JP2001002605A - Production of diols - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a mixture of butanediol and a specific diol in high yield by allowing a mixture of succinic acid and a specific dicarboxylic acid to react with hydrogen in the presence of a specific catalyst and water. SOLUTION: A mixture of (A) succinic acid and (B) a dicarboxylic acid of the formula: HOOC-R-COOH (R is a 3-20C saturated divalent hydrocarbon) and (C) hydrogen are allowed to react with each other in the presence of (D) a catalyst prepared by carrying one or more metals selected from ruthenium and tin, rhenium, molybdenum, palladium, silver and nickel supported by carbon carrier that is preliminarily treated with hydrogen peroxide and/or ozone aqueous solution and (E) water under a pressure of 1-25 Mpa, at 100-300 deg.C to obtain a mixture of 1,4-butandiol and a diol of the formula: HO-CH2-R-CH2OH. As a mixture of the component A and the component B, are cited preferably a mixtures of dicarboxylic acids including the component A, glutaric acid and adipic acid.

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 Unexamined Patent Publication No. 9-12492), a catalyst comprising ruthenium-tin-platinum supported on a carrier (Japanese Unexamined Patent Publication No.
No. 59190), a catalyst prepared by impregnating activated carbon with a solution containing a supporting component coexisting with a carbonyl compound having 5 or less carbon atoms and having ruthenium-tin-platinum supported on activated carbon (JP-A-10-15388), (Japanese Patent Application Laid-Open No. 10-71332) proposes a catalyst in which ruthenium-tin-platinum having a prescribed metal loading state is supported on activated carbon by using activated carbon in contact with the catalyst. 1,4-butanediol,
The selectivity of 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 composed of palladium and a rhenium compound and using a tertiary alcohol as a solvent.
The reaction rate was 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 used 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 the acid because it contains an acid. It is suitable as a raw material for direct hydrogenation.

In US Pat. No. 5,698,749, 1,4-butanediol can be obtained in relatively high yield from maleic acid by using a catalyst in which palladium-silver-rhenium is supported on activated carbon which has been previously subjected to nitric acid oxidation treatment. 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 the same catalyst as described in US Pat. No. 71332, it is difficult to obtain 1,4-butanediol in high yield from succinic acid contained in the above mixture of dicarboxylic acids. .

[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. 1,4-butanediol, 1,1
An object of the present invention is to provide a method for producing a mixture of diols containing 5-pentanediol and 1,6-hexanediol in high yield.

[0007]

Means for Solving the Problems As a result of intensive studies by the present inventors to solve the above problems, surprisingly, ruthenium and tin and ruthenium and tin were added to a carbonaceous carrier previously treated with an aqueous solution of hydrogen peroxide and / or ozone. Rhenium, molybdenum, palladium, silver, by using a catalyst supporting at least one metal selected from nickel, 1,4-butanediol, 1,4-butanediol from a mixture of succinic acid and a dicarboxylic acid containing glutaric acid and adipic acid The inventors have found that 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 [7]
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 a catalyst and water to produce a mixture composed of 1,4-butanediol and a diol represented by the following formula (2). Ruthenium and tin and rhenium, molybdenum, on a carbonaceous support previously treated with a hydrogen peroxide solution and / or an aqueous ozone solution as a catalyst.
A process for producing diols, comprising using a catalyst prepared by supporting at least one metal selected from palladium, silver and nickel. 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 diols according to [1].

[3] The method for producing diols according to [1] or [2], wherein the carbonaceous carrier is activated carbon. [4] The method for producing diols according to [1] to [3], wherein the pretreatment is a treatment with a hydrogen peroxide solution. [5] The metal supported on the carbonaceous carrier is ruthenium-tin-
The method for producing diols according to [1] to [4], which is rhenium. [6] 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 process for producing diols according to [1] to [5], which is a mixture of dicarboxylic acids containing adipic acid. [7] Temperature: 100 ° C. to 300 ° C., pressure: 1 MPa to 25
The method for producing diols according to [1] to [6], 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 mixture of adipic acid contained in a mother liquor separated by crystallization. A mixture of dicarboxylic acids. In the present invention, the mother liquor may be used as it is, or when the hydrogen reduction activity of the catalyst is reduced due to some contaminants, a solution that has undergone steps such as decatalysis, dehydration, and denitrification may be used.

