JP2001157841A - Catalyst for hydrogenating carboxylic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst capable of obtaining an alcohol group in high yield notwithstanding type of carboxylic acid, even if any type of carboxylic acid is used, and further to provide a method for manufacturing an alcohol group by direct hydrogenation using the catalyst. SOLUTION: The catalyst having ruthenium and tin supported on an activated carbon wherein the catalyst is a zinc chloride-activated carbon, and the volume of the microporosity of which the radius of the microporosity is not more than 10 Å is from 0.03 cm3/g to 0.8 cm3/g, the volume of the microporosity of which the radius of the microporosity is 10A-100 Å is from 0.5 cm3/g to 2.0 cm3/g, total volume of the microporosity is from 1.2 cm3/g to 3.0 cm3/g and the specific surface area is 800 m2/g to not more than 2000 m2, and a method for manufacturing an alcohol group by hydrogenating carboxylic acid in the presence of water using said catalyst are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst used for producing alcohols by directly hydrogenating a carboxylic acid with hydrogen as a raw material without going through an esterification step in the presence of water, and a catalyst for direct hydrogenation. And a method for producing alcohols.

[0002]

BACKGROUND OF THE INVENTION Alcohols are useful substances that are widely used in various industrial fields. Especially diols are polyester resin, urethane foam and urethane paint,
Useful as a raw material for adhesives. As a method for producing 1,4-butanediol, for example, as one of such diols, many methods have been reported for producing succinic acid or maleic acid by hydrogenation. The best known method is to hydrogenate an ester of succinic or maleic acid at high temperature and pressure using a copper catalyst. However, in this method, the carboxylic acid cannot be directly hydrogenated, and the carboxylic acid must be once converted into an ester and then hydrogenated, resulting in a problem that the production process becomes long.

On the other hand, several methods have been proposed for producing 1,4-butanediol by directly hydrogenating succinic acid or maleic acid. The catalyst system consisting solely of ruthenium-iron oxide (US Pat. No. 4,82
7,001), a catalyst in which ruthenium-tin is supported on porous carbon having a BET surface area of 2000 m ² / g or more (JP-A-5-246915), and a silica in which ruthenium and tin are modified with titanium and / or alumina. Selected from the group consisting of ruthenium and tin, ruthenium and tin, and a catalyst supporting an alkali metal compound or an alkaline earth metal on a carrier (JP-A-6-239778), ruthenium, platinum and rhodium. Catalyst in which at least one of the above-mentioned and tin are supported on a carrier (Japanese Unexamined Patent Publication No.
No. 65644), a method in which an excess hydrogen is circulated through a reaction system using a catalyst in which ruthenium and tin are supported on a carrier, and a reaction is carried out while entrained products are removed from the system (Japanese Patent Application Laid-Open No. H9-0995). -12492), a catalyst containing ruthenium-tin-platinum supported on a carrier (JP-A-9-59190), and a solution containing a supported component in which a carbonyl compound having 5 or less carbon atoms coexists with activated carbon. Catalyst in which activated ruthenium-tin-platinum is supported on activated carbon
No. 15388), a catalyst in which ruthenium-tin-platinum having a prescribed metal loading state by using activated carbon previously contacted with nitric acid is supported on activated carbon (Japanese Unexamined Patent Publication No.
However, in any of the methods using any of the catalysts, the selectivity of the hydrogenated products of 1.4-butanediol, tetrahydrofuran and γ-butyrolactone is not sufficient, and The yield of butanediol was unsatisfactory.

Japanese Patent Application Laid-Open No. 7-82190 proposes a method in which a catalyst comprising palladium and a rhenium compound is used to carry out hydrogenation using a tertiary alcohol as a solvent, but the reaction rate is still insufficient. . As described above, the prior art discloses an example of direct hydrogenation using a catalyst using activated carbon as a carrier, and several studies have been made on the specific surface area of activated carbon and a pretreatment method.

