JP2888509B2 - Method for producing octa-2,7-dien-1-ol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to an improved process for producing octa-2,7-dien-1-ol by reacting butadiene with water.

[0002] 1-octanol produced by hydrogenating octa-2,7-dien-1-ol is useful as a raw material for a plasticizer such as dioctyl phthalate, and octa-2,7-dien-1-ol. To an oxo reaction, and hydrogenating the resulting product to give 1,9
-Nonanediol is useful as a raw material for producing a polyester having excellent hydrolysis resistance.

[0003]

2. Description of the Related Art The reaction itself of synthesizing octa-2,7-dien-1-ol by reacting butadiene and water in the presence of a palladium catalyst is known. As is well known, a palladium catalyst is a very expensive noble metal catalyst. Therefore, in order to mass-produce octa-2,7-dien-1-ol at low cost on an industrial scale, the following technical requirements 1) to 4) are required. It is important to solve the issues.

1) A high reaction rate can be achieved at an industrially acceptable range of palladium catalyst concentration (about several milligram atoms in terms of palladium atom per liter of reaction mixture). 2) Octa-2,7-diene. -3) the selectivity to -1-ol is sufficiently high, 3) the activity of the palladium catalyst is stably maintained over a long period of time, 4) the produced octa-2,7-dien-1-ol is a palladium catalyst. Is efficiently separated from the reaction mixture without a decrease in activity.

[0005] Usually, octa-2,7-dien-1-ol is separated by distilling a reaction mixture containing a palladium catalyst.
When the distillation temperature exceeded about 120 ° C., a tendency was observed that the palladium catalyst was metallized and deactivated.

As a method for solving the above technical problem, the following manufacturing method has already been proposed (Japanese Patent Publication No. 63-63).
-37774).

(1) In a sulfolane aqueous solution containing a carbonate and / or bicarbonate of a monodentate tertiary amine having a basic constant (pKa) of 7 or more, butadiene and octa-2,
The butadiene is reacted with water in the presence of the palladium compound and at least 6 moles of hydrophilic monodentate phosphine per gram atom of palladium while maintaining the molar ratio of 7-dien-1-ol to 0.6 or more. Thereby synthesizing octa-2,7-dien-1-ol, (2)
Extracting at least a part of the reaction mixture obtained in the step (1) with a saturated aliphatic hydrocarbon, a monoolefinic hydrocarbon or an alicyclic hydrocarbon to give octa-2,7-
The dien-1-ol is extracted and separated, and (3) at least a part of the raffinate containing the catalyst component in the step (2) is recycled to the octa-2,7-dien-1-ol synthesis step in the step (1). For producing octa-2,7-dien-1-ol.

According to this method, octa-2,7-dien-1-ol can be produced with a high reaction rate and a high selectivity even in the presence of a low-concentration palladium catalyst. It can be separated from the reaction mixture without lowering and the palladium catalyst can be recycled and used. However, it has been clarified that even in this method, there is a problem to be solved when continuous operation is performed for a long time on an industrial scale. That is, although the extract obtained in separating octa-2,7-dien-1-ol from the reaction mixture is a very small amount of a palladium catalyst, phosphorus compound, formation of such tertiary amines and sulfolane Minutes elute.
Of the eluted components, especially for expensive palladium catalysts,
A method for efficiently recovering the mixture by washing with a sulfolane water-soluble solution in the presence of a water-soluble phosphine has already been proposed. (Japanese Unexamined Patent Publication No. 3-232831, USP
5,118,885).

[0009]

SUMMARY OF THE INVENTION The above-mentioned JP-A-3-23
According to the method described in JP-A-2831, the eluted palladium catalyst component is effectively recovered. However, in the case where octa-2,7-dien-1-ol is to be produced economically and operation stability is to be continuously increased, it is necessary to minimize the process loss of various components required for the reaction as much as possible. There is. It is necessary to replenish all components lost due to elution from the outside.If the replenishment amount increases, not only is it not economical, but also the operation to maintain the reaction mixture composition constant becomes complicated, and the operation stability deteriorates. It turned out that a problem occurred.

According to a known method, the eluted sulfolane is obtained by evaporating a distillation bottom solution of octa-2,7-dien-1-ol to remove by-products having a higher boiling point than sulfolane. Collected by Since sulfolane is a relatively expensive solvent, conditions must be set to increase the recovery. However, when the recovery rate of sulfolane is increased, it is inevitable that the amount of components having similar boiling points, such as lactone, increases. this,
Synthesis of octa-2,7-dien-1-ol
When recycled to the extent, the octa from the reaction mixture -
Extraction obtained when separating 2,7-dien-1-ol
Tendency for elution amount of tertiary amine and a palladium catalyst into the exudates increases were observed. As a method of avoiding this, a method of removing components such as lactone which is hardly soluble in water by extracting the sulfolane obtained by the above-mentioned evaporation with water has been proposed. Although most of the impurities are removed by this method, when an attempt is made to increase the extraction rate of sulfolane, the amount of water used increases, so that not only a water evaporation step is required but also a small amount of lactone. It is inevitable to mix impurities such as. Therefore, the recovered sulfolane aqueous solution is used for synthesizing octa-2,7-dien-1-ol.
When operating for a long period of time, the reaction mixture
Obtained when separating kuta-2,7-dien-1-ol.
Tendency elution amount of the tertiary amine to extract that increases were observed. The concentration of the tertiary amine is octa-
Since the reaction rate in the synthesis step of 2,7-dien-1-ol is controlled, if this is not kept constant, the composition of the reaction mixture varies. In the continuous extraction process, if the composition of the reaction mixture fluctuates, the extraction rate of various components changes, and the balance of all components fluctuates, which is a major problem in maintaining operation stability. It turns out. Is In continuous reaction, the smaller the change in composition of the reaction mixture,
Needless to say, driving stability is improved. Further, it goes without saying that the smaller the loss to be added from the outside, the higher the operation stability. Furthermore, it goes without saying that the smaller the amount of loss to be added from the outside, the more economical. An object of the present invention is to provide a method for producing octa-2,7-dien-1-ol that solves the above problems.

