JP5187675B2 - Method for producing hydroxyketone from trivalent or higher alcohol and catalyst used therefor - Google Patents

Description

The present invention relates to a method for producing a hydroxyketone using a supported copper catalyst using a trivalent or higher-valent alcohol having an adjacent hydroxyl group as a raw material.

Hydroxy ketones represented by acetol are used as chemical intermediates and pharmaceutical intermediates and are important substances in the chemical industry, but no efficient production method has been found so far. Conventionally, such a hydroxyketone has been synthesized by oxidative dehydrogenation of a diol (Patent Document 1) or hydrogenation of a hydroxycarboxylic acid. All of these reactions have an essential problem of excessive oxidative decomposition or excessive reduction because the product has a functional group called ketone.
In recent years, there is a method of producing acetol from formaldehyde, carbon monoxide and hydrogen (Patent Document 2). However, this method requires a high reaction pressure, the reaction device needs to be a pressure device, and a rhodium compound as a catalyst. From the viewpoints of capital investment, running cost, and reaction efficiency, such as using a noble metal and using a solvent for the reaction, the reaction was problematic.
Further, even if the reaction is carried out using an acid catalyst such as aluminum oxide, which is a known catalyst, focusing on the dehydration reaction, the selectivity of the target product, hydroxyketone, is low and efficient, as shown in a comparative example described later. It was not a typical catalyst.
Furthermore, among methods disclosed in recent years, there is known a method of producing monohydroxyacetone by gas phase contact reaction of glycerin using copper and / or copper oxide supported on silica as a catalyst (Patent Document 3). The application is characterized in that chromium is not used as a catalyst component, but the yield of the target product, dihydroxyacetone, is not sufficient, and the addition of nitrogen and hydrogen as diluent gases results in a low space-time yield. Has the disadvantages.

Japanese Patent Publication No. 61-16256 Japanese Examined Patent Publication No. 4-11534 JP 2007-8850 A

The object of the present invention is to solve the above-mentioned conventional technical problems, and in particular, by adopting a catalyst suitable for production of hydroxyketone, it is possible to efficiently produce hydroxyketone from trihydric or higher alcohols with high selectivity. It is to provide a way to do.

As a result of diligent study, the present inventors have used a catalyst carrier composite in which copper is supported on a specific carrier as a catalyst, so that a primary hydroxyl group having a hydroxyl group adjacent thereto by dehydration reaction of a trivalent or higher alcohol can be obtained. It has been found that what has been dehydrated to form an enol form forms a ketone form by tautomerism in the reaction system, and the present invention has been completed.

That is, an important feature of the present invention is that a catalyst carrier composite having a copper content of 1 to 10% by weight and having copper supported on one or more kinds of carriers selected from aluminum oxide and zirconium oxide is used as a catalyst. There is an important technical significance in the fact that it has been adopted and in combination with the dehydration reaction of trihydric or higher alcohols. With this, for the first time, the primary hydroxyl group with a neighboring hydroxyl group is dehydrated to form an enol form. Can form ketone bodies by tautomerism in the reaction system.

That is, according to the present invention, in producing hydroxyketone from a trihydric or higher alcohol having an adjacent hydroxyl group, the reaction as a whole proceeds with a dehydration reaction, and as a catalyst , the copper content is 1 to 10% by weight, There is provided a method for producing a hydroxyketone using a catalyst carrier composite in which copper is supported on a carrier selected from aluminum oxide and zirconium oxide.

  In addition, according to the present invention, there is provided the above production method, wherein the catalyst carrier is a catalyst carrier containing aluminum oxide.

  In addition, according to the present invention, there is provided the above production method, wherein the catalyst carrier is a catalyst carrier containing zirconium oxide.

Moreover, according to this invention, the trivalent or more alcohol is glycerol, The said manufacturing method whose hydroxyketone is 1-hydroxyacetone is provided.

In addition, according to the present invention, there is provided the above production method wherein the catalyst carrier is a catalyst carrier containing aluminum oxide, the trivalent or higher alcohol is glycerin, and the hydroxyketone is 1-hydroxyacetone.

