JP2000355563A - Production of diol mixture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a diol mixture useful as a raw material for polyester resin, urethane foam or the like in high yield by directly hydrogenating, namely, reducing a mixture of dicarboxylic acids. SOLUTION: This mixture of 1,4-butanediol and a compound of the formula: HO-CH2-R-CH2OH is obtained by introducing a dicarboxylic acid mixture of succinic acid and a compound of the formula: HOOC-R-COOH (R is a 3-20C alkylene), a catalyst carrying Ru-Sb-Pt on a carbonaceous carrier (e.g. activated carbon) treated with steam and/or carbon dioxide and water into an autoclave, injecting hydrogen thereinto and reacting preferably under the condition of 100-300 deg.C temperature and 1M-25M Pa pressure. The raw material dicarboxylic acid mixture is preferably recovered from an oxidation reaction liquid of cyclohexanone and/or cyclohexanol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for directly hydrogenating a dicarboxylic acid mixture containing succinic acid, glutaric acid, and adipic acid without using an esterification step to obtain 1,4.
-Butanediol, 1,5-pentanediol, 1,6
A process for producing a diol mixture containing hexanediol. Diols are useful substances as raw materials for polyester resins, urethane foams, urethane paints, and adhesives.

[0002]

2. Description of the Related Art There have been reported many methods for producing 1,4-butanediol by hydrogenating succinic acid or maleic acid. For example, the best known method is to use a copper-based catalyst. However,
In this method, succinic acid cannot be directly reduced,
The carboxylic acid must be once converted to an ester and then reduced, which lengthens the production process.

On the other hand, there have been proposed some methods for producing 1,4-butanediol by directly reducing succinic acid or maleic acid. A catalyst consisting of ruthenium-iron oxide (US Pat. No. 4,827,
001), ruthenium-tin with a BET surface area of 2000 m
² / g or more of catalyst supported on porous carbon
No. 46915), a catalyst in which ruthenium and tin are supported on silica modified with titanium and / or alumina (Japanese Unexamined Patent Publication No.
116182), ruthenium and tin, and a catalyst in which an alkali metal compound or an alkaline earth metal is supported on a carrier (Japanese Patent Laid-Open No. 6-239778), and tin and at least one selected from ruthenium, platinum and rhodium are used as a carrier. Using a supported catalyst (JP-A-7-165644), a catalyst in which ruthenium and tin are supported on a carrier, excess hydrogen is passed through the reaction system, and the reaction is carried out while removing entrained products to the outside of the system. (Japanese Patent Application Laid-Open No. Hei 9-12492)
No.), a catalyst containing ruthenium-tin-platinum supported on a carrier (JP-A-9-59190), and ruthenium-tin prepared by impregnating activated carbon with a solution containing a supported component coexisting with a carbonyl compound having 5 or less carbon atoms. A catalyst in which platinum is supported on activated carbon (JP-A-10-15388); a catalyst in which ruthenium-tin-platinum is supported on activated carbon in which the metal-supported state is specified by using activated carbon in contact with nitric acid in advance (JP-A-10-15388) -71332) has been proposed,
In any of the methods using the catalyst, the selectivity of 1.4-butanediol, tetrahydrofuran, and γ-butyrolactone was not sufficient, and the yield of 1,4-butanediol was unsatisfactory. Japanese Patent Application Laid-Open No. 7-82190 proposes a method of performing hydrogenation using a catalyst comprising palladium and a rhenium compound and using a tertiary alcohol as a solvent, but the reaction rate is still insufficient.