[0011]

The present inventors have made intensive studies to develop a method for producing octa-2,7-dien-1-ol free from the above-mentioned problems, and as a result, completed the present invention. I came to.

According to the present invention, there are provided the following objects: (1) a monodentate tertiary coordination compound having a basic constant (pKa) of 7 or more;
Butadiene and octa-2,7-diene- in an aqueous sulfolane solution containing carbonates and / or bicarbonates of secondary amines
By maintaining the molar ratio of 1-ol to 0.6 or more and reacting butadiene with water in the presence of a palladium compound and a phosphonium salt, octa-2,7-diene-
1-ol is synthesized and (2) octa-ol is extracted by extracting at least a part of the reaction mixture obtained in the step (1) with a saturated aliphatic hydrocarbon, a monoolefinic hydrocarbon or an alicyclic hydrocarbon.
(3) separating at least a part of the raffinate containing the catalyst component obtained in the step (2) with the octa-2,7-diene-ol of the step (1);
(4) octa-2,7-diene obtained in step (2)
The extract containing 1-ol is washed with an aqueous solution of sulfolane in the presence of water-soluble phosphine, and separated into an aqueous layer of sulfolane and a washed extract layer. (5) At least the aqueous layer of sulfolane obtained in step (4) A part is fed to the extraction step (2), and (6) octa-2,7-dien-1-ol is distilled by distilling the washed extract layer obtained in the step (4).
Acquire product fractions and recover sulfolane
In the method for producing octa-2,7-dien-1-ol, the distillation in the step (6) is carried out in the presence of a hydroxide, carbonate or bicarbonate of an alkali metal or alkaline earth metal. B) octa-2,7-diene-1 obtained in step (6)
The product fraction containing all is washed by contacting it with carbon dioxide and water, and the resulting wash water is subjected to the step
Feed to (4) washing process with sulfolane aqueous solution
And the sulfolane recovered in step (6)
The cleaning step with aqueous sulfolane solution in step (4)
Octa-2,7-diene, wherein the sul-1-
This is achieved by providing a method of manufacturing oars.

According to the present invention, the lactone and the lactone hydrolyzed acid which are present in the recovered sulfolane and cause a problem so far do not substantially exist.
It has been clarified that the recovered sulfolane can be recycled without extracting with water. As a result, the reaction
Separation of octa-2,7-dien-1-ol from the mixture
Thus, the amount of the tertiary amine and the palladium catalyst eluted into the extract obtained at the time of the reduction is reduced, and the load of the recovered amine and the palladium catalyst is significantly reduced. In the extraction process, it is important to keep the sulfolane, water and tertiary amine concentrations in the reaction mixture constant. From the viewpoint of operation management, it is preferable that sulfolane and water necessary for concentration control can be independently fed so as to cope with all fluctuations. The recovered sulfolane necessary to economy and operability can be ensured without evaporation of water is significantly improved.

Further, octa-2,7-diene-1-o
Part of the water that must be consumed supplemented with synthesis reactions Lumpur, without using the sulfolane recovered process this
Octa-2,7-dien-1-ol obtained in (6)
Tertiary amine which cannot be recovered in the extractant recovery step [step (4)] and is lost in a very small amount can be effectively recovered in the aqueous layer by using carbon dioxide gas for washing the product fraction containing the <br/> wear is Heading. Thereby, the loss of the tertiary amine is further reduced.

In the present invention, the reaction mixture is usually
Obtained when separating octa-2,7-dien-1-ol.
It is extracted Bleeding carbon dioxide and unreacted butadiene is recovered from, then an extractant and tertiary Amin is recovered by distillation. From extraction agent and the residual liquid was distilled tertiary amines, octatriene and octa-1,7-diene -3
-After separating low boiling products such as ol,
2,7-Dien-1-ol is separated by distillation. However, when octa-2,7-dien-1-ol alone is not required, it is separated by distillation as a mixture with a low-boiling product,
The resulting mixture can be subjected to, for example, hydrogen reduction.