According to the present invention, there is also provided the above production method wherein the catalyst carrier is a catalyst carrier containing zirconium oxide, the trivalent or higher alcohol is glycerin, and the hydroxyketone is 1-hydroxyacetone.

In addition, according to the present invention, in producing hydroxyketone from a trivalent or higher-valent alcohol having an adjacent hydroxyl group, the reaction proceeds as a whole by a dehydration reaction, and copper is selected from aluminum oxide and zirconium oxide as a catalyst. There is provided a catalyst for producing hydroxyketone comprising a copper-catalyst support composite supported on a catalyst.

  Moreover, according to this invention, the said catalyst whose catalyst carrier is a catalyst carrier containing an aluminum oxide is provided.

  According to the present invention, there is also provided the above catalyst, wherein the catalyst carrier is a catalyst carrier containing zirconium oxide.

Moreover, according to this invention, the trivalent or more alcohol is glycerol, The said catalyst whose hydroxyketone is 1-hydroxyacetone is provided.

According to the present invention, copper supported on a particular carrier selected copper from aluminum oxide and zirconium oxide - using a catalyst carrier complex, and, by proceeding in the dehydration reaction as a reaction whole, 3 with adjacent hydroxyl groups A hydroxyketone can be efficiently produced from a higher- valent alcohol with a high selectivity.

The present invention comprises a method for producing a hydroxyketone with a high selectivity from a trihydric or higher alcohol having an adjacent hydroxyl group, and a specific hydroxyketone production catalyst used in the production method. As you did.
The copper-catalyst support composite which is the catalyst of the present invention is a copper-catalyst support composite in which copper is supported on one or more kinds of catalyst supports selected from aluminum oxide and zirconium oxide.

The catalyst used is significantly different from the dehydration reaction, which is a feature of the overall reaction of the present invention, as compared with a normal dehydration reaction. In general, when an alcohol dehydration reaction is performed, the use of an acid catalyst is widely used, and an olefin or an ether is obtained by the reaction. In the dehydration reaction in the present invention, the direct product is expected to be an olefin. In particular, in the glycerin reaction, hydroxyl groups related to dehydration are present at the 1- and 2-positions, and the hydroxyl group at the 1-position is selectively dehydrated. To produce enol alcohol, which isomerizes to produce hydroxyacetone.
This reaction is particularly characteristic in that it is not a dehydration reaction with a solid acid such as alumina or silica-alumina, which is usually used as an acid catalyst, but usually uses copper that is not classified as an acid catalyst as a catalyst component. .

  Copper in the catalyst for producing hydroxyketone according to the present invention is a commercially available product, a product obtained by reducing a commercially available product, a product obtained by thermally decomposing copper oxide, hydroxide, carbonate, nitrate, acetate or the like, or known after pyrolysis. Any form such as those reduced by the method can be used as the catalyst. Similarly, for a copper-catalyst carrier composite, a commercially available product, a product obtained by reducing a commercially available product, a product obtained by thermally decomposing a metal hydroxide, carbonate, nitrate, acetate, etc. on a catalyst support, or after pyrolysis Any form such as those reduced by a known method can be used as a catalyst.

As a method for supporting copper on the catalyst carrier in the copper-catalyst carrier composite, a known method such as an impregnation method or a coprecipitation method can be used.
For example, a composite obtained by drying, firing, and reducing a precipitate obtained by dissolving copper nitrate in water together with aluminum nitrate, which is a precursor of the catalyst carrier component, and adding an alkaline aqueous solution thereto is used as a catalyst. Is possible.
The content ratio of copper: catalyst support in the copper-catalyst support composite can be selected within a range of 1.00% or more by weight% of copper. If the copper: copper content ratio in the catalyst support is less than 1.00, sufficient catalytic activity cannot be obtained. Further, the copper catalyst can be used without using a support.

