JP3276413B2 - Method for producing compound having carbonyl group and / or carboxyl group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a compound having a carbonyl group and / or a carboxyl group which is important as an intermediate material for a physiologically active substance or an amino acid. More specifically, the present invention relates to a method for efficiently producing a compound having a carbonyl group and / or a carboxyl group from inexpensive polyhydric alcohol.

[0002]

BACKGROUND OF THE INVENTION Dihydroxyacetone (or a dimer thereof), hydroxypyruvic acid, hydroxyacetone, pyruvic acid, glyceraldehyde (or a compound having a carbonyl group and / or a carboxyl group) Its dimer), oxymalonic acid,
Glyceric acid, lactic acid and the like are extremely important as intermediates for producing physiologically active substances and amino acids. It is conceivable that these intermediates are derived from glycerin having a primary hydroxyl group and a secondary hydroxyl group, 1,2-propylene glycol, or a derivative thereof from the basic skeleton.

Conventionally, various methods have been proposed for oxidizing glycerin to induce glycerin oxide. For example, J. Org. Chem .. 52 , 2318 (1987) describes a method for glyceric acid by nitric acid oxidation or mercury oxidation of glycerin, but is not a preferable method from the viewpoint of pollution and wastewater treatment. British Patent No. 1051614 describes a method for producing glyceraldehyde by electrolytic oxidation, but the raw material glycerin has a dilute concentration and is difficult to apply practically. Also, JP-A-62-210994, JP-A-2-86089 and Journal of American Ch.
Emical Society , 59, 301 (1937) describes a method for producing dihydroxyacetone in which the secondary hydroxyl group of glycerin is oxidized by an enzymatic reaction using Acetobacter ( Acetobacter Sp .). JP-A-1-207255 further proposes a method of chemically synthesizing dihydroxyacetone by peroxidizing glycerin in an organic solvent with peracetic acid.

However, in both of the above-mentioned methods using microorganisms and chemical synthesis methods, the raw material glycerin concentration during the reaction is as low as 5 to 15% by weight, and the resulting dihydroxyacetone concentration is low. There are many problems. In addition, pyruvic acid is produced by a gas phase oxidation reaction of lactic acid. However, these oxidation products or dimers thereof are thermally unstable and easily isomerize depending on pH. It is necessary to strictly control the reaction conditions below for the synthesis. However, there is a disadvantage that the reaction under mild conditions requires a long time. Further, it is necessary to carry out the reaction at a low concentration in order to alleviate the reaction alienation due to molecular association of the starting polyhydric alcohol, which is not satisfactory in terms of productivity and is not an industrially advantageous method.

[0005]

Means for Solving the Problems The present inventors have developed a high-productivity process capable of efficiently producing a corresponding compound having a carbonyl group and / or a carboxyl group from a polyhydric alcohol by a catalytic oxidation method. Therefore, as a result of intensive research aiming at obtaining a low yield of by-products in a high yield, obtaining a high concentration, and achieving a high reaction rate, the use of a specific catalyst component and a catalyst carrier has led to The inventors succeeded in achieving these objects and completed the present invention.

[0006] Namely, the present invention provides bi as catalytic component
Smuth / platinum, cerium / platinum or cerium / bismuth
A catalyst in which platinum is supported on a carrier having at least one physical property selected from the following (a) to (d) and having an ash content of 15% by weight or less and made of activated carbon and / or carbon black: Using a fixed bed reactor, glycemic
Phosphorus or 1,2-propylene glycol in air or oxygen
And processes for the preparation of compounds of a mixed gas having a carbonyl group and / or carboxyl groups, characterized in that the catalytic oxidation of nitrogen, the physical properties of the responsible body: (a) activated carbon and / or a specific surface area of the carbon black is 500 meters ² / g (B) Activated carbon and / or carbon black has a bulk density of 8
200 g / l or less (c) activated carbon and / or pore volume of the carbon black is 0.3 ml / g or more (d) an average pore diameter of the activated carbon and / or carbon black is concerned under 20nm or less.

[0007]

[0008]

[0009] Activated carbon and carbon blackOfThe properties are as follows
Has at least one physical property selected from (a) to (d)
And the ash content is preferably 15% by weight or less.
No. If it is more than 15% by weight, the catalytic activity decreases.
, Preferably 5% by weight or less, more preferably
Not more than 2% by weight. However, even if the ash content is low,
Heavy iron, nickel, cobalt, chromium, manganese, etc.
What contains metal should be reduced as much as possible
preferable. This is due to the incorporation of these heavy metals,
Reduction of catalytic activity and catalytic selectivity in catalytic oxidation of
Because it can have a significant effect,
You.