In the present invention, the distillation according to the step (6) is performed by using a hydroxide of an alkali metal or an alkaline earth metal,
It is carried out in the presence of carbonate or bicarbonate. The amount of hydroxide, carbonate or bicarbonate of the alkali metal or alkaline earth metal is not particularly limited, but the lactone and lactone present in the extract obtained by distillation of the extractant and the tertiary amine are hydrolyzed. It becomes the formed acid equivalents or more with
It is rather preferred that amount, in particular, an equivalent amount or 5 times
It is more preferable that the amount be as follows . The alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate can be added as a solid or as an aqueous solution.

According to the present invention, in step (6)
<br/> product fraction having containing octa-2,7-dien-1-ol, which is the under carbon dioxide atmosphere, and washed with water.

[0018] 0 is not particularly limited to the amount of water used in this, since water is consumed in the synthesis reaction of octa-2,7-dien-1-ol, of water consumed in the reaction. 5-
About equivalent weight is preferable. As the carbon dioxide gas, a dedicated carbon dioxide gas may be used, but it is preferable to use an off-gas that is partially purged in the plant. Carbon dioxide gas may be normal pressure or pressurized, but a pressurized system of 20 atm or less is more preferable. The washing temperature varies depending on the degree of pressurization, but is generally preferably 50 ° C. or less, at which the carbonate of the tertiary amine is hardly decomposed. The washing water is fed to the step (4), and charged into the catalyst liquid through the step (2).

Further, sulfolane because it is recovered in high purity state by evaporation from the remaining bottom liquid was distilled off octa-2,7-dien-1-ol in the above, can be directly circulated and reused.

In the step (4) in the present invention, the water-soluble phosphine to be present when the extract containing octa-2,7-dien-1-ol obtained in the step (2) is washed with an aqueous sulfolane solution includes: The following general formula (I)

[0021]

Embedded image (Wherein, M represents an alkali metal), is preferred. Specific examples of the alkali metal represented by M in the general formula (I) include lithium, sodium, and potassium. The amount of the water-soluble phosphine is preferably at least 1 equivalent to the palladium atom contained in the extract obtained in the step (2). When the water-soluble phosphine is not present, step (2) 30-40% approximately of a palladium catalyst contained in the extract obtained in only can not be recovered in sulfolane solution, water
With sex phosphine, Ru can be recovered from 90% to 100% of the palladium catalyst contained in the extract obtained in step (2) in sulfolane solution. Moreover, at that time, the amount of the phosphorus compound eluted into the extract containing octa-2,7-dien-1-ol does not increase. The upper limit on the use is not water-soluble phosphine, the amount used is contained in the extract layer was washed obtained in step (4) Li
An amount corresponding to the amount of the phosphorus compound, that is, an amount equivalent to the mole of the phosphorus compound eluted out of the reaction system is preferable. Step (4)
Is used in the step (6) described above.
2,7-dien-1-ol obtained in
It is preferable to use the washing water obtained by the washing operation of the product fraction containing . The sulfolane in the extract obtained in the step (2) is collected in the aqueous layer together with the palladium to form an aqueous sulfolane solution. The washing operation in the step (4) is preferably performed in an atmosphere of carbon dioxide. The partial pressure of carbon dioxide is greater than 3 atmospheres ( absolute pressure ) and 20 atmospheres
( Absolute pressure ), preferably 4 to
It is preferably 16 atmospheres ( absolute pressure ) . The recovery rate of the palladium catalyst and the phosphorus compound in the aqueous solution of sulfolane hardly changes depending on the pressure of carbon dioxide. The pressure of carbon dioxide has a significant effect on the recovery of tertiary amines, and the higher the pressure of carbon dioxide, the higher the recovery of tertiary amines, and the partial pressure of carbon dioxide rises above 20 atmospheres ( absolute pressure ) . Nearly 100% of the tertiary amine is recovered. From being efficiently recovered with the extractant by distillation in the tertiary amine after step (6), not dare to be the high partial pressure of carbon dioxide in step (4).

[0022] The temperature at which the washing in step (4), in order to recover the palladium catalyst while maintaining its activity, it is preferred to employ a temperature in the range of 0 to 80 ° C., of 5 to 30 ° C. More preferably, a temperature in the range is employed . Washing operation is a batch method, a continuous method any of the
It may be carried out in a system, and is carried out using a commonly used extraction / washing device.

In the step (6) of the present invention, when the washed extract layer obtained in the step (4) is subjected to a distillation operation, it is preferable to add dimethylglyoxime to the extract layer in advance. Dimethylglyoxime is effective in suppressing metalation of palladium catalyst in steam Tomekan solution. Dimethylglyoxime was added in a molar ratio of 1 to palladium atoms dissolved in the washed extract layer.
It is preferably 0 or more. Note that if the recovery of the palladium catalyst in step (4) is long as it is effectively implemented, Engineering
When distilling the washed extract layer obtained in step (4), it is not necessary to add dimethylglyoxime to the extract layer . By recovering the palladium catalyst in step (4) and stabilizing the palladium catalyst during the distillation operation in step (6) with dimethylglyoxime,
Metallization of the palladium catalyst in the boiler liquid can be suppressed, and a stable distillation operation is guaranteed.

