliphatic carboxylic acids having 2 to 6 carbon atoms, and dioxane. In this method, for example, propylene is subjected to a hydroformylation reaction in the presence of a rhodium-phosphorous compound complex catalyst, and then the aldehyde product is separated by distillation, and an organic liquid containing a high-boiling by-product and a catalyst is produced. When the hydroformylation reaction is carried out by charging the reactor repeatedly as necessary, rhodium can be recovered from the organic liquid containing the high-boiling by-products and the catalyst by adding the above-mentioned compound and activated carbon to the organic liquid. This is done each time the catalyst is adsorbed. It is said that Group Ⅰ noble metals can be recovered from activated carbon after adsorption treatment by conventional methods such as roasting.

■ JP-A No. 60-212233 describes a method for separating and recovering rhodium by extracting it with a complexing reagent from the product of oxo synthesis, in which a cationic, anionic or nonionic surfactant is added to an aqueous solution of the complexing agent. A method of adding solubilizing agents is shown.

■ E, J, Dufek and G, R, Li
5t, Journal of the America
an Oil Chemists' 5ocie
ty, 54. 278-278 (1977) discloses a method of using an aqueous HCN solution containing triethanolamine as an extractant in extracting rhodium from hydroformylated vegetable oil or its ester.

■ J, P, Fr1edrich, G, RoL
ist and V, E.

5ohns, Journal of the
American Oil Che+++1st
s'5ociety, 50.455-458 (19
73), methyl oleate is subjected to a hydroformylation reaction in the presence of triphenyl phosphite and an active rhodium catalyst supported on an alumina carrier, followed by filtration to separate the filtrate residue into the alumina carrier and the filtrate. The liquid is distilled to separate the formylated methyl stearate, which is a hydroformylation product, and the soluble rhodium catalyst, and the separated soluble rhodium catalyst is combined with the alumina support and calcined in a kiln, and the alumina support is activated by the firing. It has been shown that the above catalyst can be reused in the hydroformylation reaction.

The flow of the catalyst in the above-mentioned conventional technology is as follows.

Method (2) Hydroformylation Reaction Adsorption during distillation - Desorption Methods (2), (2), (2) Hydroformylation Reaction (During distillation) Adsorption (Activation by roasting) (2) Method (2) Hydroformylation reaction - Extraction (2) Method Hydroformylation - Extraction (2) Method Distillation of the filtrate - activating the catalyst by combining it with the residue from the filtration process and calcination Problems to be solved by the invention However, the above-mentioned method uses an alkaline earth metal silicate such as magnesium silicate as a recovery adsorbent. ■ Japanese Patent Application Publication No. 4
According to the method of Publication No. 9-121793, the recovery rate of the catalyst is said to be about 98.5%, but when the present inventors implemented this method, they found that the adsorption properties of the catalyst were extremely poor and However, there was a problem in that the desorption performance of the catalyst (soluble complex) once adsorbed was also poor. Additionally, since this method performs distillation before adsorbent treatment, if the product of the hydroformylation reaction has a high boiling point, the catalyst may undergo thermal deterioration during the distillation process, resulting in a decrease in activity. was there.

When the activated carbon described in Japanese Patent Publication No. 53-3993 (1) above or Japanese Patent Publication No. 53-3995 (1) above is used as a recovery adsorbent, the Group In addition, the recovery of Group I noble metals from activated carbon after adsorption treatment by roasting requires a high-temperature calcination process, the loss of the catalyst is not negligible, and It is disadvantageous in that the organic phosphorus compound added cannot be recovered.

On the other hand, as an adsorbent for recovery,
When the nitric acid-treated activated carbon described in Publication No. 3994 is used, the adsorption rate of group (III) noble metal complexes is excellent, but recovery of group (III) noble metals from the activated carbon after adsorption treatment by roasting is It is disadvantageous in that it requires a high-temperature calcination step, the loss of the catalyst is not negligible, and the organic phosphorus compound added as a ligand cannot be recovered.