[0005] As a general method for producing activated carbon, a raw material carbonaceous pyrolysis step called an activation step is performed. As the activation method, a gas activation method using various oxidizing gases (steam, carbon dioxide, air, etc.) Chemical activation methods using dehydrating salts and acids (calcium chloride, magnesium chloride, zinc chloride, phosphoric acid, sulfuric acid, alkalis such as caustic soda and caustic potash) are known. At present, the gas activation method is widely and most widely adopted in the United States and the world, and occupies the mainstream of activated carbon production. The chemical activation method is currently produced only for special applications.

Due to such a difference in the activation method, activated carbons having different pore distributions as physical properties of the activated carbon can be obtained. For example, zinc chloride activated powdered coal develops pores having a pore radius of 10 to 100 ° called transitional pores, and the pore volume is specifically large. The use of such activated carbon as a carrier for a direct hydrogenation catalyst of dicarboxylic acid is not described in the above-mentioned prior art. Also, U.S. Pat.
No. 8,749 describes that 1,4-butanediol can be obtained in a 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, nothing is described about the results of the hydrogenation-reduction reaction of glutaric acid or adipic acid.

JP-A-11-60523 discloses that 1,6-hexanediol can be obtained in high yield from adipic acid by using a catalyst in which activated carbon previously treated with acid and supporting ruthenium-tin-platinum is used. However, as described in JP-A-10-71332, this catalyst is used to convert succinic acid or maleic acid into 1,
It is difficult to obtain 4-butanediol in high yield.

[0008]

DISCLOSURE OF THE INVENTION The present invention relates to a catalyst capable of obtaining alcohols in high yield by direct hydrogenation using any carboxylic acid as a raw material, regardless of the type of carboxylic acid, and a catalyst therefor. An object of the present invention is to provide a method for producing alcohols by direct hydrogenation of a carboxylic acid using a catalyst. In particular, it is an object of the present invention to provide a catalyst capable of obtaining diols in high yield using any of succinic acid, glutaric acid and adipic acid as a raw material, and a method for producing diols by direct hydrogenation using the catalyst. Aim.

[0009]

Means for Solving the Problems As a result of intensive studies by the present inventors to solve the above-mentioned problems, surprisingly, fine pores having a pore radius of 10 ° or more and 100 ° or less, called transitional pores, are used as activated carbon pores. Using activated carbon having a large pore volume as a carrier, and a catalyst supporting ruthenium, tin and platinum, regardless of the type of carboxylic acid, it is possible to obtain alcohols in high yield using any carboxylic acid as a raw material. The present invention was found to be a catalyst that can be made, and the present invention has been completed.

That is, the present invention relates to [1] ruthenium,
A catalyst in which tin and platinum are supported on activated carbon, wherein the activated carbon is zinc chloride activated carbon; and [2] a catalyst in which ruthenium, tin and platinum are supported on activated carbon. pore radius of the activated carbon pore volume of less than 10 Å 0.03 cm ³ / g or more 0.8 cm ³ / g
Hereinafter, the pore volume with a pore radius of 10 ° to 100 ° is 0.5 cm ³ / g to 2.0 cm ³ / g, and the total pore volume is 1.2 cm ³ / g to 3.0 cm ³ / g. Hereinafter, a carboxylic acid hydrogenation catalyst having a specific surface area of 800 m ² / g or more and less than 2,000 m ² / g, [3] a carboxylic acid and / or carboxylic anhydride in the presence of a catalyst and water. A method for producing an alcohol by reacting with hydrogen to produce an alcohol, wherein the catalyst for hydrogenating a carboxylic acid according to [1] or [2] is used as the catalyst, [4] The carboxylic acid is at least one dicarboxylic acid selected from dicarboxylic acids represented by the general formula (1), and the carboxylic anhydride is at least one dicarboxylic anhydride represented by the general formula (2). Feature 3] The method of producing alcohol according,

[0011]