In the step (1) of the present invention, octa-2,7-dien-1-ol has a basic constant (pK
a) In a sulfolane aqueous solution containing a carbonate and / or bicarbonate of a monodentate tertiary amine having 7 or more, the molar ratio of butadiene to octa-2,7-dien-1-ol is 0.6 or more. And reacting butadiene with water in the presence of a palladium compound and a phosphonium salt. Butadiene and Octa-2,7
The molar ratio of -dien-1-ol needs to be maintained at 0.6 or more, and is preferably maintained in the range of 0.8 to 1.6. Butadiene and octa-2,7-diene-
If the molar ratio of 1-ol is less than 0.6, the accumulation of insoluble polymer in the reaction mixed solution, deactivation of the palladium catalyst, decrease in the reaction rate and reaction selectivity, further steps
When (2) separates octa-2,7-dien-1-ol from the reaction mixture, the amount of the palladium catalyst eluted into the extract increases. Butadiene and octa-
The upper limit of the molar ratio of 2,7-dien-1-ol is not particularly limited, but is usually preferably 20 or less. Butadiene and octa-2,7-dien-1-ol
If the molar ratio is greater than 20 , the amount of butadiene recovered will increase, and the reaction mixture will become heterogeneous, and the extraction performed following the octa-2,7-dien-1-ol synthesis reaction will be performed. In operation, the amount of sulfolane and the like eluted into the extract is increased, and it is economically disadvantageous such that a large reactor is required.

As butadiene, any of industrially available polymerization grade products, chemical reaction grade products, and hydrocarbon mixtures commonly referred to in petrochemicals as C4 fractions can be used. However, in consideration of the reaction rate and the ease of recovery of unreacted butadiene, it is preferable to use polymerization grade products and chemical reaction grade products.

The monodentate tertiary amine carbonate and / or bicarbonate having a basic constant (pKa) of 7 or more used in the step (1) of the present invention is octa-2,7-diene- The reaction rate is remarkably improved while maintaining the selectivity to 1-ol at a high level, the activity of the palladium catalyst is stabilized, and the octa-2,7-diene is extracted in the extraction step (2) following the reaction step (1). It has the effect of increasing the extraction rate of -1-ol. Such monodentate tertiary amines include, for example, tolmethylamine, triethylamine, tri - n-butylamine, 1- ( N, N-dimethylamino ) -2-propanol, N, N-dimethyl-2. −
Methoxyethylamine, N-methylmorpholine, N,
N, N ', N'-tetramethylhexamethylenediamine and the like. Among these, the reaction results, boiling point,
Considering various points such as solubility and cost, trimethylamine or triethylamine is preferred. Monodentate 3rd
The above-mentioned excellent effect of the addition of the carbonate and / or bicarbonate of a tertiary amine is attributed to the carbonate and / or bivalent of a monodentate or bidentate tertiary amine having a pKa of less than 7, such as pyridine and dipyridyl. Carbonates, and even those having a strong bidentate coordination ability such as N, N, N ', N'-tetramethyldiaminoethane and N, N-dimethyl-2-aminopropiononitrile even when pKa is 7 or more. When tertiary amine carbonates and / or bicarbonates are used, they are not sufficiently expressed.

The carbonate and / or bicarbonate of a monodentate tertiary amine having a pKa of 7 or more is converted into a carbonate and / or bicarbonate ion and a monodentate tertiary amine in a reaction system. present as 衡 mixture (see below equilibrium), the abundance ratio of the tertiary carbonate and / or bicarbonate of an amine in the reaction conditions will depend on the temperature and the partial pressure of carbon dioxide in the reaction system.

[0028]

Embedded image Therefore, the reaction is usually carried out at a partial pressure of carbon dioxide of about 1 to 1
This is performed in a state where the pressure becomes 0 atm (absolute pressure). Considering the reaction performance, extraction efficiency, and the amount of tertiary amine eluted in the extraction layer obtained in step (2), the tertiary amine carbonate and / or bicarbonate are added to the reaction mixture. It is preferably used in such an amount that the range is 5 to 10% by weight.

Water is present in the reaction system as an aqueous sulfolane solution. The aqueous sulfolane solution not only does not adversely affect long-term continuous use, but also allows the product to be separated by extraction from the reaction mixture. Further, it has the effect of increasing the reaction rate and increasing the selectivity to octa-2,7-dien-1-ol. Considering the solubility of butadiene and the extraction efficiency of octa-2,7-dien-1-ol, the concentration of water in the aqueous sulfolane solution is 7 by weight of water and sulfolane.
It is desirable to maintain 0:30 to 30:70, preferably 60:40 to 40:60. When the amount of water increases, the reaction rate tends to decrease, and when the amount of water decreases, the extraction rate of octa-2,7-dien-1-ol decreases,
In addition, the amount of the sulfolane and the catalyst component eluted into the extract tends to increase.

