JPH0768157B2 - Hydroformylation method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for hydroformylating an olefinic compound. More specifically, the present invention relates to a method for economically performing a hydroformylation reaction of an olefinic compound by suppressing the deactivation of a hydroformylation catalyst and the formation of a high boiling by-product.

[Conventional technology]

A method for producing an aldehyde by hydrolyzing an olefinic compound having 4 to 30 carbon atoms with carbon monoxide and hydrogen in the presence of a rhodium or cobalt catalyst modified with a trivalent organic phosphorus compound is well known. There is. Further, in the hydroformylation reaction of a branched olefinic compound, a hydroformylation reaction is carried out using a rhodium catalyst modified with an oxide of a trivalent organic phosphorus compound, and a trivalent organic phosphorus compound is added to the obtained reaction product solution. A method has been proposed in which addition and distillation are performed, and the produced aldehyde is obtained by distilling, while the bottom liquid containing the rhodium catalyst is recycled to the reaction system of the hydroformylation reaction (Japanese Patent Laid-Open No. 59-76034). No. 59-95235, etc.).

However, when the reaction product liquid is separated into a hydroformylation reaction product and a catalyst liquid by distillation, and when the catalyst liquid is repeatedly circulated and reused, a reaction by-product having a higher boiling point than the aldehyde produced in the catalyst liquid (hereinafter, High boiling point by-products) accumulate, and the volume of the entire catalyst liquid increases by the amount corresponding to the volume of the accumulation, so that it becomes impossible to maintain the operation operation with the reaction vessel having the defined volume. Therefore, not only the generated aldehyde but also the high-boiling-point by-product must be taken out of the reaction system by some means in an amount commensurate with the amount produced.

As a method for removing high boiling by-products in the catalyst liquid, a certain amount of circulating catalyst liquid containing high boiling by-products is extracted according to the production amount of high boiling by-products, circulating catalyst liquid containing high boiling by-products. Is subjected to vacuum distillation or steam distillation (see JP-A-56-45436, etc.) to selectively distill only high-boiling by-products, and the like.

[Problems to be Solved by the Invention]

However, a hydroformylation reaction product obtained by a hydroformylation reaction of an olefinic compound having 4 to 30 carbon atoms, that is, an aldehyde or alcohol having 1 carbon more than the starting olefinic compound and a catalyst liquid will be separated by distillation. In such a case, the boiling points of the reaction product and the high-boiling by-product are both high, and the degree of vacuum is industrially limited, so the distillation temperature must be raised. For this reason,
During the distillation, the amount of high boiling by-products whose main component is the polycondensation product of the reaction product was not negligible, and the deactivation of the catalyst, which is thought to be due to the high distillation temperature, was also not negligible. Therefore, it is economically disadvantageous.

Even if the degree of vacuum is increased by a special method, the boiling point difference between the unreacted olefin, the aldehyde and alcohol of the reaction product, and the high boiling by-products is very large. Since the temperature of the top must be extremely low, a refrigerant is required, which is economically disadvantageous. If the hydroformylation reaction product remains, the temperature of the distillation column will be lowered and the high boiling rate will be low, but this will reduce the yield of the desired product. Therefore, in the separation of the hydroformylation reaction product of an olefinic compound having 4 to 30 carbon atoms and the catalyst solution, the product can be quantitatively separated by distillation at a relatively low temperature, and the formation of a high boiling by-product and It has been desired to develop a method capable of suppressing the deactivation of the catalyst.

[Means for Solving the Problems]

The present inventors have arrived at the present invention as a result of earnest studies in order to solve the above problems in view of the above-mentioned state of the art.