On the other hand, oxygen-containing C4 hydrocarbon raw materials include:
Maleic anhydride or maleic acid obtained by air oxidation of butane is preferred because it is industrially produced, but dicarboxylic acids by-produced when adipic acid is produced by oxidizing cyclohexanone and / or cyclohexanol. Is also a suitable raw material. That is, if an industrially useful compound can be obtained using this dicarboxylic acid as a raw material, the waste generated in the production of adipic acid can be reduced.In addition to succinic acid, glutaric acid and adipine are generally included in addition to succinic acid. It is expected that not only 1,4-butanediol but also industrially useful diols such as 1,5-pentanediol and 1,6-hexanediol can be produced together with 1,4-butanediol because of containing acid. It is suitable as a raw material for hydrogenation.

US Pat. No. 5,698,749 discloses the use of a catalyst in which palladium-silver-rhenium is supported on activated carbon which has been previously subjected to nitric acid oxidation to obtain 1,4-butanediol from maleic acid in a relatively high yield. However, there is no description about the results of the hydrogenation-reduction reaction of glutaric acid or adipic acid. Also, JP-A-11-60523 describes that 1,6-hexanediol can be obtained in high yield from adipic acid using a catalyst in which activated carbon previously treated with acid carries ruthenium-tin-platinum. However, as described above, from the results of hydrogenation of succinic acid using this catalyst described in JP-A-10-71332, a high yield of 1,4-butanediol was obtained from succinic acid in dicarboxylic acid. It is difficult to get in.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a mixture of succinic acid, glutaric acid, and a dicarboxylic acid containing adipic acid which are by-produced when oxidizing cyclohexanone and / or cyclohexanol to produce adipic acid. From 1,4-butanediol, 1,5-pentanediol,
An object of the present invention is to provide a production method for obtaining a mixture of diols containing 1,6-hexanediol in high yield.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, surprisingly, ruthenium, tin and platinum were supported on a carbonaceous carrier previously treated with steam and / or carbon dioxide. 1,4-butanediol from a mixture of succinic acid and a dicarboxylic acid containing glutaric acid and adipic acid,
The inventors have found that 1,5-pentanediol and 1,6-hexanediol can be produced with good yield, and have completed the present invention.

That is, the present invention provides the following [1] to [5]
This is a method for producing diols. [1] A mixture comprising succinic acid and a dicarboxylic acid represented by the following formula (1) is reacted with hydrogen in the presence of water and a catalyst having ruthenium, tin and platinum supported on a carbonaceous carrier, and reacted with 1,4-
In a method for producing a mixture comprising butanediol and a diol represented by the following formula (2), a catalyst prepared by supporting ruthenium, tin and platinum on a carbonaceous carrier previously treated with steam and / or carbon dioxide is used. For producing a diol mixture. HOOC-R-COOH (1) ( wherein, R represents a divalent hydrocarbon group having a saturated carbon number of _{3~20) HO-CH 2 -R-} CH 2 OH (2) ( in the formula, R is the same as R in formula (1). [2] The mixture of succinic acid and the dicarboxylic acid of formula (1) is a mixture of dicarboxylic acids including succinic acid, glutaric acid, and adipic acid. The method for producing a diol mixture according to [1].

[3] The method for producing a diol mixture according to [1] or [2], wherein the carbonaceous carrier is activated carbon. [4] succinic acid, glutaric acid, wherein a mixture comprising succinic acid and a dicarboxylic acid of the formula (1) is recovered from an oxidation reaction solution of cyclohexanone and / or cyclohexanol;
The method for producing a diol mixture according to any one of [1] to [3], which is a mixture of dicarboxylic acids containing adipic acid. [5] Temperature: 100 ° C. to 300 ° C., pressure: 1 MPa to 25
The method for producing a diol mixture according to any one of [1] to [3], wherein the mixture of dicarboxylic acids is reacted with hydrogen under the conditions of MPa.