The physical properties required when using activated carbon and / or carbon black as a carrier are as follows. (A) The specific surface area of the activated carbon and / or carbon black is at least 500 m ² / g. (B) The bulk density of the activated carbon and / or carbon black is 8
(C) activated carbon and / or carbon black has a pore volume of 0.3 ml / g or more (d) activated carbon and / or carbon black has an average pore diameter of 20 nm or less

That is, since the specific surface area of the carrier greatly affects the high dispersibility of the catalyst component, the specific surface area is required to be 500 m ² / g or more. If the specific surface area is less than 500 m ² / g, the reaction of the present invention cannot proceed efficiently. It is preferably at least 800 m ² / g, more preferably at least 1000 m ² / g, particularly preferably at least 1200 m ² / g. The bulk density of the support is a very important item and needs to be 800 g / liter or less, and if it is larger than this, the reaction efficiency per unit weight of the catalyst component is greatly reduced. It is preferably at most 600 g / l, more preferably at most 400 g / l, particularly preferably at most 200 g / l. The pore volume of the carrier needs to be 0.3 ml / g or more, and if it is less than this, the reaction of the present invention does not proceed efficiently. Preferably 0.6 ml /
g or more, more preferably 0.9 ml / g or more, particularly preferably 1.1 ml / g or more. The average pore diameter of the support must be 20 nm or less, and if it is larger than this, the catalytic activity is greatly reduced. Preferably 10 nm or less,
It is more preferably at most 6 nm, particularly preferably at most 4 nm. In the case where activated carbon and carbon black are used in the present invention, their properties are as described in the above (a) to (d).
It is necessary to have at least one physical property selected from the following, and it is not necessary to satisfy all the physical property requirements. However, it is more effective to use one that satisfies the requirements of these physical properties as much as possible.

Activated carbon as a catalyst carrier used in the present invention may be derived from any raw material such as coconut shell, wood, coal, beet char or petroleum pitch.
In particular, coconut shells and petroleum pitches with low ignition residue or low ash content are effective. Activated carbon may be activated by steam activation or chemical activation.
In some cases, a chemical activation having a higher activation effect is more effective as a carrier. Activated carbon as a catalyst carrier used in the present invention may be a commercially available one as it is, or may be used after adjusting the pore distribution or reducing ash by appropriate pretreatment, for example, acid treatment. . As the commercially available granular and powdered activated carbon used in the present invention, those generally used for water treatment and for water-soluble food purification are mainly used. For example, granular Shirasagi series (WH, Sx, KL) manufactured by Takeda Chemical and Powdered activated carbon represented by carbofin, granular activated carbon manufactured by Norit
(ROX, RAX, DARCO, C, ELORIT, etc.) and powder (AZ
O, PN, ZN, etc.), Kureha Chemical's bead-shaped activated carbon (BAC)
Is mentioned. Commercially available carbon black is also effective as a catalyst carrier for carrying out the reaction of the present invention, and includes, for example, carbon black manufactured by Cablack. However, the activated carbon and carbon black used in the present invention are not particularly limited to these activated carbon and carbon black.

The supported catalyst used in the present invention is obtained by supporting the above-mentioned catalyst components on the above-mentioned carrier in a conventional manner, simultaneously or stepwise, and activating them with various reducing agents. Used for oxidation reaction of polyhydric alcohol. For example, in the case of an activated carbon carrier, a catalyst composition obtained by supporting the catalyst component used in the present invention on granular activated carbon in a conventional manner is converted into a suitable reducing agent such as formalin, hydrazine, sodium borohydride, hydrogen or It is obtained by performing a reduction treatment with methyl alcohol or the like.

[0014]

Here, the oxidation route when glycerin or 1,2-propylene glycol is used as the polyhydric alcohol having a primary hydroxyl group and a secondary hydroxyl group will be described below with reference to the drawings.

Glycerin oxidation pathway: As shown in FIG. 1, glycerin is oxidized by a route via dihydroxyacetone and glyceraldehyde depending on whether a secondary hydroxyl group is first oxidized or a primary hydroxyl group is oxidized. The route is divided into two routes. That is, this route includes the following five processes. Formation of dihydroxyacetone by oxidation of glycerin. Formation of hydroxypyruvic acid by oxidation of dihydroxyacetone. Formation of glyceraldehyde by oxidation of glycerin. Formation of glyceric acid by oxidation of glyceraldehyde. Generation of hydroxypyruvic acid by oxidation of glyceric acid. Generation of oxymalonic acid by oxidation of glyceric acid. Here, glyceraldehyde and dihydroxyacetone, which are the products of the present invention, exist as an equilibrium mixture of glyceraldehyde dimer and dihydroxyacetone dimer, respectively, so that the concentration is adjusted or p is adjusted.
The equilibrium can be shifted toward the monomer by adjusting H or the like.