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(Wherein R ₁ and R ₂ each independently represent a divalent hydrocarbon group having 2 to 20 carbon atoms.) [5] The carboxylic acid is succinic acid, glutaric acid, adipic acid, cyclohexane It is a carboxylic acid containing at least one selected from dicarboxylic acid, maleic acid, fumaric acid and terephthalic acid, and the carboxylic anhydride is a carboxylic anhydride containing at least one selected from succinic anhydride and maleic anhydride. [3] The method for producing an alcohol according to [4], [6] the carboxylic acid and / or the carboxylic anhydride is a mixture of carboxylic acids including succinic acid, glutaric acid, and adipic acid [5]. ]
The method for producing an alcohol according to [7], wherein the carboxylic acid and / or carboxylic anhydride is cyclohexanone and / or
Or a mixture of carboxylic acids containing succinic acid, glutaric acid, and adipic acid recovered from an oxidation reaction solution of cyclohexanol, [8] a method for producing an alcohol, [8] a temperature of 100 ° C to 300 ° C. ℃, hydrogen pressure 1
The method for producing an alcohol according to any one of [3] to [7], wherein the carboxylic acid and / or carboxylic anhydride is reacted with hydrogen under the conditions of MPa to 25 MPa.

Hereinafter, the present invention will be described in detail. The carboxylic acid hydrogenation catalyst of the present invention is prepared by supporting ruthenium, tin and platinum on activated carbon produced by a specific production method. The activated carbon used in the present invention is zinc chloride activated carbon. The method for producing zinc chloride activated carbon may be a known method, and details thereof are described in, for example, "Activated Carbon Reader 2nd Edition" (edited by Hiroshi Yanai, edited by Nobuo Ishizaki, Nikkan Kogyo Shimbun) and the like. Activated carbon produced by a production method including a step of impregnating with a concentrated solution of zinc chloride, using a sawdust, a low-ash peat, straw, a reed, a nut, a lump, and the like as a raw material, followed by firing. Further, this activated carbon may be treated with hot water or the like before carrying ruthenium, tin and platinum to remove impurities.

This zinc chloride activated carbon has a characteristic that pores having a pore radius of 10 ° or more and 100 ° or less, called “traditional pores”, are developed and the pore volume is specifically large. The relationship between the pore radius and the pore volume in the zinc chloride activated carbon is such that when the pore volume and the BET specific surface area are measured by a nitrogen gas adsorption method, the pore volume with a pore radius of less than 10 ° is 0.03 cm ^3. / G or more and 0.8 cm ³ / g or less, the pore volume with a pore radius of 10 ° or more and 100 ° or less is 0.5 cm ³ / g or more and 2.0 cm ³ / g or less, and the total pore volume is 1. It is 2 cm ³ / g or more and 3.0 cm ³ / g or less, and the specific surface area is 800 m ² / g or more and less than 2000 m ² / g. More preferably the pore volume less than the pore radius 10Å is less 0.04 cm ³ / g or more 0.7cm ³ / g, 100Å volume of pores over pore radius 10Å is 0.
7 cm ³ / g or more and 1.8 cm ³ / g or less, and the total pore volume is 1.4 cm ³ / g or more and 2.7 cm ³ / g or less;
The specific surface area is not less than 1000 cm ² / g and not more than 1800 m ² / g.

The pore volume of a general steam activated carbon has a pore radius of 10 ° or more and is called a traditional pore.
細孔 The pore volume of not more than 0.02 cm ³ / g or more and 0.4 cm ³
/ G or less. In order to obtain a high yield of alcohols irrespective of the type of carboxylic acid as the object of the present invention, it is necessary to use activated carbon having a large pore volume of a traditional pore as a carrier. That is, a pore volume having a pore radius of 10 ° to 100 ° is 0.5 cm ³ / g or more.
It is necessary to use activated carbon of 0 cm ³ / g or less.

On the other hand, the strength of the catalyst is required to maintain its structure, so that the activated carbon used as the carrier must have the relationship between the pore radius and the pore volume. That is, the pore volume having a pore radius of less than 10 ° is 0.03 cm ³ / pore volume having a pore radius of less than 10 °.
g and 0.8 cm ³ / g or less, and the total pore volume is 1.
2 cm ³ / g or more 3.0cm and a ³ / g or less, a specific surface area should be less than 800 m ² / g or more 2000 m ² / g.