Hereinafter, the present invention will be described in detail. The raw material used in the production of diols containing 1,4-butanediol in the present invention is a mixture of succinic acid and a dicarboxylic acid of the formula (1), particularly a dicarboxylic acid containing succinic acid, glutaric acid and adipic acid. It is a mixture of acids. One example of such a raw material is a mixture of dicarboxylic acids by-produced when nitric acid is produced from cyclohexanenone and / or cyclohexanol to produce adipic acid, for example, a mother liquor obtained by crystallizing and separating adipic acid. In the present invention, the mother liquor may be used as it is, or when the hydrogen reduction activity of the catalyst is reduced by some impurities, decatalysis, dehydration,
Those that have undergone steps such as denitrification can also be used.

The hydrogen reduction catalyst used in the present invention is prepared by supporting ruthenium, tin and platinum on a carbonaceous carrier. Activated carbon is preferred as the carbonaceous carrier, but carbon black, graphite and the like can also be used. The surface area of the carbonaceous carrier is not particularly limited, but preferably has a surface area of nitrogen adsorption-BET before treatment with water vapor and / or carbon dioxide of 600 to 2,000 m ² / g. In the present invention, the carbonaceous carrier is used for adjusting the catalyst after having been subjected to a pretreatment in which the carbonaceous carrier is previously treated with steam and / or carbon dioxide.

In the steam treatment, the carbonaceous carrier may be held while flowing steam. The amount of water vapor with respect to the carbonaceous carrier is not particularly limited, but when the amount of water vapor is converted to water, the volume / hr is preferably 0.01 to 50 times the volume of the carbonaceous carrier. The processing temperature is preferably from 400 to 1000C.
More preferably, it is 600 to 950 ° C. The treatment time is several minutes to several hours, depending on the amount of water vapor and the treatment temperature.
More preferably, 0.5 to 6 hours. The treatment pressure is not particularly limited, but is preferably from normal pressure to several tens of atmospheres.

Similar to the steam treatment, the carbon dioxide treatment is performed by holding the carbonaceous carrier at a temperature of 400 to 1000 ° C., more preferably 600 to 950 ° C., for several minutes to several hours under a stream of carbon dioxide. The amount of carbon dioxide is desirably 0.1 to 50 times the volume / hr of the volume of the carbonaceous carrier when converted to the volume of carbon dioxide at normal temperature and pressure. Carbon dioxide may be diluted with air or an inert gas such as nitrogen, or steam.

As a method for supporting ruthenium, tin and platinum on the carbonaceous carrier subjected to steam treatment and / or carbon dioxide treatment, any method commonly used for adjusting a supported catalyst such as an immersion method, an ion exchange method, and an impregnation method can be used. Can be used. In the case of the immersion method, a raw material compound of a metal component to be supported is dissolved in a solvent such as water to prepare a solution of the metal compound, and a carbonaceous carrier which has been subjected to steam treatment and / or carbon dioxide treatment is immersed in the solution and the carrier is immersed. Carry it. The order in which the metal components are supported on the carrier is not particularly limited, and all metals may be supported simultaneously or each component may be supported individually.

As the raw material of the metal component used for the preparation of the catalyst, although it depends on the preparation method of the catalyst, it is usually a mineral acid salt such as a nitrate, a sulfate, a hydrochloride, an organic acid salt such as an acetate, a hydroxide,
An oxide, an organometallic compound, or the like can be used. The valence of the metal in the raw material of the metal component is not particularly limited,
0 to 4 valences are preferred.

The carbonaceous carrier carrying the metal component is dried,
Then, if desired, the catalyst is calcined and reduced to obtain a catalyst. Drying is usually carried out at a temperature of 200 ° C. or lower under reduced pressure or by flowing a dry gas such as nitrogen or air. The calcination is usually performed at a temperature of 100 to 600 ° C. while flowing nitrogen, air and the like. The reduction may be performed by either liquid phase reduction or gas phase reduction. Usually, hydrogen is used as the reducing gas,
The gas phase reduction is carried out at a temperature of 500 ° C. The supported amount of ruthenium, tin, and platinum is 0.5 to 5 as a metal for the carrier.
0% by weight, preferably 1 to 10% by weight. The ratio of ruthenium and tin is preferably from 1: 0.1 to 1: 2, more preferably 1: 1: ruthenium: tin as an element ratio as a metal.
0.2 to 1: 1. The ratio of platinum to ruthenium is not particularly limited, but is preferably in the range of 1: 0.1 to 1: 5.