The hydrogen reduction catalyst used in the present invention is prepared by supporting ruthenium, tin and at least one metal selected from rhenium, molybdenum, palladium, silver and nickel on a carbonaceous carrier. Activated carbon is preferred as the carbonaceous carrier, but carbon black, graphite and the like can also be used. Although the surface area of the carbonaceous carrier is not particularly limited, the nitrogen adsorption-BET surface area before treatment with an aqueous solution of hydrogen peroxide and / or ozone is 600 to 2.0.
Those having a surface area of 00 m ² / g are preferably used. In the present invention, the carbonaceous carrier is used for adjusting the catalyst after pre-treatment with a hydrogen peroxide solution and / or an ozone aqueous solution in advance.

In the treatment with hydrogen peroxide solution, the carbonaceous carrier may be charged into the hydrogen peroxide solution and maintained at room temperature or under heating for several minutes to several tens of hours. The concentration of the hydrogen peroxide solution is not particularly limited, but is preferably 1 to 70% by weight, particularly preferably 5 to 60% by weight. The processing temperature is preferably from 30 to 100 ° C, more preferably from 80 to 95 ° C. The treatment time depends on the concentration of the hydrogen peroxide solution and the treatment temperature, but is at least several minutes to several tens of hours, more preferably 1 hour to 20 hours. The carbonaceous carrier treated with hydrogen peroxide is sufficiently washed with water to remove adhering hydrogen peroxide, and is used for catalyst preparation.

[0013] In the ozone aqueous solution treatment, for example, a carbonaceous carrier is put into water and kept at normal temperature or under heating, and ozone gas obtained from an ozone generator is blown. The ozone gas may be generated from air or may be generated from pure oxygen. Further, it may be diluted with an inert gas such as nitrogen.
The concentration of ozone is preferably in the range of 0.01 to ³⁰ g / Nm3. The processing temperature is preferably from 30 to 100 ° C, more preferably from 50 to 95 ° C. The processing time is several minutes to several tens of hours, depending on the ozone concentration and the processing temperature. The ozone-treated carbonaceous carrier is used for catalyst preparation after washing with water. Further, the carbonaceous carrier which has been treated with the hydrogen peroxide solution may be further treated with an ozone aqueous solution.

As a method for supporting ruthenium and tin and at least one metal selected from the group consisting of rhenium, molybdenum, palladium, silver and nickel on a carbonaceous carrier treated with aqueous hydrogen peroxide and / or ozone, an immersion method or an ion exchange method Any method generally used for adjusting a supported catalyst such as an impregnation method can be used. When the immersion method is used, 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 the solution is pretreated with a hydrogen peroxide solution and / or an ozone aqueous solution by the above method. The porous carrier is immersed in the carrier. 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, usually, mineral salts such as nitrates, sulfates, hydrochlorides, organic acid salts such as acetates, hydroxides, and the like.
An oxide, an organometallic compound, or the like can be used. The carbonaceous carrier supporting the metal component is dried, and then, if desired, 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. In addition, firing is usually 100 to 60.
This is carried out at a temperature of 0 ° C. while flowing nitrogen, air and the like. The reduction may be performed by either liquid phase reduction or gas phase reduction. Usually, gas phase reduction is performed at a temperature of 200 to 500 ° C. using hydrogen as a reducing gas. The supported amount of ruthenium and tin is 0.5 to 50% by weight, preferably 1 to 10% by weight, as a metal, based on the carrier. The ratio of ruthenium to tin is preferably an elemental ratio of ruthenium: tin of 1: 0.1 to 1: 2, more preferably 1: 0.2 to 1: 1.

In the present invention, in addition to ruthenium and tin, at least one metal selected from rhenium, molybdenum, palladium, silver, and nickel is supported. Of these, rhenium is particularly preferred. The supported amount of rhenium, molybdenum, palladium, silver, and nickel is preferably 0.1 to 5, more preferably 0.2 to 2, based on ruthenium as an elemental ratio.