According to the results examined by the present inventors, there may be a difference between the measurement results of the pore volume and the BET specific surface area by the nitrogen adsorption method depending on the measuring device. The present inventors measured using Shimadzu Micromeritex ASAP-2400 (made by Shimadzu Corporation). The data processing for calculating the pore volume used the BJH method. It should be noted that as a result of the data processing by this apparatus, the pore radius from 5 ° to 1500
Although the data of 半径 is obtained, the pore radius measured by the nitrogen adsorption method is generally about 8 ° to 500 ° as generally known, and the pore radius of less than 10 ° in the present invention is substantially less than 10 °. A pore radius of about 8 to less than 10 is referred to, and a total pore volume refers to a pore volume of a pore radius of substantially about 8 to 500.

It is not clear why the activated carbon having such a pore structure exhibits a particularly effective effect when used as a catalyst carrier for direct hydrogenation of dicarboxylic acid. In comparison, since the pore volume called a transitional pore having a pore radius of 10 ° or more and 100 ° or less is large, the diffusion of carboxylic acid and hydrogen in the catalyst pores proceeds smoothly, especially when dicarboxylic acid is used as a raw material. Presumed that the diffusion of the dicarboxylic acid and the intermediate hydroxycarboxylic acid proceeded smoothly, and the hydrogenation of the dicarboxylic acid to the hydroxycarboxylic acid and further to the diol proceeded efficiently.

As a method for supporting ruthenium, tin and platinum on activated carbon, any method generally used for preparing a supported catalyst such as an immersion method, an ion exchange method, and an impregnation method can be used. In the case of the immersion method, a starting compound of the metal component to be supported is dissolved in a solvent such as water to prepare a solution of the metal compound, and activated carbon is immersed in the solution to be supported on 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.

The starting compound of the metal component used in the preparation of the catalyst is usually a mineral acid salt such as nitrate, sulfate or hydrochloride, an organic acid salt such as acetate, a hydroxide, An oxide, an organometallic compound, or the like can be used. Among them, a water-soluble raw material compound is preferable. Specifically, ruthenium raw material compounds include ruthenium chloride, ruthenium nitrate, ruthenium acetylacetonate, ruthenium carbonyl, and the like. Tin raw materials include tin chloride (II), sodium stannate, tin acetate (II), and the like. As a raw material of platinum, chloroplatinic acid, platinum nitrate, platinum acetylacetonate, platinum chloride, platinum bromide, platinum cyanide and the like are preferably used.

The carbonaceous carrier carrying the metal component is dried,
Then, if necessary, after calcining, it is reduced to obtain a catalyst. Drying is usually performed at a temperature lower than 100 ° C. 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. for 1 hour to 24 hours while flowing nitrogen, air and the like. The reduction may be performed by either liquid phase reduction or gas phase reduction. Hydrogen, hydrazine vapor, formalin, carbon monoxide and the like can be used as the reducing gas used for the gas phase reduction. As the temperature, a temperature of 150C to 500C is preferable. The calcined catalyst is charged in a container, heated to a desired temperature, and then filled with a reducing gas to perform reduction.
This reduction operation may be repeated as desired. Also,
The reducing operation may be performed by flowing a reducing gas through the container.
As the reducing agent used in the liquid phase reduction, a reducing agent such as sodium borohydride, lithium aluminum hydride, diethyl zinc or the like can be used in addition to the reducing agent used in the gas phase reduction.

The activated carbon supporting the metal component is suspended in a solvent such as water and / or alcohol, and reduced using the above-described reducing agent at a temperature of room temperature to 250 ° C. and a pressure of normal pressure to 20 MPa. It can be done by doing. A method in which hydrogen is used as a reducing gas and gas phase reduction is performed at a temperature of 150 ° C. to 500 ° C. for 30 minutes to 24 hours can be preferably used. In the catalyst of the present invention, the supported amounts of ruthenium and tin are each 0.1% as metal to the support.
It is 5 to 50% by weight, preferably 1 to 10% by weight. The ratio of ruthenium and tin is as follows:
The tin ratio is preferably from 1: 0.1 to 1: 2, and more preferably from 1: 0.2 to 1: 1.3. The supported amount of platinum is preferably 0.01 to 5, more preferably 0.1 to 2, as a metal relative to ruthenium in elemental ratio.