The extraction methods described in (1) and (2) above do not necessarily provide a high extraction rate of the catalyst, and also have operational disadvantages, making them difficult to adopt industrially. In particular, the extraction method described in item (1) above uses HCN, which is extremely toxic, and therefore has problems in handling.

Journal of the Ameri above
can 0il(:hemists' 5ociety
, 50.455-458 (1973)) requires a calcination step at a high temperature (SOO°C), the recovery rate of the catalyst is about 98%, and the loss of the catalyst cannot be ignored, and the The organic phosphorus compounds added as ions cannot be recovered, and the organic phosphorus compounds are mixed into the product.
It could not be said to be industrially satisfactory due to the complexity of the process.

The present inventors have long been aware of the
The inventors have been conducting intensive research on hydroformylation reactions in the presence of group noble metal complex catalysts, and have discovered the industrially advantageous method described below, leading to the completion of the present invention.

Means for Solving the Problems The method for producing a hydroformylated compound of the present invention involves treating an unsaturated compound with a H2/CO mixed gas in the presence of a catalyst consisting of a group (I) noble metal complex having an organic-phosphorus compound as a ligand. a step (A) of reacting with a hydroformylation reaction, a step (A) of bringing the reaction solution from the previous step (A) into contact with an activated carbon-based adsorbent to adsorb the Group I noble metal complex contained in the reaction solution ( B).

Step (C) of supplying the reaction solution after the adsorption treatment in the previous step (B) to a distillation column and performing distillation to recover the organic phosphorus compound and separating the hydroformylated compound as a product.
, and a step (D) of bringing the adsorbent after separation of the reaction liquid in step (B) into contact with a desorption liquid to elute the group (I) noble metal complex adsorbed on the adsorbent. It is something.

The present invention will be explained in detail below.

Step (A) of the present invention involves reacting an unsaturated compound with a H2/Go mixed gas in the presence of a catalyst consisting of a group (I) noble metal complex having an organic phosphorus compound as a ligand. It consists of a step of carrying out a chemical reaction.

Examples of unsaturated compounds include olefins such as propylene, butene, heptene, and diisobutylene, carbonyl compounds,
Various unsaturated compounds conventionally used in hydroformylation reactions can be used, including aromatic compounds, unsaturated compounds, or esters thereof. In particular, one of the features of the present invention is that it can be applied to cases where the raw material has a high boiling point, such as a higher unsaturated fatty acid or an ester thereof, and the reaction product also has a high boiling point.

A Group Ⅰ noble metal complex having an organophosphorus compound as a ligand can be easily prepared from a Group Ⅰ noble metal compound and an organophosphorus compound such as phosphites or phosphines by a known complex formation method. . In this case, the group (I) noble metal may further contain a ligand other than the organophosphorus compound, such as an acetylacetonate group, a cyclopentagenyl group, a carbonyl group, a carboxyl group, a halogen atom, or a hydrogen atom. A complex can also be formed by supplying a compound and an organic phosphorus compound to a reaction system.

Group III noble metal compounds used to form the complex include oxides, chlorides, bromides, fluorides, iodides, etc. of Group III noble metals such as ruthenium, rhodium, palladium, osmium, iridium, and platinum; nitrates, sulfates,
Examples include acetates, cyanides, hydrides, carbonyl complexes, and amine complexes. Among these, rhodium compounds are particularly important. Examples of rhodium compounds include rhodium oxide, rhodium nitrate, rhodium trichloride, rhodium acetate, rhodium sulfate, rhodium dicarbonyl chloride, and rhodium chlorpentamine chloride.

As the organic phosphorus compound used to form the complex, phosphites or phosphines are used.

Examples of the phosphites include trimethyl phosphite, triethyl phosphite, tricyclohexyl phosphite, triphenyl phosphite, chlordiphenyl phosphite, and tetraphenylethylene diphosphite. Particularly suitable are triethyl phosphite and triphenyl phosphite.

Examples of phosphine include trimethylphosphine, triethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, chlordiethylphosphine, tris(aminoamyl)phosphine, tris(N,N-dimethylanilyl)phosphine, tris(〇-tolyl) Examples include phosphine, phenyldiisopropylphosphine, phenyldiamylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, chlordiethylphosphine, and trianylylphosphine.