Oxidation pathway of 1,2-propylene glycol: As shown in FIG. 2, the oxidation of 1,2-propylene glycol is carried out by oxidizing a secondary hydroxyl group first or oxidizing a primary hydroxyl group. Thus, the route is divided into a route via hydroxyacetone and a route via lactic acid. That is, this route is composed of the following four processes. Production of hydroxyacetone by oxidation of 1,2-propylene glycol. Formation of pyruvate by oxidation of hydroxyacetone. Production of lactic acid by oxidation of 1,2-propylene glycol. Production of pyruvate by oxidation of lactic acid.

Next, in the production method of the present invention, suitable reaction conditions can be divided into various modes depending on the compound to be oxidized and the target compound to be obtained. (1) First, as a first embodiment, there is a case where dihydroxyacetone is produced from glycerin or hydroxyacetone from 1,2-propylene glycol using the catalyst of the present invention. In this case, the reaction temperature is preferably as low as possible, and is preferably -20 to 60C, and more preferably -10 to 10C.
The temperature is preferably 60 ° C, more preferably 0 to 40 ° C. When the reaction temperature exceeds 60 ° C., the oxidation of primary hydroxyl groups is promoted, and the yields of dihydroxyacetone and hydroxyacetone decrease. On the other hand, if the reaction temperature is lower than -20 ° C, the reaction rate is drastically reduced, which is not practical. The oxidation reaction is preferably performed in an acidic atmosphere, and the pH is preferably maintained at 7 to 1, preferably 6 to 2, and more preferably 4 to 2. The pH may be adjusted by maintaining acidity by a carboxyl group generated by a partial parallel reaction, or by adding an acid. The molar ratio of oxygen to polyhydric alcohol is preferably oxygen: polyhydric alcohol in the range of 0.1: 1 to 100: 1, but 0.25: 1 to 3
0: 1 is preferred, and more preferably 0.5: 1 to 10:
1 is good. As the catalyst, bismuth / platinum or cerium
Use of bismuth / platinum is preferred, but if the molar ratio of oxygen is too large, the selectivity of the catalyst may change.

(2) In a second embodiment, lactic acid is produced from glycerin, oxymalonic acid, or 1,2-propylene glycol from glycerin via glyceraldehyde using the catalyst of the present invention. is there. In this case, the reaction temperature is 0 to 80 ° C, preferably 30 to 60 ° C,
More preferably, the temperature is 30 to 50 ° C. When oxidizing a primary hydroxyl group to a carboxyl group, it is preferable to carry out the oxidation reaction in a basic atmosphere from the viewpoint of the reaction rate and the yield. However, an oxidation reaction in a basic atmosphere generates an alkali metal salt of a compound having a carboxyl group, so that a neutralization step is required to obtain the compound having a carboxyl group itself. When a metal other than platinum is used as a catalyst element as a catalyst, the pH is preferably adjusted to 7.5 to 13 since the oxidation reaction hardly proceeds unless the reaction is carried out in a basic atmosphere . If you want to use the white gold as the catalyst element,
It has the characteristic that the reaction proceeds even in an acidic atmosphere, and in this case, it is not necessary to add an alkali, so that a compound having a carboxyl group itself can be produced. In the case of platinum, the reaction rate is higher when oxidized in a basic atmosphere having a pH of 8 or more, but platinum is easily eluted in a basic atmosphere. Therefore, when platinum is used as a catalyst element, p
H is 7.5 to 1, preferably 6 to 2, and more preferably 4
It is better to keep it at ~ 2. The molar ratio of oxygen to polyhydric alcohol is oxygen: polyhydric alcohol, 0.1: 1 to 10
0: 1 is preferable, but 0.5: 1 to 20: 1 is preferable, and 1: 1 to 5: 1 is more preferable. As a catalyst can increase the reaction rate by using a cerium-platinum is a catalyst noble earth <br/> earth element-containing. If the catalyst poisoning by oxygen is remarkable, cerium, bismuth,
The use of platinum is preferred.