In the present invention, the raw materials used for producing alcohols are carboxylic acids and / or carboxylic anhydrides. Specifically, aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, and pelargonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid , Pimelic acid, suberic acid, azelaic acid, sebacic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, methylmalonic acid, α-methylglutaric acid, β-methylglutaric acid, 2, 2-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3.3-dimethylglutaric acid, 2-ethyl-2-methylsuccinic acid, 2,2
Aliphatic saturated dicarboxylic acids and aliphatic saturated dicarboxylic anhydrides such as 5,5-tetramethylhexane diacid, 3-methyl adipic acid, succinic anhydride, adipic anhydride, polyadipic anhydride, acrylic acid, Crotonic acid,
Aliphatic unsaturated monocarboxylic acids such as isocrotonic acid, vinyl acetic acid and methacrylic acid, fumaric acid, maleic acid, maleic anhydride, methyl maleic acid, methyl fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, and muconic acid; Aliphatic unsaturated dicarboxylic acids such as 2-methylmusconic acid, acetylenedicarboxylic acid, 1-propyne-1,3-dicarboxylic acid, and aliphatic polycarboxylic acids such as aliphatic unsaturated dicarboxylic anhydride, methinetricarboxylic acid and ethylenetricarboxylic acid Carboxylic acids, cyclohexanecarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,
Aliphatic alicyclic mono- and dicarboxylic acids such as 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3,3-tetramethyleneglutaric acid, cholanic acid, lithocholic acid, cholic acid, benzoic acid, toluic acid, dimethyl Benzoic acid, cumic acid, phthalic acid, phthalic anhydride,
Aromatic carboxylic acids such as isophthalic acid and terephthalic acid and aromatic carboxylic anhydrides.

Of these, dicarboxylic acids represented by the following general formula (1) and dicarboxylic anhydrides represented by the following general formula (2) are preferred. Specifically, succinic acid, glutaric acid, adipic acid, cyclohexanedicarboxylic acid, Examples include maleic acid, fumaric acid, terephthalic acid, succinic anhydride, and maleic anhydride. Carboxylic acids and / or carboxylic anhydrides having no nitrogen, sulfur or phosphorus elements in the molecule are preferred.

[0025]

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(In the formula, R ₁ and R ₂ each independently represent a divalent hydrocarbon group having 2 to 20 carbon atoms.) An unsaturated carboxylic acid and an unsaturated carboxylic anhydride are used as raw materials. When used, saturated alcohols are obtained by hydrogenation reaction using the catalyst of the present invention, and when aromatic carboxylic acids and aromatic carboxylic anhydrides are used as raw materials, alicyclic alcohols are used. Is obtained.

Further, the starting carboxylic acid may be any mixture of a plurality of carboxylic acids, a mixture of a plurality of carboxylic anhydrides, or a mixture of a carboxylic acid and a carboxylic anhydride. Absent. A preferred mixture of dicarboxylic acids is a mixture containing succinic acid, glutaric acid and adipic acid. Further, dicarboxylic acids which are by-produced when oxidizing cyclohexanone and / or cyclohexanol to produce adipic acid include succinic acid, glutaric acid, and adipic acid, and are particularly preferable raw materials of the present invention. If a useful compound can be obtained using this dicarboxylic acid as a raw material, the amount of waste generated during the production of adipic acid can be reduced, and this by-product contains succinic acid, glutaric acid, and adipic acid. Can also produce industrially useful diols such as 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, regardless of the type of the carboxylic acid raw material of the catalyst of the present invention. It is particularly preferable because it is an optimal raw material for exhibiting the characteristic that alcohols can be obtained in high yield.