In the present invention, succinic acid, glutaric acid, adipic acid and a catalyst in which ruthenium and tin and at least one metal selected from rhenium, molybdenum, palladium, silver and nickel are supported on a carbonaceous carrier and water are present. Of the dicarboxylic acid mixture consisting of The amount of water in the reaction is 0.5 to 1 with respect to the dicarboxylic acid mixture.
It is 00 weight times. 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 temperature of the hydrogenation reduction is 50-40.
The temperature is preferably 0 ° C, more preferably 100 to 300 ° C. The pressure is 0.5 to 40 MPa, more preferably 1
MPa to 25 MPa.

The reduction reaction may be carried out either continuously or batchwise. The reaction type may be any of a liquid phase 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 the diol. If necessary, these diols may be purified by a usual purification method, for example, distillation separation. can do.

[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 <Treatment of activated carbon with aqueous hydrogen peroxide> Granular activated carbon (particle size: 10 to 20 mesh, nitrogen adsorption-BET surface area: 1)
400 m ² / g) 10 g of 10% hydrogen peroxide water 150 g
And heated at 95 ° C. for 5 hours with stirring. After cooling,
The activated carbon was filtered and washed with 100 ml of water five times. The obtained activated carbon was dried with hot air at 120 ° C. for 5 hours. <Preparation of Ru-Sn-Re catalyst> 2.00 g of ion-exchanged water and 0.39 g of ruthenium chloride trihydrate were placed in a 100 ml eggplant-shaped flask and dissolved. Add tin chloride (I
0.20 g of (I value) .dihydrate was added and dissolved. Further, 0.22 g of rhenium heptoxide was added and dissolved. To this solution, 3.00 g of the activated carbon treated with the above-described hydrogen peroxide solution was added, and the mixture was shaken at room temperature for 15 hours. 70 using an evaporator
After distilling off water at 20 ° C. and 20 torr, baking was performed at 150 ° C. for 2 hours in a nitrogen gas atmosphere, and then 45 ° C. in a hydrogen atmosphere.
Reduction treatment was performed at 0 ° C. for 2 hours. Switch back to a nitrogen gas atmosphere,
After cooling to room temperature, it was allowed to stand in a 0.1% oxygen / nitrogen atmosphere for 2 hours. 5.0 wt% ruthenium according to the above method.
A catalyst in which 3.5% by weight tin-5.6% by weight rhenium was supported on activated carbon was prepared.

<Succinic acid, glutaric acid, adipic acid mixture
Reduction reaction of waste> Autoclave of 100ml capacity
10 g of water, succinic acid, glutaric acid, adipic acid
1 g of the mixture of above and 0.3 g of the catalyst prepared by the above method were charged.
The atmosphere in the autoclave was replaced with nitrogen at room temperature.
After that, 20kg / cm of hydrogen^TwoPress in and heat up to 180 ° C
did. When the temperature reaches 180 ° C, 150 kg of hydrogen is injected.
/ Cm ^TwoAnd A hydrogenation-reduction reaction is performed at this pressure for 6 hours.
Was. After the reaction, the catalyst is separated by decantation
Then, the catalyst was washed with purified water. By decantation
Combine the separated reaction solution and catalyst washing solution to
Conversion and diol yield were determined by liquid chromatography.
It was determined by analysis by gas chromatography. The result
Succinic, glutaric, and adipic acid conversion rates
91%, 94% and 82%, respectively, and 1,4-butane
All, 1,5-pentanediol, 1,6-hexane
The diol yields were 84%, 92%, and 76%, respectively.
there were.

[0022]

Example 2 <Adjustment of Ru-Sn-Mo catalyst> Example 1
(NH4) 6M in place of 0.22 g of rhenium heptaoxide
A catalyst was prepared in the same manner as in Example 1 except that 0.08 g of o7O24 tetrahydrate was used. By this, 5.0% by weight
A catalyst having ruthenium-3.5% by weight tin-1.5% by weight molybdenum supported on activated carbon was prepared. <Hydrogen reduction reaction of succinic acid, glutaric acid, adipic acid mixture> A hydrogenation reaction was performed in the same manner as in Example 1 except that the ruthenium-tin-molybdenum / activated carbon catalyst prepared above was used as a catalyst. As a result, the conversion rates of succinic acid, glutaric acid and adipic acid were 87%, 91% and 8%, respectively.
0%, and the yields of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol were 81%, 89%, and 73%, respectively.