In the present invention, the dicarboxylic acid mixture comprising succinic acid, glutaric acid and adipic acid is hydrogenated and reduced in the presence of water and the above-mentioned catalyst in which ruthenium, tin and platinum are supported on a carbonaceous carrier. The amount of water in the reaction is 0.5 to 100 times the weight of the dicarboxylic acid mixture. More preferably, it is 1 to 20 times. The amount of water in which the total amount of the dicarboxylic acid is dissolved at the hydrogenation reduction temperature is preferable. The hydrogenation reduction temperature can be performed at 50 to 400 ° C. Further, a temperature of 100 to 300C is preferred. 0.5 pressure
~ 40MPa, more preferably 1MPa ~ 25MPa
It is.

The reduction reaction may be carried out either continuously or batchwise. The reaction type may be any of a liquid suspension reaction and a fixed bed flow reaction. In the present invention, a mixture of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol is obtained as a diol, and these diols can be purified by a usual purification method, for example, distillation separation. .

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to embodiments. Among the reaction results, the conversion of the raw material was calculated from the analytical value of liquid chromatography,
The yield of the diols was calculated from the analytical value of gas chromatography. Further, a mixture of succinic acid, glutaric acid and adipic acid was obtained by subjecting a mother liquor obtained by crystallizing and separating adipic acid to dehydration and denitrification. The composition was determined by liquid chromatography to be 23% by weight of succinic acid, 60% by weight of glutaric acid,
Adipic acid was 17% by weight.

[0020]

Example 1 <Steam treatment of activated carbon> Granular activated carbon (particle size 10 to 20 mesh, nitrogen adsorption-BET surface area 1400
(m ² / g) 10 g was maintained at 900 ° C., and water was flowed at a rate of 10 g / hr under normal pressure for 1 hour to perform steam treatment. After the steam treatment, the mixture was cooled to room temperature while flowing nitrogen. <Adjustment of catalyst> 0.48 g of chloroplatinic acid hexahydrate was placed in a 100 ml eggplant flask, and 3.36 ml of 5N hydrochloric acid was added to dissolve the same. To this solution, 0.51 g of tin chloride (II) dihydrate was added and dissolved, and 0.84 g of ruthenium trichloride trihydrate was added and dissolved. To this solution was added 4.53 g of the activated carbon treated with steam, and the mixture was shaken at room temperature for 15 hours. 70 ° C., 20 torr using an evaporator
After distilling off water at r, the mixture was calcined at 150 ° C. for 2 hours in a nitrogen gas atmosphere, and then reduced at 450 ° C. for 2 hours in a hydrogen atmosphere. The atmosphere was returned to a nitrogen gas atmosphere, cooled to room temperature, and allowed to stand in a 0.1% oxygen / nitrogen atmosphere for 2 hours. According to the above method, a catalyst having 6.1% by weight ruthenium-5.0% by weight tin-3.4% by weight platinum supported on activated carbon was prepared.

<Hydrogen reduction reaction of a mixture of succinic acid, glutaric acid and adipic acid> In a 100 ml autoclave, 5 g of water, 2.1 g of a mixture of the above succinic acid, glutaric acid and adipic acid and the catalyst prepared by the above method were used. After charging 15 g and replacing the atmosphere in the autoclave with nitrogen at room temperature, 20 kg / cm ^{2 of} hydrogen was injected under pressure, and the temperature was raised to 180 ° C. When the temperature reached 180 ° C., hydrogen was injected and 150
kg / cm ² . The hydrogenation reduction reaction was performed at this pressure for 6 hours. After completion of the reaction, the catalyst was separated by decantation, and the catalyst was washed with purified water. The conversion rate of each dicarboxylic acid and the yield of diol were determined by liquid chromatography and gas chromatography analysis by combining the reaction solution separated by decantation and the catalyst washing solution. As a result, the conversion rates of succinic acid, glutaric acid, and adipic acid were 71%, 77%, and 70%, respectively, and the yields of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol were obtained. Are 67%, 74% and 67% respectively
Met.