Particularly preferably used in the present invention,
The dicarboxylic acid mixture by-produced when producing adipic acid by nitric acid oxidation of cyclohexanone and / or cyclohexanol is a filtrate obtained by crystallizing and separating adipic acid. In the present invention, the filtrate may be used as it is, but when the hydrogenation activity of the catalyst decreases, it is preferable to use a filtrate that has undergone steps such as decatalysis, dehydration, and denitrification of the nitric acid oxidation catalyst. In the present invention, a hydrogenation reaction of a carboxylic acid and / or a carboxylic anhydride is carried out in the presence of water using a catalyst in which the above-mentioned ruthenium, tin and platinum are supported on activated carbon. The amount of water in the reaction is 0.5 to 100 times the weight of the carboxylic acid and / or carboxylic anhydride. More preferably, it is 1 to 20 times by weight. The amount of water in which the total amount of the carboxylic acid or carboxylic anhydride is dissolved at the hydrogenation temperature is preferred. The temperature of the hydrogenation reaction is preferably from 100 to 300 ° C, more preferably from 130 to 250 ° C. Hydrogen pressure is 1 to 25 MPa, more preferably 5 MPa to 20 M
Pa.

The hydrogenation 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, when a dicarboxylic acid mixture of succinic acid, glutaric acid, and adipic acid, which is a by-product of producing adipic acid by nitric acid oxidation of cyclohexanone and / or cyclohexanol, is used as a hydrogenated product, A mixture of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol is obtained, and these diols can be purified by a usual purification method, for example, distillation separation as required.

[0030]

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 dehydrating and denitrifying a filtrate obtained by crystallizing and separating adipic acid. 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.

[0031]

Example 1 Activated carbon having a grade name of "Taiko SGP" manufactured by Nimura Chemical Industry Co., Ltd. was used as a catalyst carrier. The pore volume and the total specific surface area of the activated carbon were measured by Nimura Chemical Industry Co., Ltd. using a nitrogen-absorbing method using Carlo Elba's soapmatic. 05cm ³ / g, pore radius 10 ° or more and 100 °
The following pore volume was 0.75 cm ³ / g, the total pore volume was 1.08 cm ³ / g, and the specific surface area was 1050 m 2 / g. Furthermore, Shimadzu Micromeritex ASAP-
When the activated carbon was measured by a nitrogen gas adsorption method using 2400, the pore volume with a pore radius of less than 10 ° was 0.52.
cm ³ / g, 100Å or less of the pore volume or pore radius 10Å is 1.02 cm ³ / g, total pore volume 2.02cm ³ /
g and specific surface area were 1786 m2 / g.

<Preparation of Ru-Sn-Pt catalyst>
0.48 g of chloroplatinic acid hexahydrate was placed in a 1-liter eggplant flask, and 3.36 ml of 5N hydrochloric acid was added to dissolve it. 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. 3.00 g of the above activated carbon was added to this solution, and the solution was allowed to stand at room temperature for 15 hours. 70 ° C. using an evaporator,
After water was distilled off at 2.7 kPa, the water was removed under a nitrogen gas atmosphere.
Baking treatment at 0 ° C for 2 hours, and then 450 ° C in a hydrogen atmosphere
For 2 hours. 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. 6.1 wt% ruthenium according to the above method-5.
A catalyst in which 0% by weight tin-3.4% by weight platinum was supported on activated carbon (the supported amount is a value based on the activated carbon) was prepared.

<Hydrogen reduction reaction of a mixture of succinic acid, glutaric acid, and adipic acid> In a 30 ml autoclave,
5 g of water, 2.1 g of a mixture of the above-mentioned succinic acid, glutaric acid and adipic acid and 0.15 g of the catalyst prepared by the above method were charged, and the atmosphere in the autoclave was replaced with nitrogen at room temperature, and then hydrogen was injected to 2.0 MPa. Then, the temperature was raised to 180 ° C. When the temperature reached 180 ° C., hydrogen was injected to 15 MPa. A hydrogenation reduction reaction was performed at this pressure for 10 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 of succinic acid, glutaric acid, and adipic acid was 94% each.
%, 94%, 97%, 1,4-butanediol,
The yields of 1,5-pentanediol and 1,6-hexanediol were 50%, 76%, and 61%, respectively.