[0023]

Example 3 <Ozone aqueous solution treatment of activated carbon> 10 g of the same granular activated carbon used in Example 1 was added to 150 g of water.
Under stirring at 90 ° C., ozone (ozone concentration: 10 g / Nm ³ ) generated by using air from an ozone generator was blown into the liquid at a rate of 100 ml / min from a gas inlet tube equipped with a glass ball filter at the tip. Heat treatment for 5 hours. After cooling, the activated carbon was filtered and washed five times with 100 ml of water. The obtained activated carbon was dried with hot air at 120 ° C. for 5 hours to obtain an activated carbon treated with an ozone aqueous solution.

<Adjustment of Catalyst> The same operation as in Example 1 was carried out except that the activated carbon treated with ozone was used in place of the activated carbon treated with hydrogen peroxide in the catalyst preparation of Example 1. <Hydrogen reduction reaction of succinic acid, glutaric acid, adipic acid mixture> A hydrogenation reduction reaction was carried out using a ruthenium-tin-rhenium catalyst supported on activated carbon treated with the above ozone aqueous solution instead of the catalyst of Example 1. . As a result, the conversion of succinic acid, glutaric acid and adipic acid was 82% each.
%, 79%, 71%, 1,4-butanediol,
The yields of 1,5-pentanediol and 1,6-hexanediol were 76%, 76%, and 68%, respectively.

[0025]

COMPARATIVE EXAMPLE 1 Ruthenium-tin-tin was prepared in the same manner as in the preparation of the catalyst in Example 1 using activated carbon not subjected to the hydrogen peroxide treatment.
The rhenium / activated carbon catalyst was adjusted. Using this catalyst, a hydrogenation reduction reaction of the dicarboxylic acid mixture was performed in the same procedure as in Example 1. As a result, the conversion rates of succinic acid, glutaric acid, and adipic acid were 78%, 75%, and 67%, respectively, and the yields of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol were as follows. 23 each
%, 24% and 21%.

[0026]

As described above, the ruthenium and tin of the present invention and at least one metal selected from rhenium, molybdenum, palladium, silver and nickel are treated in advance with a hydrogen peroxide solution and / or an ozone aqueous solution. Diol containing 1,4-butanediol, 1.5-pentanediol and 1,6-hexanediol from a mixture of dicarboxylic acids including succinic acid, glutaric acid and adipic acid by using a catalyst having a porous carrier supported on the carrier. The mixture can be produced in high yield.

Continued on the front page F term (reference) 4H006 AA02 AC41 AC46 BA05 BA11 BA14 BA16 BA21 BA23 BA25 BA28 BA29 BA55 BA81 BB31 BD70 BE20 BE31 BE32 BE60 FE11 FG28 FG29 4H039 CA60 CB40

Claims (7)

[Claims] 1. A mixture comprising 1,4-butanediol and a diol represented by the following formula (2) by reacting a mixture comprising succinic acid and a dicarboxylic acid represented by the following formula (1) with hydrogen in the presence of a catalyst and water: In the method for producing the above, ruthenium and tin and rhenium, at least one metal selected from molybdenum, palladium, silver and nickel were supported on a carbonaceous carrier which had been previously treated with a hydrogen peroxide solution and / or an aqueous ozone solution as a catalyst. A method for producing diols, comprising using a catalyst. 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. The production of diols according to claim 1, wherein the mixture comprising succinic acid and the dicarboxylic acid of the formula (1) is a mixture of dicarboxylic acids containing succinic acid, glutaric acid and adipic acid. Law. 3. The method according to claim 1, wherein the carbonaceous carrier is activated carbon. 4. The method for producing a diol according to claim 1, wherein the pretreatment is a treatment with a hydrogen peroxide solution. 5. The method for producing a diol according to claim 1, wherein the metal supported on the carbonaceous carrier is ruthenium-tin-rhenium. 6. The mixture comprising succinic acid and the 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 according to any one of claims 1 to 5, characterized in that: 7. A temperature of 100 ° C. to 300 ° C. and a pressure of 1 MPa.
The method for producing diols according to any one of claims 1 to 6, wherein the mixture of dicarboxylic acids is reacted with hydrogen under the condition of -25 MPa.