That is, the gist of the present invention is that in a hydroformyl reaction zone, in the presence of a trivalent organophosphorus compound and / or a Group VIII noble metal catalyst modified with an oxide of a trivalent organophosphorus compound, an off-line catalyst having 4 to 30 carbon atoms. After reacting the volatile compound with carbon monoxide and hydrogen to hydroformylate and distilling the reaction product liquid extracted from the reaction zone to separate a distillate containing an unreacted olefinic compound and a hydroformylation reaction product, In the hydroformylation method in which a non-distillate containing a Group VIII noble metal catalyst or a catalyst solution derived therefrom is circulated to the reaction zone, distillation of the reaction product solution is performed to distill the reaction product solution extracted from the reaction zone. Distilled under reduced pressure at a column bottom temperature of 130 ° C or lower to obtain 60 to 99% of unreacted olefinic compounds and 40% of hydroformylation reaction products contained in the reaction product liquids. First-stage distillation for distilling 95%, and the bottoms of the first-stage distillation are steam-distilled at a column bottom temperature of 130 ° C. or lower to substantially remove unreacted olefinic compounds and hydroformylation reaction products. The second stage distillation in which the solvent is distilled off, and the hydroformylation method is characterized in that it is carried out in two stages.

The present invention will be described in more detail below.

The step of the hydroformylation reaction in the method of the present invention is carried out according to a conventional method. Usually, a solution containing rhodium and a trivalent organic phosphorus compound and / or an oxide of a trivalent organic phosphorus compound, which is circulated from the circulation step described later, is used as a catalyst solution, and an olefinic compound having 4 to 30 carbon atoms is added to the solution. And the reaction is carried out by supplying water gas.
If desired, a catalyst and a solvent can be additionally supplied. The catalyst can be prepared in the reaction system by adding a rhodium compound and optionally a trivalent organophosphorus compound and / or an oxide of the trivalent organophosphorus compound to the step of the hydroformylation reaction. Alternatively, a trivalent organic phosphorus compound and / or an oxide of a trivalent organic phosphorus compound may be mixed in a solvent, and carbon monoxide may be introduced into the mixture to form an active rhodium catalyst, which is then added to the reaction system.

Of the Group VIII noble metal compounds used for catalyst preparation, examples of the rhodium compound include inorganic acid salts such as rhodium nitrate and rhodium sulfate; organic acid salts such as rhodium acetate, sodium rhodium oxalate, potassium rhodium malate; [RhL ₆ ]
X ₃ , [RhL ₅ H ₂ O] X ₃ , [RhL ₅ (OH)] X ₂ , [RhL ₅ (N
O ₂ )] X ₂ , [Rh (Py) ₃ (NO ₃ ) ₂ ] (wherein X is NO
▲ ^- ₃ ▼, OH ^- or , L represents NH ₃ , and Py represents pyridine)
And the like, such as amine complex salts. Of these, rhodium nitrate and rhodium acetate are preferably used.

Examples of the other Group VIII noble metal compounds include, for example, ruthenium trichloride, ruthenium compounds such as tetraamminehydroxochlororuthenium chloride; palladium hydride, palladium chloride, palladium cyanide, palladium iodide, palladium nitrate, palladium acetate, and sulfuric acid. Palladium compounds such as palladium; osmium trichloride,
Osmium compounds such as chloroosmic acid; iridium compounds such as iridium tribromide, iridium tetrabromide, iridium trifluoride, iridium trichloride, iridium carbonyl; platinum acid, platinous iodide, sodium hexachloroplatinate, trichloro ( Examples include platinum compounds such as ethylene) potassium diplatinate.

Examples of the trivalent organic phosphorus compound include arylphosphines such as triphenylphosphine, tritolylphosphine, and trianisylphosphine; tributylphosphine,
Alkylphosphines such as trioctylphosphine; Alkylarylphosphines having both an alkyl group and an aryl group; Triphenylphosphite (triphenylphosphite), arylphosphites such as tritolylphosphite; Triethylphosphite, tripropylphosphine Alkylphosphites such as fit and tributylphosphite; bis (diphenylphosphino) methane, 1,2-bis (diferphosphino) ethane, 1,4-bis (diphenylphosphino) butane, 1,2-bis ( Examples thereof include polydentate phosphines such as diphenylphosphinomethyl) cyclobutane and 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino) butane.