In the step (1) of the present invention, the palladium compound to be present in the reaction system is not particularly limited. As the palladium catalyst, for example, a palladium compound that has been proposed to be used in a synthesis reaction of octa-2,7-dien-1-ol can be used. Specific examples of these palladium compounds include palladium acetylacetonate, π-allyl palladium acetate, π-allyl palladium chloride, palladium acetate, palladium carbonate, palladium nitrate, palladium chloride, sodium chloroparadate, bisbenzonitrile palladium chloride, bistrinitride triphenylphosphine palladium chloride, bis (triphenylphosphine) palladium acetate, bis (1,5-cyclooctadiene diethyl yl)
Palladium, bis-π-allyl palladium and the like can be mentioned. Since the active species of the true palladium catalyst in the synthesis reaction of octa-2,7-dien-1-ol is a low-valent palladium complex, when a divalent palladium compound is used as a catalyst, it is added to the reaction system. The active species of the palladium catalyst can also be formed by reduction with butadiene present in the palladium catalyst.However, by reacting the divalent palladium compound with a reducing agent in the same reaction system or in a separate reaction vessel, An active species can be formed and used. Examples of the reducing agent used for this purpose include an alkali metal hydroxide, an alkali metal carboxylate, sodium borohydride, zinc dust, magnesium, and hydrazine. The amount of the palladium compound to be present in the reaction system is not particularly limited, but is industrially preferably 0.5 to 50 milligram atoms, more preferably 0.5 to 5 milligram atoms per liter of the reaction mixture. Desirably, it is present in an amount that results in a concentration of milligram atoms.

In the step (1) in the present invention, the phosphonium salt to be present in the reaction system is represented by the following general formula (I)
I)

[0032]

Embedded image (Wherein, R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and R ³ may have a hydrogen atom or a substituent. A hydrocarbon group having 1 to 5 carbon atoms, M represents an alkali metal, and X represents a hydroxyl group or a hydrocarbonyloxy group). General formula (I
In I), the hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ and R ² includes methyl, ethyl, n-propyl,
alkyl groups such as n-butyl, n-pentyl and n-octyl; aliphatic hydrocarbon groups such as alkenyl groups such as 2-propenyl, 3-butenyl and 1-pentenyl; lipids such as cycloalkyl groups represented by cyclohexyl And cyclic hydrocarbon groups; and aryl hydrocarbon groups such as aryl groups such as phenyl and tolyl, and aralkyl groups such as benzyl. Examples of the hydrocarbon group having 1 to 5 carbon atoms R ³ represents methyl, ethyl, alkyl groups such as propyl; can be exemplified allyl, an aliphatic hydrocarbon group such as an alkenyl group such as 4-pentenyl. Examples of the substituent include a di (lower alkyl) amino group such as a dimethylamino group; a cyano group; a formula —SO ₃ M or —COOM (where M represents an alkali metal such as lithium, sodium, and potassium) And the like. Further, specific examples of the alkali metal represented by M include lithium, sodium and potassium. The amount of the phosphonium salt used depends on the reaction rate and the selectivity to octa-2,7-dien-1-ol, the long-term stabilization of the activity of the palladium catalyst, and the subsequent extraction step (2).
In consideration of the effect of suppressing the elution of the palladium catalyst into the extract in the above, the amount is usually 6 mol or more, preferably 10 mol or more per gram atom of palladium. Although there is no strict upper limit for the amount of phosphonium salt used, phosphonium salts are generally used in amounts of 1 to 1 gram atom of palladium.
It is used in such an amount as to be 50 mol or less, preferably 8 mol or less.
It is used in such an amount as to be 0 mol or less.

The phosphonium salt represented by the general formula (II) is prepared by converting the phosphine represented by the general formula (I) in the presence of a palladium compound and water containing a carbonate ion and / or a bicarbonate ion. General formula (III) at least equimolar to phosphine

[0034]

Embedded image (Wherein R ¹ , R ² and R ³ are as defined above).

The synthesis reaction of octa-2,7-dien-1-ol is usually carried out at a temperature of 50 to 110 ° C. As the reaction device, a gas-liquid contact type device known per se, such as a stirring type reaction tank and a bubble column type reaction tank, can be used.

As described above, the step (2) in the present invention
In the above, octa-2,7-dien-1-ol is separated by extracting at least a part of the reaction mixture with an extractant, but octa-2,7-ol can be used as an extractant. Saturated aliphatic hydrocarbons, monoolefinic hydrocarbons and alicyclic hydrocarbons having a lower boiling point than dien-1-ol. Specific examples of these include n-
Butane, isobutane, n-pentane, n-hexane, n
- heptane, n- octane, saturated aliphatic hydrocarbons such as isooctane; butene, monoolefinic hydrocarbons such as isobutene; cyclohexane, shea click Rohekisen, include alicyclic hydrocarbons such as methylcyclohexane, and as butadiene source Butane contained in the C4 fraction of
A mixture of hydrocarbons such as butene and isobutene can be mentioned. Among these, n-pentane, n-hexane, cyclohexane and methylcyclohexane are particularly preferably used. These extractants may be used alone or as a mixture. The extractant is obtained by the synthesis reaction of octa-2,7-dien-1-ol in consideration of the extraction efficiency of octa-2,7-dien-1-ol and the elution amount of the catalyst component and sulfolane in the extract. It is used in an amount in the range of 0.3 to 3 by volume ratio to the obtained reaction mixture.