The hydroformylation reaction is carried out in a high pressure reactor at 10 to 300
The reaction is carried out under a pressure of approximately 10 to 100 kg/cm" when a rhodium complex is used as a catalyst. The reaction temperature is about 80-180℃,
The reaction time is often about several hours.

Step 1 Step (B) consists of bringing the reaction solution from the previous step (A) into contact with an activated carbon-based adsorbent to adsorb the Group I noble metal complex contained in the reaction solution.

Examples of activated carbon-based adsorbents include: (1) activated carbon, (2) oxidation-treated activated carbon, and (2) oxidation-treated activated carbon further supporting an organic phosphorus compound.

The activated carbon in (1) or the activated carbon before the oxidation treatment in (1) or (2) has a pore distribution with a pore diameter in the range of 20 to 3 ooA and a pore volume of 0.35 ml/g or more (that is,
Pore diameter is 20~3oo5. It is desirable to use activated carbon whose value obtained by integrating the pore volume of only the pores in the range of 0.35 ml/g or more, and when activated carbon that falls outside of this limit is used as a raw material, The adsorption rate of group noble metal complexes decreases.

- The following method is adopted as the oxidation treatment method for activated carbon in ■ or ■.

(a) Method of oxidizing with nitric acid Activated carbon is immersed in a nitric acid aqueous solution and stirred as necessary. The treatment temperature is usually set in the range from room temperature to the boiling point of the nitric acid aqueous solution, and may be cooled if necessary. The processing time is several minutes to several hours. The higher the nitric acid concentration, the lower the treatment temperature or the shorter the treatment time, and the lower the nitric acid concentration, the higher the treatment temperature or the longer treatment time. Practical conditions include a nitric acid aqueous solution concentration of about 10 to 60% by weight or more, a treatment temperature of room temperature to about 90° C. or more, and a treatment time of about 5 minutes to 3 hours or more. For example, when the nitric acid concentration is 60% by weight, the treatment is performed at room temperature for 5 to 20 minutes, and when the nitric acid concentration is 10% by weight, the treatment is performed at 90° C. for about 3 hours.

After nitric acid treatment, wash with water to remove nitrate ions,
Further dry if necessary.

(b) Method of oxidizing with air or oxygen Activated carbon is oxidized by keeping it under high temperature conditions in air or oxygen atmosphere. The oxidation temperature is usually 300 to 600°C, preferably 350 to 550°C in the case of air, and usually 200 to 45°C in the case of oxygen.
The temperature is selected from the range of 0°C, preferably from 250 to 40'O'C, and the treatment time is about 0.5 to 2 hours.

Among the above oxidation methods, the nitric acid oxidation method is industrially most suitable, and the oxidation method using air or oxygen can also be employed industrially.

As the organic phosphorus compound supported on the oxidized activated carbon in step (2), phosphites or phosphines as described in the description of step (A) are used. The organic phosphorus compound supported on the oxidized activated carbon may be the same or different from the organic phosphorus compound used to form the complex, but it is more convenient to use the same type.

The amount of organic phosphorus compound supported on oxidized activated carbon is 0.
．． It is preferable to set the amount in the range of 1 to 5 mmol/g. If the amount of the organic phosphorus compound supported is too small, the desorption ability of the group (I) noble metal complex from the adsorbent will be insufficient; If the amount is too large, the adsorption ability of the group Ⅰ noble metal complex to the adsorbent will decrease.

Among activated carbon-based adsorbents, in terms of adsorption and desorption properties of catalysts, the above-mentioned adsorbent (2), in which an organic phosphorus compound is further supported on oxidized activated carbon, is particularly preferred.The next most preferred is the above-mentioned oxidized Although treated activated carbon has excellent adsorption properties for catalysts, it has the disadvantage that its desorption properties are inferior to the adsorbents (3).