Examples of oxides of trivalent organic phosphorus compounds include arylphosphine oxides such as triphenylphosphine oxide, tritolylphosphine oxide and trianisylphosphine oxide; tributylphosphine oxide,
Alkylphosphine oxide such as trioctylphosphine oxide; Alkylarylphosphine oxide having both an alkyl group and an aryl group; Arylphosphite oxide such as triphenylphosphite oxide (triphenyl phosphate) and tritolylphosphite oxide; Triethylphosphine Alkyl phosphite oxides such as fit oxide, tripropyl phosphite oxide and tributyl phosphite oxide; alkylaryl phosphite oxides having both alkyl and aryl groups; bis (diphenylphosphino) methane dioxide, 1,2-bis (Diphenylphosphino) ethane dioxide, 1,4-bis (diphenylphosphino) butane dioxide, 1,2-bis (diphenylphosphinomethyl) cyclobutane dioxide, 2,3- - isopropylidene -
Examples thereof include polydentate phosphine oxides such as 2,3-dihydroxy-1,4-bis (diphenylphosphino) butane dioxide.

These trivalent organic phosphorus compounds and / or oxides of the trivalent organic phosphorus compounds have a phosphorus atom per 1 atom of the Group VIII noble metal in the system of the hydroformylation reaction.
It is present in an amount of 2 to 1000 atoms, preferably 2 to 500 atoms. If the amount of phosphorus atoms is too small, the stability of the catalyst will decrease, and conversely, if the amount of phosphorus atoms is too large, the hydroformylation reaction rate will tend to decrease.

In order to prepare an active catalyst in advance from a Group VIII noble metal compound and a trivalent organic phosphorus compound and / or an oxide of a trivalent organic phosphorus compound, both are mixed in the above ratio,
It may be treated with carbon monoxide or oxo gas.
The conditions are as follows: carbon monoxide partial pressure 1 to 200 kg / cm ² , preferably 1 to 100 kg / cm ² , temperature 10 to 200 ° C., preferably 20 to
It can be appropriately selected from the range of 150 ° C. and the time of several minutes to several hours.

The catalyst concentration in the reaction zone is usually 1-1000 mg / group, preferably 2-500 mg / group VIII noble metal atom.

Examples of the olefinic compound having 4 or more and 30 or less carbon atoms to be subjected to the hydroformylation reaction include 1-butene and 1-butene.
Linear α-olefins such as pentene, 1-hexene, 1-octene, 1-decene; 2-butene, 2-pentene, 2
-Linear internal olefins such as hexene, 3-hexene, 2-octene, 3-octene; isobutylene, 2-methyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 2- Methyl-1-hexene, 3-methyl-1-hexene, 2-methyl-1-heptene, 3-
Mono-branched α-olefins such as methyl-1-heptene and 4-methyl-1-heptene; 2,3-dimethyl-1-butene,
2,3-dimethyl-1-pentene, 2,4-dimethyl-1-pentene, 2,3-dimethyl-1-hexene, 2,4-dimethyl-1-hexene, 2,5-dimethyl-1-hexene, 3,4-
Hyperbranched α-olefins such as dimethyl-1-hexene;
And double bond isomers thereof. In addition to the above, propylene, butene, isobutylene, or
Olefin oligomer isomer mixture such as dimer to tetramer of lower olefin such as C4 fraction obtained in large amount from thermal cracking of naphtha or catalytic cracking of light oil; allyl alcohol, acrolein acetal, acetic acid Vinyl, styrene, alkyl vinyl ether, methyl oleate,
Substituted olefins such as cinnamic acid and 1-acetoxy-2- (1-naphthoxy) ethylene can be used.