  In the method for producing hydroxyketone according to the present invention, it is an important feature that a polyhydric alcohol having an adjacent hydroxyl group is used as copper or copper and a catalyst carrier complex as a catalyst, and the reaction as a whole proceeds by a dehydration reaction.

  The reaction apparatus used in the production of the hydroxyketone of the present invention is not particularly limited. For example, a predetermined amount of catalyst precursor is put into a gas phase flow reaction apparatus and reduced by a known method to form an active catalyst layer in the gas phase flow reaction apparatus. It is possible to produce a hydroxyketone by supplying a raw material polyhydric alcohol.

As the trihydric or higher alcohol as a raw material, a polyhydric alcohol having an adjacent hydroxyl group is used. Specific examples of the trivalent or higher alcohol having an adjacent hydroxyl group include glycerin and 1,2,3-butanetriol.

  Examples of hydroxy ketones obtained from these raw materials include hydroxy acetone, 2-hydroxy-3-butanone, and 1-hydroxy-2-butanone.

The method for producing hydroxyketone of the present invention is preferably used for producing hydroxyketone from a trivalent or higher alcohol having an adjacent hydroxyl group. Specifically, it is used for production of hydroxyacetone from glycerin and production of 2-hydroxy-3-butanone and 1-hydroxy-2-butanone from 1,2,3-butanetriol.
Moreover, even if the raw material trihydric or higher alcohol is a mixture, the corresponding hydroxyketone can be produced at the same time.

  The reaction temperature of the method for producing hydroxyketone of the present invention can be applied in the range of 150 ° C. to 400 ° C., and the temperature range of 200 ° C. to 350 ° C. is suitable. In order to allow the reaction to proceed sufficiently, it is preferably 200 ° C. or higher, particularly preferably 225 ° C. or higher. Further, in order to keep the product selectivity good, 350 ° C. or lower is preferable, and a more preferable reaction temperature is in the range of 225 ° C. to 300 ° C.

The water in the trihydric or higher alcohol as a raw material can be used in the range of 0 to 98% by weight, and preferably in the range of 30 to 70% by weight. When the water content of the trihydric or higher alcohol is in the range of 30 to 70% by weight, the reaction efficiency is remarkably excellent, and the target product hydroxyketone can be obtained with high selectivity.

Hereinafter, although the effect of the present invention is explained concretely based on an example, the present invention is not limited to these.
The fixed bed atmospheric pressure gas flow reactor used in Examples and Comparative Examples is a reactor having an inner diameter of 10 mm and a total length of 300 mm, having a carrier gas inlet and a raw material inlet at the upper end and a gas outlet at the lower end. It has a reaction crude liquid collection container (cooling).
The catalyst weight used in Examples and Comparative Examples was all 0.5 g. Commercially available reagents (manufactured by Wako Pure Chemicals, special grade) were used as catalyst raw materials for copper-aluminum oxide as a catalyst.
The reaction crude liquid collected in the collection container is measured by gas chromatography. After calibration curve correction, the yield of hydroxyacetone and the remaining amount of raw materials such as glycerin are determined, and the conversion rate (moles) is determined from this value. %) And selectivity (mol%).

<Example 1>
(Production of copper-aluminum oxide catalyst)
Sodium hydroxide (manufactured by Wako Pure Chemicals, special grade reagent) was added to a solution of 212.8 g of copper nitrate (Wako Pure Chemicals, special grade reagent) and aluminum nitrate (Wako Pure Chemicals, special grade reagent) 220.3 g in 5 L of water. ) A precipitate formed when 154.1 g of a solution dissolved in 1 L of water is added is dried and fired to obtain a catalyst precursor. The catalyst precursor is placed in a fixed bed atmospheric pressure gas flow reactor and reduced in a hydrogen stream to form a copper-aluminum oxide catalyst.