The extraction operation in step (2) is preferably performed in an atmosphere of carbon dioxide. The partial pressure of carbon dioxide is 3
The pressure is preferably greater than the atmospheric pressure ( absolute pressure ) and less than 20 atm ( absolute pressure ), more preferably 4 to 16 atm ( absolute pressure ) . The partial pressure of carbon dioxide 3 care
Below the pressure ( absolute pressure ) , not only the amount of the tertiary amine eluted increases, but also the eluted amount of the palladium catalyst increases with time. Further, the stability of the extraction interface composed of the extract and the catalyst solution is poor. On the other hand, 20 care about the partial pressure of carbon dioxide
It is not economical to make the pressure higher than the pressure ( absolute pressure ) because unnecessary carbon dioxide more than the elution suppressing effect of the palladium catalyst is used. As the temperature in the extraction operation, in order to suppress the elution of the palladium catalyst and the tertiary amine, a temperature in the range of 0 to 40 ° C is preferably used, and a temperature in the range of 5 to 30 ° C is more preferable. . When the extraction operation is performed at a temperature higher than 40 ° C., the third
Not only does the amount of tertiary amine elute increase, but also the generated octa-2,7-dien-1-ol undergoes a decomposition reaction with the same catalyst system, resulting in a decrease in selectivity. Furthermore, octa
As the 2,7-dien-1-ol is decomposed, the elution amount of the palladium catalyst increases with time. As the extraction temperature decreases, the elution amount of the palladium catalyst and the elution amount of the tertiary amine tend to decrease, but when the extraction is performed at a temperature lower than 0 ° C., the separability of the extraction interface deteriorates. As the extraction device used in the step (2), an industrially-used agitated extractor, an RDC extractor, a perforated plate tower, or the like can be applied. Industrially, the extraction operation is performed in a continuous manner by providing a sufficient standing tank for phase separation.

At least a part of the raffinate (sulfolane aqueous solution) containing the catalyst component thus obtained is fed to the octa-2,7-dien-1-ol synthesis reaction step (1) and reused. Is done. The water-soluble phosphine used in the step (4) is completely converted into a phosphonium salt in the washing step in the step (4) or in the extraction step (2) fed in a state contained in the aqueous sulfolane layer in the step (5). Therefore, in the step (3), the raffinate fed to the octa-2,7-dien-1-ol synthesis reaction step of the step (1) does not contain water-soluble phosphine. If necessary, a part of the raffinate may be taken out, subjected to a catalyst activation treatment, and then circulated to the above synthesis reaction step.

[0039] In the method of the present invention, step a catalyst system or we eluted Ingredient is step by extraction operation in (2) (4)
In, a palladium catalyst, a phosphorus compound, a part of a tertiary amine and sulfolane are recovered, and in step (6), a carbon dioxide gas, an extractant, a tertiary amine and sulfolane are recovered. A trace amount of each of the above-mentioned unrecovered components is lost to the outside of the system as a palladium catalyst, a phosphorus compound and sulfolane, together with a high-boiling substance from a distillation bottom liquid, and a tertiary amine as a low-boiling fraction. Thus, each component of the loss amounts are added to the newly catalyst system. Everything to add
The can Ingredient, a chemical solution according to the amount to be each additional prepared by dividing a combination according to the batch or purpose, but is added intermittently or continuously, for the tertiary amines, pre dioxide Carbonate and / or in the presence of carbon and water
Alternatively, it is desirable to supply as an aqueous solution after conversion to bicarbonate. An aqueous palladium catalyst, a phosphonium salt and a sulfolane may be present in the aqueous carbonate solution, but an aqueous solution of a tertiary amine carbonate and / or bicarbonate, an aqueous sulfolane solution containing a palladium catalyst and a phosphonium salt, and A method in which the aqueous solution of sulfolane is separately added to the catalyst system by dividing into three portions is preferable because the composition of the reaction solution can be kept constant and stable operation can be achieved.

[0040]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 A continuous reaction was carried out using the following apparatus under the following operating conditions, and the reaction results in a steady state were examined.

Reactor temperature controller, stirrer, butadiene feed pump,
A stainless steel pressure-resistant reactor equipped with a catalyst liquid circulation pump, carbon dioxide inlet, pressure regulating valve, and level gauge. The reaction mixture is sent to the extraction device via a pressure reducing valve.

Extractor A mixer-settler extractor equipped with a pressure reducing valve, a pressure regulating valve, a thermometer, a stirrer, an extractant feed pump, a liquid level gauge and an interface meter. The raffinate catalyst liquid is quantitatively fed to the reactor through a catalyst storage tank by a catalyst feed pump. Extract is fed to <br/> cleaning apparatus according to a sulfolane solution of the extract in the extraction liquid feed pump.

Washing device using aqueous solution of extract for sulfolane A washing device comprising an extract feed pump, a water feed pump, a static mixer and a stationary tank . Lower sulfolane solution layer is fed to the catalyst tone made vessel and extraction device with additional circulating pump. The upper layer of the washed liquid extract is fed to a distillation apparatus via a pressure reducing valve.