In the method of the present invention, usually the catalyst liquid itself containing the Group VIII noble metal and the trivalent organic phosphorus compound and / or the oxide of the trivalent organic phosphorus compound circulated from the circulation step is used as the reaction medium, The solvent can also be used. As the solvent, any solvent can be used as long as it dissolves the catalyst and does not adversely affect the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, dodecylbenzene; alicyclic hydrocarbons such as cyclohexane; ethers such as dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran; diethyl phthalate And esters such as bis (2-ethylhexyl) phthalate are used. Further, aldehydes or alcohols produced by the hydroformylation reaction can be used as the solvent.

The reaction temperature is usually 50 to 170 ° C, preferably 90 to 1
It is in the range of 50 ° C.

As carbon monoxide and hydrogen, usually, a water gas having a molar ratio of hydrogen to carbon monoxide of 1/5 to 10/1 is used, and particularly, the hydrogen gas having a ratio of 1/2 to 5/1. Is preferred. The partial pressure of water gas is usually in the range of ^{20 to} 500 kg / cm ² , but is preferably in the range of 50 to 300 kg / cm ² .

The reaction can be performed in either a continuous system or a batch system.

In the method of the present invention, the reaction product liquid extracted from the hydroformylation reaction zone is first distilled under reduced pressure at a column bottom temperature of 130 ° C. or lower, and each of the unreacted olefinic compounds contained in the reaction product liquid. Of the hydroformylation reaction product is distilled off (first stage distillation).

In the first stage distillation, unreacted olefinic compounds having a relatively low boiling point are mainly separated by distillation.

The degree of decompression for keeping the bottom temperature of the distillation column at 130 ° C. or lower depends on the composition of the reaction product liquid, particularly, the olefinic compound used. That is, the boiling point of an olefin having 4 to 30 carbon atoms is in the range of approximately 0 ° C. to 400 ° C., and is therefore selected from the range of atmospheric pressure to 0.05 mmHg depending on the distillation temperature conditions. Further, the number of stages of the distillation column is not particularly limited, but a low number of stages is preferable in order to prevent pressure loss, and usually several stages, preferably simple distillation is performed.

By the combination of the first-stage distillation under the controlled conditions as described above and the second-stage distillation to be described later, the catalyst is effectively hydroformylated while suppressing the deactivation of the catalyst and the formation of high boiling by-products. It can be separated from the product liquid and recycled. By setting the tower bottom temperature to a temperature condition of 0 to 120 ° C., particularly 50 to 110 ° C., a more remarkable effect can be obtained.

By the first-stage distillation, 60 to 99% of the unreacted olefinic compound and 40 to 95% of the hydroformylation reaction product contained in the hydroformylation reaction product liquid, respectively, preferably,
Distill 80-90% and 40-90% respectively. That is, a part of the unreacted olefinic compound and the hydroformylation reaction product is left at the bottom of the column together with the Group VIII noble metal catalyst component.

The first-stage distillation can be performed in either a batch system or a continuous system. Also, this first stage distillation can be performed in multiple stages.

The bottoms of the first-stage distillation are further steam-distilled at a column bottom temperature of 130 ° C. or lower to substantially distill the remaining unreacted olefinic compound and hydroformylation reaction product (second-stage distillation). .

If the bottom temperature of the distillation column is 130 ° C or lower, the pressure condition and the amount of steam used can be selected independently of each other and are not critical at all, so they are contained due to the hydroformylation reaction product. It may be selected according to the boiling point of the high-boiling by-product, etc., but it is usually carried out at a pressure of normal pressure to several mmHg and a ratio of steam to distillate of 0.1 to several hundreds by weight. The number of stages of the distillation column is not particularly limited, but it is economical to keep the hydroformylation product as little as possible in the bottoms, and it is usually carried out in the range of simple distillation to distillation of several tens of stages. . Distillation can be performed either in a batch system or a continuous system.

In addition, the second-stage distillation can obtain the above-mentioned predetermined effects by combining with the above-mentioned first-stage distillation, but the column bottom temperature is 0 to 120 ° C., particularly 50 to 110 ° C. By setting it below, a more remarkable effect can be obtained.