<Example 2>
(Production of hydroxyketone)
From the upper part of the fixed bed atmospheric pressure gas flow reactor where the copper-aluminum oxide catalyst layer is set, nitrogen is added as a carrier gas at 10 ml / min. The flow rate was. The 30 wt% glycerin aqueous solution as the raw material was supplied to the catalyst layer at a rate of 1.8 ml / h for reaction. Table 1 shows the glycerin conversion rate and hydroxyacetone selectivity depending on the reaction temperature.
Table 1 shows the dehydration reaction of glycerol with a copper-aluminum oxide catalyst.

From the results of the table, it can be seen that, under the reaction conditions in which the glycerin conversion is 98%, the hydroxyacetone selectivity is 92% and the by-product is very small.

<Example 3>
(Production of copper-aluminum oxide catalyst with varying copper content)
A copper-aluminum oxide catalyst in which the content ratio of copper and aluminum oxide was changed in accordance with Example 1 was prepared and subjected to a hydroxyacetone production reaction. Other conditions were the same as in Example 2.
Table 2 shows the glycerin dehydration reaction with the copper-aluminum oxide catalyst with different copper contents.
The results are shown in Table 2.

From the results in the table, it can be seen that the copper content has a good conversion rate and selectivity from 1.0 wt% to 100 wt%.

< Reference example >
(Manufacture of copper catalyst)
To a solution in which 303.8 g of copper nitrate (manufactured by Wako Pure Chemicals, special grade reagent) was dissolved in 5 L of water, a solution in which 110.0 g of sodium hydroxide (made by Wako Pure Chemical Industries, special grade reagent) was dissolved in 1 L of water was added. The precipitate formed at this time is dried and calcined to obtain a catalyst precursor. 0.5 g of the catalyst precursor was placed in a fixed bed atmospheric pressure gas flow reactor and reduced in a hydrogen stream to obtain a copper catalyst.

<Example 4 >
(Production of copper-zirconium oxide catalyst)
Sodium hydroxide (Wako Pure Chemical Industries, Ltd.) was added to a solution obtained by dissolving 200.3 g of copper nitrate (Wako Pure Chemical Industries, special grade reagent) and zirconyl nitrate dihydrate (Wako Pure Chemical Industries, special grade reagent) 73.9 g in 5 L of water. Manufactured, special grade reagent) The precipitate formed when 120.9 g of a solution dissolved in 1 L of water is added is dried and fired to obtain a catalyst precursor. 0.5 g of the catalyst precursor was placed in a fixed bed atmospheric pressure gas flow reactor and reduced in a hydrogen stream to obtain a copper-zirconium oxide catalyst.

<Example 5 >
(Production of copper-zirconium oxide-aluminum oxide catalyst)
Copper nitrate (Wako Pure Chemicals, special grade reagent) 156.3 g, Aluminum nitrate 9 hydrate (Wako Pure Chemicals, special grade reagent) 161.8 g, and zirconyl nitrate dihydrate (Wako Pure Chemicals, special grade reagent) The precipitate formed when 57.6 g of water dissolved in 5 L of water and 150.9 g of sodium hydroxide (made by Wako Pure Chemicals, special grade reagent) dissolved in 1 L of water was added, dried and calcined to form a catalyst. Let it be a precursor.
0.5 g of the catalyst precursor was placed in a fixed bed atmospheric pressure gas flow reactor and reduced in a hydrogen stream to obtain a copper-zirconium oxide-aluminum oxide catalyst.

<Example 6 >
The experiment was conducted using the catalysts described in Examples 1, 4 and 5 with the reaction temperature fixed at 250 ° C. Other conditions were the same as in Example 2.
Table 3 shows the influence on the dehydration reaction of glycerin due to the difference in the catalyst carrier.
The results are shown in Table 3.

From the results in Tables 2 and 3, the reaction proceeds even with a copper catalyst without a carrier alone, but when aluminum oxide and zirconium oxide are used as a catalyst carrier, the glycerin conversion rate, hydroxyacetone is higher than that with a copper catalyst alone. It can be seen that the selectivity is high and an efficient reaction proceeds. Further, the reaction proceeds with a composite carrier of aluminum oxide and zirconium oxide.