Distillation apparatus butadiene recovery column (recovery of butadiene and carbon dioxide), extractant recovery column (recovery of extractant and tertiary amine),
A distillation apparatus provided with a thin-film evaporator (separation of eluted palladium catalyst and eluted phosphorus compound and high-boiling cut) and a purification tower (purification of octa-2,7-dien-1-ol).

Sulfolane recovery device A falling film type evaporator equipped with an alkaline aqueous solution feed pump . Evaporated in a falling film evaporator the liquid is allowed to stand, the washing <br/> purification device sulfolane rich lower layer due to the sulfolane solution of the extract, the upper layer of the high boiling liquid is fed to a distillation apparatus.

Octa-2,7-dien-1-ol washing device A mixing and stirring device provided with a carbon dioxide gas feed port and a standing tank . Miscellaneous equipment various tanks, the reaction mixture in the reaction vessel in the catalyst preparation tank operating conditions and operating results steady state (homogeneous solution) The composition of sulfolane 34 wt%, water 30 wt%, Application Benefits ethyl <br/> triethanolamine 9 0.8% by weight, palladium catalyst (catalyst formed from palladium acetate) 1.7 milligram atoms / liter (converted to palladium atoms), formula

[0047]

Embedded image Are maintained at 60 mmol / l, butadiene 1.1 mol / l, and octa-2,7-dien-1-ol 0.9 mol / l, at a reaction temperature of 70 ° C and a reaction pressure of 14.5 kg. / Cm ² G (pressurized with carbon dioxide) and the residence time of the reaction solution was 1.0 hour.

[0048] The above mixture, the volume ratio 0.66 of the reflected response mixture and the extractant (n- hexane solution containing triethylamine traces), carbon dioxide gas under a pressure of 4 atmospheres (absolute pressure), 20
Extraction was performed continuously under the condition of ° C. The product, butadiene, triethylamine and sulfolane in the extract after 55 days were analyzed by gas chromatography, the palladium catalyst by atomic absorption analysis, and the phosphorus compound by colorimetry. The 7-dien-1-ol concentration was 11.2% by weight, and the amount of the solvent and the catalyst eluted in the extractant was 2.0 pp of a palladium catalyst (atomic conversion).
m, a phosphorus compound (phosphorus atom terms) 5.6 ppm, sulfolane 1.2 wt%, Application Benefits ethylamine 0.5 wt%, was 0.15% by weight of water.

The extract 1000 parts by weight of sulfolane rich lower layer 14 parts by weight recovered from sulfolane recovery device against (including sulfolane 12 parts by weight), octa -2,7
17 parts by weight of an aqueous solution recovered from a washing device for dien-1-ol, and diphenylphosphinobenzene-m
- continuously adding an aqueous solution 0.032 parts by weight containing a lithium salt 31 wt% of the sulfonate in a ratio of this, the temperature 20
The mixture was mixed with a static mixer under a carbon dioxide gas pressure of 4 ° C. and 4 atm ( absolute pressure ) , and the mixture was separated in a stationary tank. As a result of the analysis of the upper layer solution, the octa-2,7-dien-1-ol concentration was 11
In terms of weight%, the elution amount of the solvent and the catalyst was 0.2 ppm of a palladium catalyst (in terms of atoms), 1.1 ppm of a phosphorus compound (in terms of phosphorus atoms), 1.25 wt% of sulfolane, 0.17 wt% of triethylamine, and 0.15 wt% of water. % By weight. As a result, it can be seen that 92.5% of the palladium catalyst, 80% of the phosphorus compound, and 66% of triethylamine were recovered in the lower layer. The lower layer was fed continuously to the extraction device.

The upper liquid was fed to a distillation apparatus . Unreacted butadiene and carbon dioxide were recovered by distillation under a pressure of 4 kg / cm ² G in a butadiene recovery tower. Next
Then , hexane was recovered together with triethylamine at an overhead temperature of 60 ° C. under normal pressure conditions and continuously fed to an extraction device. The bottom liquid of the extractant recovery tower was continuously fed to the thin film evaporator. Here, a compound having a boiling point equal to or lower than sulfolane was evaporated, and a palladium catalyst, a phosphorus compound and high-boiling substances eluted in the extraction step were cut. The can solution contained 5% by weight of sulfolane. The evaporate is fed to a purification tower, and the distillate containing octa-2,7-dien-1-ol as a main fraction is brought into contact with 17 parts by weight of an off gas containing carbon dioxide gas of an extraction system and 17 parts by weight of water. Was. Further oct low-boiling product was obtained after <br/> was cut-2,7-dien-1-ol of G
C purity was 99.8%.

The bottom liquid of the refining column includes a sulfolane and high boiling products, a 40 wt% aqueous solution containing sodium hydroxide 0.6 parts by weight was added in sulfolane recovery device, in a falling film type evaporator After evaporation, the mixture was allowed to stand, and the lower layer was fed to a washing device using an aqueous solution of sulfolane as an extract. The upper layer liquid was fed to the thin film evaporator, and the falling film type can liquid was returned to the thin film evaporator.