The bottoms of the second-stage distillation can be reused as it is or by circulating it to the reaction zone as a catalyst liquid derived through a treatment such as distillation.

When a Group VIII noble metal modified with an oxide of a trivalent organic phosphorus compound is used as the catalyst, the stability of the catalyst can be increased by adding the trivalent organic phosphorus compound during distillation. In order to use the catalyst liquid separated and recovered through the first-stage and second-stage distillation again as a hydroformylation reaction catalyst, the trivalent organophosphorus compound should be converted to the corresponding oxide by oxidation at the same time as or after the distillation. Good.

Here, when the non-distilled fraction is oxidized at the same time as the distillation operation to convert the trivalent organic phosphorus compound into the oxide, for example, molecular oxygen may be present in the distillation column for distillation. Usually, by distilling while introducing a small amount of air into the distillation column, the distillation and the oxidation of the trivalent organic phosphorus compound can be carried out simultaneously. For example, in a vacuum distillation column, some air generally leaks, but even with this amount of air, the oxidation of the trivalent organic phosphorus compound proceeds. When the oxidation does not proceed sufficiently in the column, the non-distilled fraction discharged as the column bottom liquid may be oxidized again by the following method.

Also, when the non-distilled fraction is oxidized after the distillation operation to convert the trivalent organic phosphorus compound to the oxide, the oxidation treatment may be carried out in the presence of molecular oxygen or peroxide according to a conventional method.

〔Example〕

Next, the mode for carrying out the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 (A) Hydroformylation reaction Obtained by dimerizing a C ₄ fraction after removing butadiene and isobutene from a BB fraction obtained from a naphtha cracker by a conventional method with a nickel-aluminum catalyst. C ₈ olefin (hereinafter referred to as “octene”) 6 was charged into 10 SUS autoclave, 0.6 g of rhodium acetate aqueous solution (containing 10% of Rh as metal) was added, and triphenylphosphine oxide was added to 1 mol of rhodium. Add 2 moles,
Maintain a total pressure of 170 kg / cm ² G with a water gas of H ₂ / CO = 1, 130 ° C
The reaction was performed at the reaction temperature of 5 hours.

After that, the autoclave was rapidly cooled, the pressure of the water gas was released, and then the whole reaction product liquid was taken out under an inert gas atmosphere. This operation was repeated 3 times to obtain the entire reaction product solution. When the obtained reaction product liquid was analyzed by gas chromatography, the conversion of octene was 90%, the yield of C ₉ aldehyde was 86%, the yield of C ₉ alcohol was 3%, and the yield of high-boiling by-products was 1%.

Triphenylphosphine was added to the reaction product solution in an amount of 8 times mol in terms of rhodium atom for stabilization.

(B) First-stage distillation The reaction product liquid after addition of triphenylphosphine obtained in (A) above was subjected to continuous simple distillation using a glass simple distillation apparatus. The distillation conditions are shown below.

Pressure: 70mmHg Column bottom temperature: 110 ℃ Feed liquid volume: 200ml / hr Distillate volume: 185ml / hr Bottoms volume: 15ml / hr Reactor time of pot: 1.0 hour Distillation time: 5 hours Shown in.

(C) Second Stage Distillation The bottom liquid obtained in (B) above was subjected to continuous steam distillation using a packed column (corresponding to 5 stages) having an inner diameter of 10 mm and a height of 1.5 m.

The distillation conditions are shown below.

Column top pressure: 60 mmHg Column bottom temperature: 110 ° C Feed liquid amount: 14 ml / hr 3 kg / cm ² G saturated steam feed amount: 10 g / hr Reflux ratio: 1 Distillate amount: 9.3 ml / hr Bottoms amount : 4.7 ml / hr Distillation time: 5 hours The distillation results are shown in Table-1.