The above-mentioned activated carbon-based adsorbent is added to the reaction liquid from the previous step (A) to adsorb the group III noble metal complex dissolved therein, and then separated from the organic liquid by means such as filtration or centrifugation. can do.

However, industrially, a column is filled with this adsorbent,
It is desirable to adsorb the Group 1 noble metal complex by supplying a reaction solution to the base and bringing it into contact with this adsorbent.

The reaction solution may be passed in either an upward flow or a downward flow, but an upward flow is more efficient because it is less likely to cause drift.

The higher the adsorption temperature in the adsorption step, the greater the adsorption amount of the group (III) noble metal complex, but if it is too high, it may cause deterioration of the group (III) noble metal complex and alteration of the target product contained in the organic liquid. .

Usually it is set at room temperature to around 120°C.

After the group (III) noble metal complex in the reaction solution introduced into the adsorption tower is adsorbed by the adsorbent, the solvent may be poured into the tower as necessary to remove the reaction solution remaining in the tower or attached to the adsorbent. remove. Even when a column is not used, it is preferable to wash the reaction liquid adhering to the adsorbent with a solvent.
For example, benzene, toluene, xylene, ethylbenzene.

Aromatic hydrocarbons such as cumene and diethylbenzene, aliphatic hydrocarbons such as heptane and hexane, etc. are used.

In step (C), the reaction solution after the adsorption treatment in the previous step (B) is fed to a distillation column and distilled, recovering the organic phosphorus compound and separating the hydroformylated compound as a product. It consists of the process of

In this distillation step, since the catalyst has already been removed in the preceding step (B), even if the hydroformylation product has a high boiling point, it does not affect the activity of the catalytic converter.

The organic phosphorus compound is separated together with the hydroformylated compound by distillation, and this organic phosphorus compound can be reused in step (A).

:EΩ step CD) consists of the step of bringing the adsorbent after separation of the reaction liquid in step (B) into contact with a desorption solution to elute the group (I) noble metal complex adsorbed on the adsorbent.

After the reaction solution adhering to the adsorbent is removed by washing with a solvent if necessary, the desorption liquid is passed through the column to desorb the group (I) noble metal complex adsorbed by the adsorbent. It is preferable that the desorbed liquid be introduced in a countercurrent direction to the direction in which the Group Ⅰ noble metal complex-containing reaction liquid was introduced in the previous adsorption operation, but this is not always possible.If a column is not used, the adsorbent may be It may be added to the desorption solution and stirred.

As the desorption liquid, JP-A-49-1 mentioned in the prior art section is used.
Although the composition consisting of a polar solvent and a tertiary amine disclosed in No. 21793 can also be used, the composition consisting of a polar solvent, an organic base, and an organic phosphorous compound has a much better desorption ability, so it is preferable to use this composition. It is particularly desirable to use it as a desorption liquid.

Examples of polar solvents include ethers such as diethyl ether, tetrahydrofuran, and dioxane, ketones such as acetone, diethyl ketone, and methyl ethyl ketone, alcohols such as methanol, ethanol, and impropatol, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, etc. Polar solvents such as esters are suitable, especially ethers.

Amines are suitable as organic bases, such as ethylamine, propylamine, butylamine, diethylamine, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, dicyclohexylethylamine, N-methylpyrrolidine, N-methylpiperidine, dimethylaniline, diethylaniline. etc. are used.

As the organic phosphorus compound, the phosphites or phosphines mentioned above are used.

The mixing amount of the organic base is about 0.05 to 5 to the polar solvent.
The amount of the organic phosphorus compound mixed is preferably about 0.01 to 1 mol/liter based on the polar solvent.

The amount of desorbed liquid is often about 3 to 15 times the amount of adsorbent packed in the column.

The temperature of the desorption operation using the desorption liquid is generally desirably higher, but in consideration of the boiling point and thermal efficiency of the desorption liquid, it is usually set at about room temperature to 50°C.

To recover the Group Ⅰ noble metal complex dissolved in the desorbed liquid after desorption treatment, the desolvent of the desorbed liquid may be removed by distillation, evaporation, or other means at a temperature that does not cause thermal deterioration of the complex. .