[0034]

Comparative Example 1 The pore volume and the specific surface area of the coal activated carbon CX-2 manufactured by Mitsubishi Chemical were measured by the nitrogen gas adsorption method using Shimadzu Micromeritex ASAP-2400 in the same manner as in Example 1. A pore volume of 10 ° or less is 0.57 cm ³ / g, a pore volume of a pore radius of 10 ° to 100 ° is 0.44 cm ³ / g, and a total pore volume is 1.0.
7 cm ³ / g and the specific surface area was 1615 m ² / g.

According to the example of JP-A-10-71332, 30% nitric acid was added to CX-2 and the mixture was treated at 95 ° C. for 3 hours. After filtering, washing and drying the activated carbon, the pore volume and the specific surface area were measured in the same manner as described above. As a result, the pore volume with a pore radius of 10 ° or less was 0.45 cm ³ /
g, the pore volume of pores having a pore radius of 10 ° or more and 100 ° or less is 0.1 g.
38 cm ³ / g, total pore volume 0.89 cm ³ / g, specific surface area 1332 m ² / g, pore radius 10-10
It was confirmed that the pore volume of 0 ° was different from the activated zinc chloride activated carbon of the present invention.

[0036]

Comparative Example 2 A pore volume and a specific surface area measured using the same method and apparatus as those of Comparative Example 1 were 0.35 cm ³ / g with a pore radius of less than 10 ° and a pore radius of 10 ° or more and 100 mm or less.
Using activated carbon having a pore volume of less than 0.23 cm ³ / g, a total pore volume of 0.61 cm ³ / g, and a specific surface area of 937 m ² / g, in the same manner as in the catalyst preparation of Example 1, A ruthenium-tin-platinum / activated carbon catalyst was prepared. 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 91%, 90% and 9%, respectively.
The yields of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol were 40%, 68%, and 55%, respectively.

[0037]

Example 2 Water 5 was added to an autoclave having a capacity of 50 ml.
g, 2.10 g of succinic acid and the catalyst prepared in Example 1.
After charging 30 g and replacing the atmosphere in the autoclave with nitrogen at room temperature, 2.0 MPa of hydrogen was injected, and 180 ° C.
Temperature. When the temperature reached 180 ° C, hydrogen was injected and
It was 5 MPa. The hydrogenation 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 reaction solution separated by decantation and the catalyst washing solution were combined, and the conversion of succinic acid and the yield of 1,4-butanediol were determined by liquid chromatography and gas chromatography. As a result, the conversion of succinic acid was 98%, and the yield of 1,4-butanediol was 88%.

[0038]

Example 3 Water 5 was placed in an autoclave having a capacity of 50 ml.
g, 2.10 g of glutaric acid and 0.30 g of the catalyst prepared in Example 1, and the atmosphere in the autoclave was replaced with nitrogen at room temperature.
The temperature was raised to 0 ° C. When the temperature reached 240 ° C., hydrogen was injected to 9.8 MPa. A hydrogenation reaction was performed at this pressure for 3.5 hours. After completion of the reaction, the catalyst was separated by decantation, and the catalyst was washed with purified water. The conversion rate of glutaric acid and the yield of 1,5-pentanediol 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 of glutaric acid was 100%, and the yield of 1,5-pentanediol was 92%.

[0039]

Example 4 Water 5 was added to an autoclave having a capacity of 50 ml.
g, 2.10 g of adipic acid and 0.30 g of the catalyst prepared in Example 1, and the atmosphere in the autoclave was replaced with nitrogen at room temperature.
The temperature was raised to 0 ° C. When the temperature reached 240 ° C., hydrogen was injected to 9.8 MPa. A hydrogenation reaction was performed at this pressure for 3.5 hours. After completion of the reaction, the catalyst was separated by decantation, and the catalyst was washed with purified water. The reaction solution separated by decantation and the catalyst washing solution were combined, and the conversion of adipic acid and the yield of 1,6-hexanediol were determined by liquid chromatography and gas chromatography. As a result, the conversion of adipic acid was 100%, and the yield of 1,6-hexanediol was 90%.