[0022]

Example 2 <Carbon dioxide treatment of activated carbon> 10 g of the same granular activated carbon used in Example 1 was kept at 900 ° C., and a mixed gas of carbon dioxide at 10 ml / min and nitrogen at 10 ml / min was flown for 3 hours. . Thereafter, the gas was cooled to room temperature using only nitrogen to obtain activated carbon treated with carbon dioxide. <Adjustment of Catalyst> The same operation as in Example 1 was carried out except that the activated carbon treated with carbon dioxide was used instead of the activated carbon subjected to the steam treatment of the catalyst preparation of Example 1.

<Hydrogen reduction reaction of succinic acid, glutaric acid, adipic acid mixture> The same operation as in Example 1 was carried out except that 0.15 g of the catalyst prepared by the above method was used instead of the catalyst of Example 1. Was. As a result, succinic acid, glutaric acid,
The conversion of adipic acid is 70%, 75% and 71%, respectively.
And the yields of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol were 66%, 72%, and 69%, respectively.

[0024]

Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that the steam treatment and the carbon dioxide treatment were not performed. Using this catalyst, the mixture of dicarboxylic acids was subjected to a hydrogenation reduction reaction in the same procedure as in Example 1. As a result, the conversion of succinic acid, glutaric acid and adipic acid was 76% each.
%, 72%, 62%, 1,4-butanediol,
The yields of 1,5-pentanediol and 1,6-hexanediol were 20%, 21% and 18%, respectively.

[0025]

As described above, succinic acid, glutaric acid and adipic acid can be obtained by using the ruthenium-tin-platinum catalyst of the present invention using a carbonaceous carrier previously treated with steam and / or carbon dioxide. A diol mixture containing 1,4-butanediol, 1.5-pentanediol and 1,6-hexanediol can be produced in high yield from a mixture of dicarboxylic acids.

Claims (5)

[Claims] 1. A mixture of succinic acid and a dicarboxylic acid of the following formula (1), which is reacted with hydrogen in the presence of water and a catalyst comprising ruthenium, tin and platinum supported on a carbonaceous carrier to give 1,4-butanediol And a method for producing a mixture comprising a diol of the following formula (2), wherein a catalyst prepared by supporting ruthenium, tin and platinum on a carbonaceous carrier previously treated with steam and / or carbon dioxide is used. Method for producing the mixture. HOOC-R-COOH (1) ( wherein, R represents a divalent hydrocarbon group having a saturated carbon number of _{3~20) HO-CH 2 -R-} CH 2 OH (2) ( in the formula, R is the same as R in the formula (1)) 2. A diol mixture according to claim 1, wherein the mixture comprising succinic acid and the dicarboxylic acid of the formula (1) is a mixture of dicarboxylic acids including succinic acid, glutaric acid and adipic acid. Method. 3. The method for producing a diol mixture according to claim 1, wherein the carbonaceous carrier is activated carbon. 4. The mixture comprising succinic acid and a dicarboxylic acid of the formula (1) is a mixture of dicarboxylic acids containing succinic acid, glutaric acid, and adipic acid recovered from an oxidation reaction solution of cyclohexanone and / or cyclohexanol. The method for producing a diol mixture according to claim 1, wherein: 5. A temperature of 100 ° C. to 300 ° C. and a pressure of 1 MPa.
The method for producing a diol mixture according to any one of claims 1 to 3, wherein the mixture of dicarboxylic acids is reacted with hydrogen under the condition of -25 MPa.