(3) As a third embodiment, when the catalyst of the present invention is used to produce hydroxypyruvic acid via glyceric acid or dihydroxyacetone obtained by an oxidation reaction from glycerin by the above-mentioned method, The temperature is preferably from 30 to 60C. The pH is preferably from 3 to 6. The molar ratio of oxygen to polyhydric alcohol is oxygen: polyhydric alcohol, preferably 0.5: 1 to 10: 1. As the catalyst, bismuth, platinum or cerium bismuth white
Gold is preferred.

(4) As a fourth embodiment, when glyceraldehyde is produced from glycerin using the catalyst of the present invention, glyceraldehyde is easily oxidized to glyceric acid, and the reaction temperature is 0 to 40. ° C is preferred,
The pH is 2 to 6, and the molar ratio of oxygen to polyhydric alcohol is oxygen: polyhydric alcohol, preferably 0.25: 1 to 2: 1.

In the oxidation reaction of the polyhydric alcohol used in the present invention, the oxidation of the primary hydroxyl group and the oxidation of the secondary hydroxyl group are basically simultaneous reactions. Accordingly, in the present invention, since a carboxyl group derived from oxidation of the primary hydroxyl group is generated, the reaction solution changes to an acidic side unless an alkali is added. However, the catalyze in the present invention as described above <br/> appropriately selected, further pH, temperature, by maintaining the optimal range of reaction conditions the molar ratio of oxygen such as for raw polyhydric alcohols, primary And the selectivity of secondary hydroxyl groups to oxidation can be controlled. That is, when the primary hydroxyl group of the polyhydric alcohol is mainly oxidized and converted into a carboxyl group, cerium / platinum is preferable as described above,
Primarily bismuth, platinum if <br/> rather cerium bismuth platinum in the case of oxidizing the secondary hydroxyl group is preferably used. As a result, a compound having a specific carbonyl group and / or a carboxyl group can be efficiently produced.

When glycerin or 1,2-propylene glycol is used as a raw material, various compounds having a carbonyl group and / or a carboxyl group can be obtained by successive reactions as described above. Therefore, when producing a compound having a specific carbonyl group and / or carboxyl group, the reaction may be carried out under reaction conditions that maximize the experimentally determined desired compound concentration in the sequential reaction. However, since the oxidation reaction product obtained from the sequential reaction becomes a mixture containing the desired compound, it is preferable to select a catalyst that can achieve a high conversion rate, particularly according to the compound obtained as described above. Further, since the obtained oxidation reaction product is a mixture, it is necessary to perform separation and purification. Separation and purification can be easily performed by a conventional method. For example, a desired compound having a carbonyl group and / or a carboxyl group can be obtained by a method such as chromatographic separation. In the present invention, a polyhydric alcohol having at least one primary hydroxyl group and at least one secondary hydroxyl group is used as a raw material. However, as described above, the primary hydroxyl groups and / or A compound having a carbonyl group and / or a carboxyl group is obtained by applying the method of the present invention to an intermediate having a secondary hydroxyl group or a similar intermediate obtained by another method. I can do it.

The oxidizing agent used in the present invention includes:
Oxygen or an oxygen-containing gas is used. For example, air or a mixed gas of oxygen and nitrogen of any composition can be used, but it is economical to use air. The reaction of the present invention can be applied to a batch system or a continuous system. The reactor may be of a stirred tank type, an injector type, a fluidized bed type, a fixed bed type, or the like. The form of the catalyst is not particularly limited, and powders, granules, molded articles and the like may be used according to the type of the reactor. In the case of a fixed-bed reactor, a catalyst in the form of granules or molded articles is used.

Hereinafter, a method for producing a compound having a carbonyl group and / or a carboxyl group using a fixed bed reactor will be described in detail. The compound having a carbonyl group and / or a carboxyl group produced by the reaction of the present invention is also extremely important as an intermediate in producing a physiologically active substance or an amino acid. , A catalyst separation step is required. Especially when the production volume is large, the catalyst separation process has a large load in terms of process, so the application of a fixed bed reactor eliminates the catalyst separation process and improves productivity such as reactions using highly concentrated raw materials. Brings great benefits in terms of For example, dihydroxyacetone, which is one of the compounds having a carbonyl group produced in the present invention, was first synthesized by a fermentation method in 1896, and is still produced by a fermentation method. The reaction has been long, and the improvement of production efficiency has become a major problem. Performing the reaction of the present invention using a fixed-bed reactor for solving such a problem brings great advantages. That is, in the present invention, a granular catalyst for a fixed bed reactor is prepared using various catalyst supports, and a polyhydric alcohol is catalytically oxidized using a fixed bed reactor filled with the catalyst to form carbonyl groups and And / or by producing a compound having a carboxyl group, the reaction of (1) a high-concentration aqueous solution (20% by weight or more) of the raw material polyhydric alcohol which is the object of the present invention,
(2) Achieving a high conversion rate and (3) omitting the step of separating the catalyst from the oxidation product, etc., and avoiding catalyst deterioration caused by physical damage of the catalyst caused by stirring in the batch reactor, etc. As a result, the durability was greatly improved.