The recovered Group (1) noble metal complex can be reused as it is as a hydroformylation reaction catalyst in step (A) without undergoing any activation treatment.

Effect The flow of the catalyst in the method of the present invention is represented by step (A) m step (B) m step CD) m step (A)--. That is, the catalyst is used again in the hydroformylation reaction after passing through the steps of hydroformylation reaction catalyst adsorption and catalyst desorption.

On the other hand, the hydroformylated compound produced in step (A) is separated through step (B)m step (C), that is, catalyst adsorption-distillation, and becomes a product.

In this distillation step, since the catalyst has already been removed in the preceding step (B), even if the product of the hydroformylation reaction has a high boiling point, it does not affect the activity of the catalyst.

When using oxidized activated carbon further supporting an organic phosphorus compound as an adsorbent, and using a composition consisting of a polar solvent, an organic base, and an organic phosphorus compound as the desorption liquid, the oxidation treatment will remove the surface of the activated carbon. The number of adsorption active sites increases, improving the adsorption ability of Group III noble metal complexes, and
Supporting the organic phosphorus compound controls the adsorption points on the surface of the activated carbon that are too active and would be difficult to desorb when adsorbing the Group I noble metal complex. Because of their excellent performance, Group III noble metal complexes are not only adsorbed almost quantitatively to the adsorbent, but also desorbed from the adsorbent almost quantitatively.As a result, they were first used in the hydroformylation reaction. In addition, the fusion compound can be used in step (B), step (C).
), that is, it is separated through distillation during catalyst adsorption and becomes a product.

In this distillation step, since the catalyst has already been removed in the preceding step (B), even if the product of the hydroformylation reaction has a high boiling point, it does not affect the activity of the catalyst.

When using oxidized activated carbon further supporting an organic phosphorus compound as an adsorbent, and using a composition consisting of a polar solvent, an organic base, and an organic phosphorus compound as the desorption liquid, the oxidation treatment will remove the surface of the activated carbon. The number of adsorption active sites increases, improving the adsorption ability of Group III noble metal complexes, and
Due to the support of the organic phosphorus compound, the activity of the adsorption sites on the surface of the activated carbon is so strong that when the group Ⅰ noble metal complex is adsorbed, 99.8% or more of the desorption medium is recovered, and moreover, hydroformyl can be used for the second and subsequent times as it is. It can be reused as a catalyst for chemical reactions.

EXAMPLES Next, the present invention will be further explained with reference to examples. below"
%, 1%" is expressed on a weight basis.

Example 1: 100 parts of methyl oleate, 0.01 part of rhodium oxide, and 0.32 parts of triethyl phosphite were charged into a 11-unit high-pressure reactor, and H2,/CO gas was added to the reactor at a reaction temperature of 120°C.
Press fit so that it is 0 kg/cm".

The reaction was carried out at 120°C for 4 hours.

The conversion rate and selectivity of the reaction from methyl oleate to methyl formyl stearate were both 99% or higher, and 100 μg/g of rhodium was dissolved in the reaction solution.

2nd 2 (Manufacture of adsorbent) Pore volume in the range of 20 to 300 pores is 0.51 m
30 g of 60% nitric acid was added to commercially available activated carbon (Diahope manufactured by Mitsubishi Chemical Industries, Ltd.) log having a pore size distribution of 1/g, and the mixture was allowed to stand at room temperature for 15 minutes, with occasional stirring during this period. Next, the activated carbon is filtered out, thoroughly washed with water, and then heated to a temperature of 1.
Vacuum drying was performed at 20°C for 2 hours.

Next, this nitric acid-treated activated carbon was added to triethyl phosphite (
Reagent grade 1) 1.7 g (1 liter per activated carbon - tso
I/g) in a tetrahydrofuran solution containing 3
The sample was left at room temperature for 0 minutes, then taken out and vacuum-dried at room temperature for 2 hours.

As a result, an adsorbent for recovery of group (I) noble metal complexes was obtained.