<Example 7 >
A commercially available catalyst (N-201 JGC Chemical, copper-chromium oxide; N-242 JGC Chemical,
An experiment was conducted using copper-aluminum oxide; G-22 Zudd Chemie Catalyst, copper-chromium oxide; T-317 Nissan Gardler, copper-aluminum oxide). Other conditions were as in Example 7.
According to Table 4 shows the results of glycerin dehydration reaction using a commercially available supported copper catalyst. The results are shown in Table 4.

<Example 8 >
Experiments were conducted using raw materials having different glycerin concentrations using commercially available catalysts (N-201, JGC Chemicals, copper-chromium oxide). Other conditions were the same as in Example 7.
Table 5 shows the influence of moisture in the raw material on the glycerin dehydration reaction.
The results are shown in Table 5.

<Example 9 >
Using the copper-aluminum catalyst described in Example 1, 1,2,3-butanetriol was dehydrated. The raw material 1,2,3-butanetriol was supplied to the reactor as a 30 wt% aqueous solution. Other conditions were the same as in Example 7.
Table 6 shows the dehydration reaction of 1,2,3-butanetriol.
The results are shown in Table 6.

<Comparative Example 1>
The reaction was carried out using only the aluminum oxide support without using copper as the catalyst. Other conditions were the same as in Example 7.
The results are shown in Table 7.

<Comparative example 2>
An experiment was conducted using a copper catalyst (copper-cerium oxide, copper-magnesium oxide, copper-zinc oxide) using another catalyst carrier as a catalyst. Other conditions were the same as in Example 7.
The results are shown in Table 8.

From the results of Tables 7 and 8, it can be seen that the reaction does not proceed efficiently unless an appropriate catalyst support is used.

According to the present invention, by using a catalyst comprising a catalyst carrier complex in which copper is supported on a specific carrier selected from aluminum oxide and zirconium oxide, and by proceeding in a dehydration reaction as a reaction total, with high selectivity, A hydroxyketone can be suitably produced from a trihydric or higher alcohol having an adjacent hydroxyl group, and an industrially superior hydroxyketone production technique that cannot be achieved by using a conventional catalyst can be provided.

Claims (10)

In producing a hydroxyketone from a trivalent or higher alcohol having a hydroxyl group adjacent thereto, the reaction proceeds as a whole by a dehydration reaction, and as a catalyst , copper is contained from 1 to 10% by weight of copper from aluminum oxide and zirconium oxide. A method for producing a hydroxyketone, comprising using a catalyst carrier composite supported on a selected carrier.   The production method according to claim 1, wherein the catalyst carrier is a catalyst carrier containing aluminum oxide.   The production method according to claim 1, wherein the catalyst carrier is a catalyst carrier containing zirconium oxide. The production method according to any one of claims 1 to 3 , wherein the trivalent or higher alcohol is glycerin and the hydroxyketone is 1-hydroxyacetone. The production method according to claim 1, wherein the catalyst carrier is a catalyst carrier containing aluminum oxide, the trivalent or higher alcohol is glycerin, and the hydroxyketone is 1-hydroxyacetone. The production method according to claim 1, wherein the catalyst carrier is a catalyst carrier containing zirconium oxide, the trivalent or higher alcohol is glycerin, and the hydroxyketone is 1-hydroxyacetone. In producing a hydroxyketone from a trivalent or higher alcohol having a hydroxyl group adjacent thereto, the reaction proceeds as a whole by a dehydration reaction, and as a catalyst , copper is contained from 1 to 10% by weight of copper from aluminum oxide and zirconium oxide. A catalyst for producing hydroxyketone comprising a copper-catalyst carrier composite supported on a selected carrier. The catalyst according to claim 7 , wherein the catalyst support is a catalyst support containing aluminum oxide. The catalyst according to claim 7 , wherein the catalyst support is a catalyst support containing zirconium oxide. The catalyst according to any one of claims 7 to 9 , wherein the trihydric or higher alcohol is glycerin and the hydroxyketone is 1-hydroxyacetone.