In the present invention, for example, glycerin 5
0 wt% aqueous solution as a catalyst component developed by the present inventors,
When catalytic oxidation with air or oxygen under acidic using a fixed bed reactor bismuth platinum or filled with supported catalyst obtained by supporting cerium bismuth platinum 80 mol%
Dihydroxyacetone, which is important as an intermediate for bioactive substances and amino acids, can be produced with a moderate yield.
Conventionally, dihydroxyacetone has been produced by a low-productivity fermentation method, but the method for producing dihydroxyacetone by catalytic oxidation is the world's first highly valuable production method. When a 50% by weight aqueous solution of 1,2-propylene glycol is reacted in the same manner in the presence of the same catalyst, hydroxyacetone as an intermediate material for amino acids can be produced in a yield of about 80 mol%. Furthermore, 5
A 0% by weight aqueous glycerin solution was used as a catalyst component under acidic conditions.
When catalytic oxidation is carried out using a fixed bed reactor packed with a supported catalyst supporting lithium / platinum , glyceric acid as an important intermediate is obtained in a yield of 80% or more. Malonic acid is obtained in high yield.
Thus, glycerin as polyhydric alcohol and 1,
There has never been an application of 2-propylene glycol to a liquid phase catalytic oxidation reaction under a high concentration of 50% by weight aqueous solution.
This is a feature unique to catalytic oxidation in a high-concentration catalyst system using a fixed-bed reactor.

The feature of the present invention is that not only can the oxidation reaction be carried out at a high concentration of the starting polyhydric alcohol, but also bismuth-platinum, cerium-platinum or cerium as a catalyst component.
Surprisingly, the selectivity of the compound having a carbonyl group and / or a carboxyl group can be drastically improved, and the catalyst separation step can be omitted by appropriately selecting the reaction conditions by applying bismuth / platinum. Etc.,
The method of the present invention is a very excellent production method for producing a compound having a carbonyl group and / or a carboxyl group which is important as an intermediate material of a high value-added physiologically active substance or amino acid from an inexpensive polyhydric alcohol.

In carrying out the method of the present invention using a fixed bed reactor, a known fixed bed reactor can be used. Among them, the packed length (L) of the catalyst packed column is particularly preferable.
A fixed-bed reactor having a ratio L / D of at least 1 and preferably at least 5 to the inner diameter (D) is filled with the supported catalyst of the present invention supported on a carrier having a particle size of more than 200 mesh, and And a polyhydric alcohol aqueous solution and oxygen or an oxygen-containing gas are introduced into the reaction tower in countercurrent or cocurrent so that the molar ratio between the polyhydric alcohol and the polyhydric alcohol becomes 0.1: 1 to 100: 1. In particular, a downward co-flow trickle bed system in which a polyhydric alcohol and oxygen or an oxygen-containing gas are introduced from the top of the reaction tower is effective. The oxidation product continuously flows out from the reaction tower outlet as a colorless and transparent aqueous solution by continuously flowing the reactor at 50 atm or less, preferably 10 atm or less, more preferably normal pressure. Primary hydroxyl group of polyhydric alcohol or 2
The catalytic hydroxyl group is oxidized to form various carbonyl groups and / or
Or p when producing a compound having a carboxyl group,
H, the temperature, and the molar ratio of oxygen to the polyhydric alcohol may be within the preferable ranges of the reaction conditions according to each of the above embodiments. In a fixed bed reaction, a reaction solution obtained from a sampling port attached in the height direction of the fixed bed reaction tower,
Alternatively, the pH can be controlled in a suitable range based on the measured pH of the reaction solution at the outlet of the reaction tower.