<Adsorption operation> 100 g of the above hydroformylation reaction solution was packed in an adsorption tower (9 mmφ x 300 mmH) filled with 10 g of the adsorbent obtained above.
The rhodium complex dissolved in the reaction solution was adsorbed by passing the solution through the bottom of the reactor. The temperature of the reaction solution was set to 100°C, and the space velocity was set to lhr.

Even after passing 100 g of the reaction solution, no rhodium was detected in the eluate.

After the adsorption operation was completed, 50 g of toluene was passed through the upper part of the adsorption tower to wash away the reaction liquid in the adsorption tower. This effluent contained no rhodium.

Engineering Fi-Engineering S) The liquid extracted from the adsorption tower is supplied to the distillation tower, and the temperature is adjusted to 0.5 mmHg.
vacuum distillation was performed.

The first fraction is triethyl phosphite, and this recovered triethyl phosphite can be used repeatedly in step (A) as a ligand for rhodium in the hydroformylation reaction, or repeatedly in the production of adsorbents for use in step (B). Can be used.

The component distilled out at a temperature of 175 to 195°C is methyl formyl stearate, which becomes the product.

Can residue is a high-boiling byproduct and is normally disposed of.

In order to desorb the rhodium complex adsorbed on the adsorbent, a desorption solution consisting of a mixture of 80 g of tetrahydrofuran, 20 g of n-butylamine, and triethylphosphite (Ig) was passed through the top of the adsorption tower. . The temperature of the desorption solution was set at 35°C.

When the amount of rhodium in the effluent in this desorption operation was measured, it was found that 9% of the rhodium used in the hydroformylation reaction.
It was found that more than 8.8% was recovered.

The effluent after the desorption operation was distilled under reduced pressure of 100 m+aHg and at a low temperature of 70° C., and separated into a solvent and a residue.

This solvent can be used repeatedly as a desorption liquid. Moreover, the residue can be repeatedly used as a hydroformylation reaction catalyst.

Reuse of Al-catalyst - A high-pressure reactor is charged with the residual liquid after distilling off the solvent under reduced pressure from the effluent after the above desorption operation and the triethyl phosphite recovered in step (C). The hydroformylation reaction of methyl oleate was carried out under the same temperature and pressure conditions as above.

Methyl oleate was converted to methyl formyl stearate at both conversion rate and selectivity of 99% or more.

Example 2 The raw activated carbon in step (B) of Example 1 was air oxidized at 400°C for 1 hour using a mouth-tally kiln, and then the air-oxidized activated carbon was mixed with 1.7 g of triethyl phosphite (1st class reagent) (activated carbon It was added to a tetrahydrofuran solution containing 1 mmol/g), left at room temperature for 30 minutes, then taken out and vacuum-dried at room temperature for 2 hours. As a result, an adsorbent for recovery of group (I) noble metal complexes was obtained.

Each step of Example 1 was repeated except that this adsorbent was used as the adsorbent in step (B).

In the reaction from methyl oleate to methyl formyl stearate in step (A), both the conversion rate and the selectivity were 99% or more, and 100 kg/g of rhodium was dissolved in the reaction solution.

No rhodium was detected in the ejected liquid after passing the reaction liquid in step (B), and rhodium was found in the effluent after the reaction liquid in the adsorption tower was washed away by passing toluene after the adsorption operation was completed. It had not been done.

In step (C), the product methyl formyl stearate was separated, and triethyl phosphite was also separated.

The measurement of the amount of rhodium in the effluent after the desorption operation in step (D) revealed that 99.8% or more of rhodium was recovered.

Example 3 An experiment similar to Example 1 was conducted except that hydridocarbonyl tris(triethylphosphine) rhodium complex (H) (Go) [P(CzHr) 313 Rh was used as the catalytic rhodium compound instead of rhodium oxide.

The amount of catalyst was 0.05 parts per 100 parts of methyl oleate.

The conversion rate and selectivity of the reaction from methyl oleate to methyl formyl stearate were both 99% or more.

Next, using this adsorbent, an adsorption operation and then a desorption operation were performed under the same conditions as in Example 1.