In the catalyst preparation tank, the palladium catalyst and phosphonium salt corresponding to the amount lost outside the reaction system were dissolved in an aqueous sulfolane solution and fed, but the palladium catalyst concentration and the phosphonium salt concentration in the reaction solution were almost constant. Was kept. Further, in order to finely adjust the sulfolane concentration and the water concentration in the reaction solution, fresh sulfolane and water were appropriately fed to an extraction device. To keep the concentration of triethylamine in the reaction solution constant, an aqueous solution of triethylamine carbonate and / or bicarbonate equivalent to 35% by weight in terms of triethylamine was fed. 1t
The triethylamine concentration in the reaction solution was kept constant by adding 0.5 kg of triethylamine per octa-2,7-dien-1-ol. This indicates that the recovery of triethylamine is about 97%.

When the operation was performed continuously for 60 days by the above operation, the operation was extremely stable and showed a certain reaction result.

Comparative Example 1 In Example 1, a sulfolane solution containing a high-boiling substance was directly added to the extract independently of water without adding sodium hydroxide.
The solution is fed to a washing apparatus using an aqueous sulfolane solution, and the distillate containing octa-2,7-dien-1-ol as a main component is washed under the same reaction conditions, extraction conditions, and distillation conditions without performing the washing. For 25 days.

Although the operation was relatively stable until the seventh day, the concentration of palladium in the extract gradually increased, and the concentration of eluted palladium was high even after the extract was washed with an aqueous sulfolane solution . Loss increased. 18
As a result of analyzing the washed extract after day, octa-2,
7-dien-1-ol concentration 9.8 wt%, elution of the solvent and the catalyst, a palladium catalyst (atomic basis) 1.
3 ppm, phosphorus compound (converted to phosphorus atom) 2.3 ppm,
The content was 1.2% by weight of sulfolane, 0.42% by weight of triethylamine, and 0.15% by weight of water. As a result, the amount of palladium catalyst to be added to keep the palladium concentration in the reaction solution constant was increased. In order to keep the concentration of triethylamine in the reaction solution constant, an additional amount of 15 kg of triethylamine was required to produce 1 t of octa-2,7-dien-1-ol.

[0056]

According to the present invention, as it is clear from the above examples, it is possible to obtain the feed can sulfolane directly to the catalyst system, over the elution amount of tertiary amine and a palladium catalyst in long And the composition of the catalyst system was easily kept constant. Further, the third loss in the octa-2,7-dien-1-ol fraction
Since the tertiary amine and sulfolane can be recovered as an aqueous solution of carbonate and / or bicarbonate, the loss of the tertiary amine and sulfolane can be minimized.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI C07B 61/00 300 C07B 61/00 300 (58) Field surveyed (Int. Cl. ⁶ , DB name) C07C 33/02-33/035 C07C 29/44-29/46 C07C 29/04

Claims (5)

(57) [Claims] (1) In a sulfolane aqueous solution containing a carbonate and / or bicarbonate of a monodentate tertiary amine having a basic constant (pKa) of 7 or more, butadiene and octa-
By maintaining the molar ratio of 2,7-dien-1-ol at 0.6 or more and reacting butadiene with water in the presence of a palladium compound and a phosphonium salt,
2,7-dien-1-ol is synthesized, and (2) at least a part of the reaction mixture obtained in the step (1) is extracted with a saturated aliphatic hydrocarbon, a monoolefinic hydrocarbon or an alicyclic hydrocarbon. By doing
(3) separating at least a part of the raffinate containing the catalyst component obtained in the step (2) with the octa-2,7-diene-ol of the step (1);
(4) octa-2,7-diene obtained in step (2)
The extract containing 1-ol is washed with an aqueous solution of sulfolane in the presence of water-soluble phosphine, and separated into an aqueous layer of sulfolane and a washed extract layer. (5) At least the aqueous layer of sulfolane obtained in step (4) A part is fed to the extraction step (2), and (6) octa-2,7-dien-1-ol is distilled by distilling the washed extract layer obtained in the step (4).
Acquire product fractions and recover sulfolane
In the method for producing octa-2,7-dien-1-ol, the distillation in the step (6) is carried out in the presence of a hydroxide, carbonate or bicarbonate of an alkali metal or alkaline earth metal. B) octa-2,7-diene-1 obtained in step (6)
The product fraction containing all is washed by contacting it with carbon dioxide and water, and the resulting wash water is subjected to the step
Feed to (4) washing process with sulfolane aqueous solution
And the sulfolane recovered in step (6)
The cleaning step with aqueous sulfolane solution in step (4)
Octa-2,7-diene, wherein the sul-1-
Oar manufacturing method. 2. The method according to claim 1, wherein the tertiary amine is trimethylamine or triethylamine. 3. The method of claim 1, wherein the phosphonium salt is in an amount of at least 6 moles per gram atom of palladium.
The manufacturing method as described. 4. The amount of water-soluble phosphine obtained in step (2)
The process according to any one of claims 1 to 3 with respect to the palladium atoms is 1 equivalent or more contained in the extract containing is octa-2,7-dien-1-ol. 5. The method according to claim 1, wherein dimethylglyoxime is added to the washed extract layer obtained in step (4) in a molar ratio of at least 10 times the molar ratio to palladium atoms in the extract layer. The manufacturing method according to any one of the above.