If the liquid phase flows in the reaction tower in one direction when the polyhydric alcohol aqueous solution is introduced from the top of the reaction tower, it greatly affects the oxidation reaction. It is preferable to use a liquid distributor consisting of a plurality of small holes. Furthermore, when the oxidation of the secondary hydroxyl group of the polyhydric alcohol is carried out particularly under acidic conditions, the inner wall of the reaction tower must be made of a material having acid resistance, and must not elute transition metal ions. In other words, the elution of metal ions such as iron, cobalt, nickel, chromium, and manganese, which are Group VIII elements of the periodic table, into the reaction system has a significant effect on the catalytic activity, especially in the oxidation of secondary hydroxyl groups of polyhydric alcohols. May be given. In such a case, it is preferable to use a GL reactor in which the inner wall of the reaction tower is coated with glass. Liquid HourlySpace Velocity (LHS
V) is set to 0.01 to 5, preferably 0.01 to 1.0. LHSV = Polyhydric alcohol aqueous solution supply rate [liter / hr] / catalyst filling volume [liter]

When the reaction of the present invention is carried out as a batch reaction in a stirred reactor, a thermometer, a pH meter, an air supply port,
A polyhydric alcohol aqueous solution and a supported catalyst are charged into a reactor equipped with an exhaust gas discharge port and a sampling port, and an oxygen-containing gas is supplied into the reaction solution at normal pressure under stirring, so that a catalytic oxidation reaction of the polyhydric alcohol is performed. Can be advanced. After completion of the reaction, the catalyst is removed by a known method (eg, a filtration method).
To give an aqueous solution containing a compound having a carbonyl group and / or a carboxyl group.

[0031]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. However, the seventh, eighth, and fifteenth embodiments correspond to the present invention.
It is out of the scope of Ming. The catalyst used in the following examples was prepared according to the preparation examples shown in Reference Examples. The product yield in this example is mol%. Examples 1 to 14
, A continuous oxidation reaction of a polyhydric alcohol was carried out by the following fixed bed reaction method, and in Examples 15 to 19, a batch oxidation reaction of the polyhydric alcohol was carried out by the following stirred tank reaction method.

Reference Example: The catalyst is prepared by a usual method. That is, commercially available wood-based steam activated granular activated carbon (10
67 g (0 to 40 mesh) is immersed in ion-exchanged water, and an aqueous solution in which 5 g of chloroplatinic acid and 0.6 g of bismuth chloride are uniformly dissolved is added to carry a catalyst component. 35
By performing the activation treatment with a weight% formalin aqueous solution, about 140 g of a 0.6% Bi, 3% Pt carbon catalyst having a water content of about 50% was obtained.

Fixed bed reaction method: inner diameter 20 mm, height 70c
m, and 30 g of the supported catalyst according to the present invention was filled into a reactor made of Pyrex on a dry product basis (filling length of catalyst: 60 cm).
A 50% by weight aqueous solution of a polyhydric alcohol from the top of the reactor;
Atmospheric pressure air was continuously fed into the reactor together in a downward cocurrent. Liquid hourly space velocity of polyhydric alcohol aqueous solution (LHS
V) was set to 0.08 to 0.15 hr ^-1 . The pH was measured for the reaction solution obtained from the lower part of the reactor. The obtained compound having a carbonyl group and / or a carboxyl group was analyzed using high performance liquid chromatography (HPLC). The HPLC measurement conditions are shown below.

High performance liquid chromatography: D-25
00 / L-6000 type Hitachi Ltd. Detector: L-3300 type (RI monitor) Column: C-61OS · Eluent: Distilled water 0.5 ml / min - pressure: 15 kgf / cm ² · Temperature: 60 ° C

Stirred tank reaction method: 2.5 g of a supported catalyst on a dry basis was placed in a 1-liter flask equipped with a temperature controller, a stirrer, an air supply port, an exhaust gas outlet, a sample outlet, and a pH meter; 500 g of a 10% by weight aqueous glycerin solution at 50 ° C. was charged. Then, an oxidation reaction was performed at 50 ° C. for 6 hours while supplying air at normal pressure and normal temperature at a rate of 6 liters / hour. After the supported catalyst in the obtained reaction solution was separated by filtration, a compound having a carbonyl group and / or a carboxyl group was analyzed using high performance liquid chromatography (HPLC). HPLC measurement conditions are the same as described above.

Example 1 A 50% by weight aqueous glycerin solution as a polyhydric alcohol, and a supported catalyst containing activated carbon having an ash content of 2% by weight or less and a specific surface area of 1500, 1000 or 700 m ² / g. 6% bismuth / 3% platinum was used. Reaction temperature 50 ° C., oxygen: polyhydric alcohol molar ratio 2: 1,
Under a condition of pH 4 to 2 and LHSV of 0.08 hr ^-1 , a continuous oxidation reaction was performed according to the above-mentioned fixed bed reaction method. Table 1 shows the results. It can be seen that the larger the specific surface area of the activated carbon, the higher the yield of dihydroxyacetone.