(D) Activity test of circulating catalyst liquid (canned liquid) (a) Pretreatment Obtained from 180 ml of octene blown with air at 100 ° C to generate 0.7 mol / concentration of peroxide and (C) above. 20 ml of the bottom solution was mixed at 20 ° C. (peroxide / Rh metal in the bottom solution (molar ratio) = 80) to completely oxidize triphenylphosphine in the bottom solution.

(B) Hydroformylation activity test 50 ml of the bottom solution after oxidation treatment obtained in (a) above and 150 ml of octene were charged into an autoclave of 0.5 (Rh metal concentration was 10 mg / equivalent), and above (A) Similarly H ₂ / CO
The total pressure was maintained at 170 kg / cm ² G with = 1 oxo gas, and the reaction was carried out at a reaction temperature of 130 ° C. for 5 hours.

The reaction results are shown in Table 1.

No decrease in hydroformylation reaction activity was observed.

Example-2 In the same manner as in Example-1, except that the reaction product liquid after addition of triphenylphosphine obtained in (A) of Example-1 was used and the distillation conditions were changed as follows, First stage distillation and second stage distillation were performed.

First stage distillation conditions Pressure: 90mmHg Column bottom temperature: 125 ° C Distillate amount: 180ml / hr Bottoms amount: 20ml / hr Second stage distillation conditions Column top pressure: 70mmHg Column bottom temperature: 120 ° C Distillate amount : 9.8 ml / hr Bottoms volume: 4.2 ml / hr The distillation results are shown in Table-1.

Further, the bottoms of the second stage distillation were subjected to an activity test in the same manner as in Example-1. The results are shown in Table-1
Shown in.

Comparative Example-1 In the same manner as in Example-1, except that the reaction product liquid after addition of triphenylphosphine obtained in (A) of Example-1 was used and the distillation conditions were changed as follows, First stage distillation and second stage distillation were performed.

1st stage distillation conditions Pressure: 120mmHg Column bottom temperature: 145 ° C Distillate amount: 171ml / hr Bottoms amount: 29ml / hr 2nd stage distillation conditions Top pressure: 90mmHg Column bottom temperature: 150 ° C Distillate amount : 6.5 ml / hr Bottoms output: 7.5 ml / hr Water vapor feed amount: 3 g / hr The distillation results are shown in Table-1.

Further, the bottoms of the second stage distillation were subjected to an activity test in the same manner as in Example-1. The results are shown in Table-1
Shown in.

Example-3 (A) Hydroformylation reaction As a raw material olefin compound, 1-acetoxy-2-
(1-naphthoxy) ethylene Charge 6 into a 10 SUS autoclave, add 12 g of rhodium acetate aqueous solution (containing 10% of Rh as metal) (rhodium concentration is 200 ml /), and add 2 mol of tripentadecylphosphine to 1 mol of rhodium, and add H. ₂ / CO
The total pressure was maintained at 200 kg / cm ² G with a water gas of = 1 and the reaction was performed at a temperature of 130 ° C. for 6 hours.

After that, the autoclave was rapidly cooled, the pressure of the water gas was released, and then the whole reaction product liquid was taken out under an inert gas atmosphere. When the reaction product liquid was analyzed by gas chromatography, the raw material conversion rate was 89%, the aldehyde yield was 85%, and the high boiling by-product yield was 4%.

(B) First-stage distillation The reaction product solution obtained in (A) above was subjected to batch distillation with a glass simple distillation apparatus. While maintaining the pressure constant, the distillation was stopped when the temperature at the bottom of the column reached 130 ° C. The distillation conditions are shown below.

Pressure: 1mmHg Column bottom temperature: 100-130 ℃ Charge amount: 1 Distillate amount: 0.6 Remaining amount of kettle: 0.4 Distillation results are shown in Table-1.

(C) Second stage distillation For the bottom liquid obtained in (B) above, the inner diameter is 10 mm and the height is 1.5 m.
Steam distillation was carried out batchwise using the packed tower (corresponding to 5 stages). The amount of water vapor is 10g /
It was gradually increased from hr to 100 g / hr. The distillation conditions are shown below.