[0040]

According to the present invention, regardless of the type of carboxylic acid, alcohols can be produced with high yield by direct hydrogenation. In particular, a mixture of dicarboxylic acids including succinic acid, glutaric acid, and adipic acid, which are by-products in producing adipic acid by nitric acid oxidation of cyclohexanenone and / or cyclohexanol, is converted to 1,4-butanediol, 1.5 A mixture of -pentanediol and 1,6-hexanediol can be produced in high yield.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 33/26 C07C 33/26 // C07B 61/00 300 C07B 61/00 300 F term (Reference) 4G069 AA03 AA14 BA08A BA08B BB02A BB02B BC22A BC22B BC70A BC70B BC75A BC75B CB02 CB70 DA05 EA02Y EC04X EC04Y EC05X EC05Y EC08X EC08Y EC09X EC09Y EC12X EC12Y EC13X EC13Y EC14X EC14Y EC18BA11 BC18 AC12 BC18 ABC18H

Claims (8)

[Claims] 1. A catalyst for hydrogenating carboxylic acid, which is a catalyst in which ruthenium, tin and platinum are supported on activated carbon, wherein the activated carbon is activated carbon with zinc chloride. 2. Activated carbon supports ruthenium, tin and platinum.
Catalyst having a pore radius of less than 10 °
Pore volume is 0.03cm^Three/ G more than 0.8cm^Three/ G or less
Below, the pore volume whose pore radius is 10 ° or more and 100 ° or less
0.5cm^Three/ G over 2.0cm^Three/ G or less
1.2 cm pore volume^Three/ G or more and 3.0 cm ^Three/ G or less, ratio
800m surface area^Two/ G or more and 2,000m^Two/ G
A catalyst for hydrogenating carboxylic acids, comprising: 3. A method for producing an alcohol by reacting a carboxylic acid and / or carboxylic anhydride with hydrogen in the presence of a catalyst and water to produce an alcohol.
Or a method for producing an alcohol, comprising using the catalyst for hydrogenating a carboxylic acid according to 2 above. 4. The carboxylic acid is at least one dicarboxylic acid selected from dicarboxylic acids represented by the general formula (1), and the carboxylic anhydride is at least one dicarboxylic anhydride represented by the general formula (2). The method for producing an alcohol according to claim 3, wherein the alcohol is a product. Embedded image (Wherein R ₁ and R ₂ each independently have _{2 to 2} carbon atoms)
Represents a divalent hydrocarbon group which is 0. ) 5. The method of claim 1, wherein the carboxylic acid is succinic acid, glutaric acid, adipic acid, cyclohexanedicarboxylic acid, maleic acid,
At least one selected from fumaric acid and terephthalic acid
A carboxylic acid containing a seed, wherein the carboxylic anhydride is at least one selected from succinic anhydride and maleic anhydride.
5. The method for producing an alcohol according to claim 3, which is a carboxylic anhydride containing a seed. 6. The method for producing an alcohol according to claim 5, wherein the carboxylic acid and / or carboxylic anhydride is a mixture of carboxylic acids including succinic acid, glutaric acid, and adipic acid. 7. The carboxylic acid and / or carboxylic anhydride is a mixture of carboxylic acids containing succinic acid, glutaric acid, and adipic acid recovered from an oxidation reaction solution of cyclohexanone and / or cyclohexanol. A method for producing an alcohol according to claim 6. 8. Temperature 100 ° C. to 300 ° C., hydrogen pressure 1MP
The method for producing an alcohol according to any one of claims 3 to 7, wherein the carboxylic acid and / or carboxylic anhydride is reacted with hydrogen under the conditions of a to 25 MPa.