Example 2 An oxidation reaction was carried out under the same conditions as in Example 1 except that activated carbon having an ash content of 2% by weight or less and a bulk density of 170, 470 or 650 g / l was used as a catalyst carrier. . As a result, as shown in Table 1, it was found that activated carbon having a bulk density of 500 g / l or less, particularly 200 g / l or less was excellent as a carrier.

Example 3 The same procedure was carried out except that activated carbon having an ash content of 5% by weight or less and a pore volume of 0.5, 0.8, 1.1, or 1.3 ml / g was used as a catalyst carrier. An oxidation reaction was performed under the same conditions as in Example 1. As a result, as shown in Table 1, the pore volume was 0.8
It has been found that activated carbon having a ml / g or more, particularly 1.3 ml / g or more is excellent as a carrier.

Example 4 Oxidation was conducted under the same conditions as in Example 1 except that activated carbon having an ash content of 2% by weight or less and an average pore diameter of 1.8, 3.5, or 12 nm was used as a catalyst carrier. The reaction was performed. As a result, as shown in Table 1, it was found that activated carbon having an average pore diameter of 4 nm or less was particularly excellent as a carrier.

Example 5 As a catalyst carrier, the bulk density was 500 g / liter or less.
The oxidation reaction was carried out under the same conditions as in Example 1 except that the ash content was 13, 5, 2, and 1% by weight of activated carbon treated with nitric acid. As a result, as shown in Table 1, the ash content was 5% by weight.
In the following, it was found that activated carbon in an amount of not more than 2% by weight was excellent as a carrier.

[0041]

[Table 1]

Example 6 A catalyst carrier having a specific surface area of 1500 m ² / g, a pore volume of 1.3 ml / g, a bulk density of 170 g / l, an average pore diameter of 3.5 nm and an ash content of 2% by weight was used. 100-4
0.6% bismuth 3 using 0 mesh granular activated carbon
% Platinum-carbon catalyst was prepared, and 50% of 1,2-propylene glycol was used as a polyhydric alcohol having a secondary hydroxyl group.
The oxidation reaction was carried out under the same conditions as in Example 1 except that an aqueous solution was used and the liquid hourly space velocity was 0.15 h ^-1 . as a result,
Hydroxyacetone was formed in a yield of 78 mol%.

Example 7 The catalyst carrier of Example 6 was used and the catalyst component was platinum 3 alone.
% Platinum carbon catalyst was prepared, and an oxidation reaction was performed under the same conditions as in Example 1. As a result, glyceric acid was 85 mol%
Was obtained in a yield of

Example 8 An oxidation reaction was carried out under exactly the same conditions as in Example 7, except that a 20% aqueous sodium hydroxide solution was continuously introduced from the middle stage of the reaction tower at a supply rate of 15% of the molar supply rate of glycerin. After the steady state, the reaction mixture at the outlet of the reaction tower was a colorless aqueous solution having a pH of 3, and its composition was glyceric acid, oxymalonic acid, and unreacted glycerin, which were 37 mol%, 49 mol%, and 14 mol%, respectively.

Example 9 Using the same catalyst and catalyst carrier as in Example 6, the molar ratio of oxygen to glycerin was 0.5, 2, 5, 10, 30.
The oxidation reaction was carried out under the same conditions as in the above fixed bed reaction method except that the reaction was changed. Table 2 shows the results.

Example 10 In Example 9, the pH of the reaction product at the outlet of the reaction tower was adjusted to 9,
The oxidation reaction was carried out under the same conditions as in Example 9 except that the adjustment was made to be 7, 5, and 2. Table 2 shows the results.

[0047]

[Table 2]

Example 11 In Example 9, the reaction temperature was changed to -10, 0, 20, 4
The oxidation reaction was performed under the same conditions as in Example 9 except that the temperature was set to 0, 50, 60, and 80 ° C. Table 3 shows the results.

Example 12 In Example 9, as a catalyst carrier, granular carbon black manufactured by Cablack Co. (ash content: 0.5% by weight, specific surface area: 1000 m ² / g, bulk density: 300 g / l, pore volume : 0.8 ml / g, average pore diameter: 5 n
The oxidation reaction was performed under the same conditions as in Example 9 except that m) was used. As a result, the yield of dihydroxyacetone was 7
8%.

Example 13 An oxidation reaction was carried out under the same conditions as in Example 6, except that the starting polyhydric alcohol was changed to a 50% aqueous glycerin solution and the catalyst was changed to 1% Ce and 5% Pt. As a result, glyceric acid was obtained with a yield of 88%.