When the amount of rhodium in the effluent from the desorption operation was measured, it was found that 93.9% or more of rhodium was recovered.

Comparative Example 1 The reaction solution after completing step (A) of Example 1 was supplied to a distillation column, and vacuum distillation was performed at 0.5'mmHg.

The product methyl formyl stearate is 175-195°C
However, the catalyst in the high-boiling components remaining in the can has undergone thermal deterioration and cannot be reused as a hydroformylation reaction catalyst as it is, so activation treatment such as roasting is required for reuse. had to be done.

Comparative Example 2 The same experiment as in Example 1 was repeated except that magnesium silicate having a particle size of 30 to 60 mesh was used as the adsorbent. When measuring the amount of rhodium in the eluate during adsorption operations,
It was found that approximately 50% of the rhodium had leaked out.

When measuring the amount of rhodium in the effluent during the desorption operation, the recovery rate of rhodium was approximately 40%, and the recovery rate of the catalyst used in the hydroformylation reaction was approximately 20 parts (50X
40/100) Tea 7'.

Effects of the Invention In the method of the present invention, the hydroformylation reaction solution is first subjected to an adsorption treatment, and the group (III) noble metal complex catalyst dissolved in the reaction solution is adsorbed onto an adsorbent. The liquid no longer contains the catalyst, so when this reaction liquid is subjected to distillation, there is no need to take into account thermal deterioration of the catalyst, even if the boiling point of the product of the hydroformylation reaction is high.

On the other hand, the Group 1 noble metal complex catalyst adsorbed on the adsorbent is eluted into the desorption liquid without undergoing thermal deterioration by bringing the adsorbent into contact with the desorption liquid.

In particular, if an oxidized activated carbon further supported with an organic phosphorus compound is used as the adsorbent, and a desorbing liquid with a composition consisting of a polar solvent, an organic base, and an organic phosphorus compound is selected, the hydroformylation reaction can be carried out first. The Group Ⅰ noble metal complex catalyst used in this process is recovered almost quantitatively (99.9% or more).

Since the recovered group (I) noble metal complex does not have a decrease in catalytic activity, it can be used repeatedly in the hydroformylation reaction as it is without any activation treatment.

Therefore, non-invention is of great significance in the chemical industry.

Claims (1)

[Claims] 1. A step of carrying out a hydroformylation reaction by reacting an unsaturated compound with H_2/CO mixed gas in the presence of a catalyst consisting of a Group VIII noble metal complex having an organic phosphorus compound as a ligand (
A), A step (B) in which the reaction solution from the previous step (A) is brought into contact with an activated carbon-based adsorbent to adsorb the Group VIII noble metal complex contained in the reaction solution, After the adsorption treatment in the previous step (B) Step (C) of supplying the reaction solution to a distillation column and performing distillation to recover the organic phosphorus compound and separating the hydroformylated compound as a product.
, and a step (D) of bringing the adsorbent after separation of the reaction liquid in step (B) into contact with a desorption liquid to elute the Group VIII noble metal complex adsorbed on the adsorbent. Method for producing hydroformylated compounds. 2. The production method according to claim 1, wherein the unsaturated compound is a higher unsaturated fatty acid and the hydroformylated compound is a higher fatty acid. 3. The Group VIII noble metal complex recovered in step (D) is subjected to step (D).
2. The production method according to claim 1, characterized in that it is reused as a hydroformylation reaction catalyst in A). 4. The organic phosphorus compound recovered in step (C) is transferred to step (A)
The manufacturing method according to claim 1, wherein the manufacturing method is reused. 5. The manufacturing method according to claim 1, wherein step (B) is carried out with the adsorbent packed in a column. 6. The production method according to claim 1, wherein the activated carbon adsorbent in step (B) is oxidized activated carbon further supporting an organic phosphorus compound. 7. The production method according to claim 1, wherein the desorbing liquid in step (D) has a composition consisting of a polar solvent, an organic base, and an organic phosphorus compound. 8. The manufacturing method according to claim 1, wherein the Group VIII noble metal is rhodium.