Column top pressure: 30 mmHg Column bottom temperature: 120 ℃ 3 kg / cm ² G saturated steam feed amount increased from 10 g / hr to 100 g / hr Reflux ratio: 1 Charge ratio: 0.3 Distillate amount: 0.22 Remaining amount of kettle: 0.08 The distillation results are shown in Table-1.

(D) Activity test of circulating catalyst solution (bottom liquid) 1-acetoxy-2- and the bottom liquid obtained in (C) above
(1-naphthoxy) ethylene and rhodium concentration of 200m
g / a were mixed so that, similarly to the above (A), H ₂ / CO
The total pressure was maintained at 200 kg / cm ² G with = 1 oxo gas, and the reaction was carried out at a temperature of 130 ° C. for 6 hours.

The reaction results are shown in Table 1.

Comparative Example-2 First-stage distillation and second-stage distillation were performed in the same manner as in Example-3 except that the reaction product liquid obtained in Example-3 (A) was used and the distillation conditions were changed as follows. Distillation was performed.

First-stage distillation conditions Distillation was stopped when the temperature at the bottom of the column reached 150 ° C while keeping the pressure constant.

Pressure: 0.1mmHg Column bottom temperature: 100-150 ° C Charge amount: 1 Distillate amount: 0.8 Remaining amount of boiler: 0.2 Second stage distillation conditions Column top pressure: 30mmHg Column bottom temperature: 120 ° C 3kg / cm ² G saturated steam Feed amount increased from 10 g / hr to 100 g / hr Reflux ratio: 1 Charge amount: 0.16 Distillate amount: 0.07 Remaining amount of kettle: 0.09 Distillation results are shown in Table-1.

Furthermore, an activity test was conducted in the same manner as in Example-3, using the bottoms liquid of the second stage distillation as the circulating catalyst liquid. The results are shown in Table-1.

[Effect of the Invention] According to the method of the present invention, a hydroformylation reaction product liquid containing a component having a wide range of boiling points, which is obtained by hydroformylating an olefinic compound having a relatively high boiling point and having 4 to 30 carbon atoms, It is possible to efficiently separate the reaction product and the catalyst liquid by suppressing high boiling and deactivation of the catalyst.

Claims (4)

[Claims] 1. An olefinic compound having 4 to 30 carbon atoms in the presence of a trivalent organic phosphorus compound and / or a Group VIII noble metal catalyst modified with an oxide of the trivalent organic phosphorus compound in the hydroformylation reaction zone. Is reacted with carbon monoxide and hydrogen to hydroformylate, and the reaction product liquid extracted from the reaction zone is distilled to separate a distillate containing an unreacted olefinic compound and a hydroformylation reaction product. In the hydroformylation method in which a non-distillate containing a group noble metal catalyst or a catalyst solution derived therefrom is circulated to the reaction zone, distillation of the reaction product solution is carried out, and the reaction product solution withdrawn from the reaction zone is heated to 130 ° C. Distill under reduced pressure at the following column bottom temperature to distill 60-99% of the unreacted olefinic compounds and 40-95% of the hydroformylation reaction product contained in the reaction product liquid, respectively. The first-stage distillation to be carried out, and the bottoms of the first-stage distillation are steam-distilled at a column bottom temperature of 130 ° C. or lower to substantially distill residual unreacted olefinic compound and hydroformylation reaction product. The second stage distillation, which comprises the step of: performing the hydroformylation method. 2. The hydroformylation method according to claim 1, wherein the first-stage distillation and the second-stage distillation are each performed at a bottom temperature of 120 ° C. or lower. 3. The hydroformylation method according to claim 1 or 2, wherein 80 to 90% of the unreacted olefinic compound and the hydroformylation reaction product contained in the reaction product liquid by the first-stage distillation are contained. Characterized by distilling 40 to 90%. 4. The hydroformylation method according to claim 1, wherein an olefinic compound having 8 to 25 carbon atoms is used as the olefinic compound.