Example 14 An oxidation reaction was carried out under the same conditions as in Example 6 except that the raw material polyhydric alcohol was changed to a 50% aqueous glycerin solution and the catalyst was changed to 1% Ce, 1% Bi, and 5% Pt. As a result, dihydroxyacetone was obtained with a yield of 88%.

Example 15 Using a 10% aqueous glycerin solution as a raw material polyhydric alcohol and a 5% Pt carbon catalyst using the carrier of Example 6, an oxidation reaction was carried out according to the above-described stirred tank reaction method. As a result, glyceric acid and dihydroxyacetone were 33% respectively,
Obtained in 4% yield.

[0053]

[Table 3]

Example 16 An oxidation reaction was carried out under the same conditions as in Example 15 except that the catalyst was changed to 1% Bi and 5% Pt. As a result, the yields of glyceric acid and dihydroxyacetone were 5% and 25%, respectively.

Example 17 An oxidation reaction was carried out under the same conditions as in Example 15 except that the catalyst was changed to 1% Ce and 5% Pt. As a result, the yields of glyceric acid and dihydroxyacetone were 83% and 7%, respectively.

Example 18 In Example 15, the catalyst was changed to 1% Ce 1% Bi 5% Pt
The oxidation reaction was performed under the same conditions as in Example 15 except that As a result, the yields of glyceric acid and dihydroxyacetone were 15% and 74%, respectively.

Example 19 An oxidation reaction was carried out under the same conditions as in Example 16 except that the catalyst carrier was changed to asbestos, silica and alumina. Table 4 shows the results.

[0058]

[Table 4]

[0059]

According to the method for producing a compound having a carbonyl group and / or a carboxyl group of the present invention, by using a supported catalyst comprising a specific metal catalyst and a carrier,
A useful compound having a carbonyl group and / or a carboxyl group can be produced at a high concentration and a high yield from inexpensive raw materials. In particular, by using a fixed-bed reactor, it is possible to perform a reaction in a high-concentration system in which the concentration of a polyhydric alcohol aqueous solution is 20% by weight or more, and the concentration of the obtained compound having a carbonyl group and / or a carboxyl group is dramatically increased. And a high productivity process such as elimination of the catalyst separation step is possible, and the ripple effect is great.

[Brief description of the drawings]

FIG. 1 is a diagram showing an oxidation pathway of glycerin.

FIG. 2 is a diagram showing an oxidation pathway of 1,2-propylene glycol.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07B 61/00 300 C07C 49/17 A C07C 45/37 51/245 49/17 59/10 51/245 B01J 23/56 301X 59 Reference: JP-A-55-28989 (JP, A) JP-A-2-17148 (JP, A) JP-A-3-151344 (JP, A) JP-A-52-116415 (JP, A) JP-A-1-3111045 (JP, A) JP-A-55-69596 (JP, A) JP-A-60-92239 (JP, A) JP-A-55-7230 (JP, A) JP-A-58-30335 (JP, A) JP-A-2-51411 (JP, A) JP-A-59-66351 (JP, A) JP-A-63-211251 (JP, A) Japan Society for Carbon Materials, Activated Carbon-Basic And Application, Japan, Kodansha Co., Ltd., September 1, 1978, 382, 384, 386 Editorial Board of the Chemical Dictionary Chemical Encyclopedia, Japan, Kyoritsu Shuppan Co., Ltd., January 10, 1979, Vol. 2 (pocket edition), 437-438, the field was terms of active charcoal (58) Survey (Int.Cl. ^7, DB name) B01J 21/00-38/74 C07B 41/06-41/08 C07C 45/37 C07C 49/17 C07C 51/245 C07C 59/10

Claims (1)

(57) [Claims] (1) Catalyst componentAs bismuth / platinum and serium
Platinum or cerium bismuth platinumAnd the following
Has at least one physical property selected from (a) to (d)
Activated carbon having an ash content of 15% by weight or less and / or
Catalyst supported on carbon black carrierFilling
Glycerin or 1,2-
Propylene glycolToAir or mixed gas of oxygen and nitrogen
soA carbonyl group characterized by catalytic oxidation and / or
Is a method for producing a compound having a carboxyl group.  Physical properties of carrier: (a) activated carbon and / or carbon black has specific surface area
500m^Two/ G or more (b) The bulk density of activated carbon and / or carbon black is 8
00g / liter or less (c) The pore volume of activated carbon and / or carbon black is
0.3 ml / g or more (d) Average pore diameter of activated carbon and / or carbon black
Diameter less than 20nm