JPS59161328A - Preparation of hydroxycarbonic acid derivative - Google Patents

Abstract

PURPOSE:To obtain the titled substance, by reacting an aliphatic aldehyde with CO in the presence of a solid acid catalyst having high activity, improved heat resistance, and long life, containing a crsytalline aluminosilicate having specific angles of diffraction of X-ray and a transition metal. CONSTITUTION:An liaphatic aldehyde (preferably formaldehyde) is reacted with CO in a reactive solvent such as acetic acid to give the titled substance. In the reaction, a crystalline alumino-silicate having angles of diffraction of X-ray at least at 7.9 deg.+ or -0.3 deg., 8.8 deg.+ or -0.3 deg., 23.2 deg.+ or -0.3 deg., 23.7 deg.+ or -0.3 deg. and 24.4 deg.+ or -0.3 deg. and a transi tion metal (preferably salt or halide of copper or silver) are added to the reaction system. FZ-1, ZSM group zeolite, etc. is used as the crystalline aluminosilicate, it and the transition metal are added separately to the reaction system, or they are integrated by impregnation, adhesion, ion exchange, etc. and added to the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hydroxycarboxylic acid derivatives,
More specifically, the present invention relates to a method for producing a hydroxycarboxylic acid derivative by reacting an aliphatic aldehyde with carbon monoxide.

Hydroxycarboxylic acids such as glycolic acid and lactic acid are important compounds. For example, glycolic acid is a useful substance as a chemical cleaning agent, a raw material for organic synthesis, a polymer raw material, and a polymer additive.

A method for producing glycolic acid among hydroxycarboxylic acids using formaldehyde as a starting material is already known. Using mineral acids such as sulfuric acid, phosphoric acid and hydrochloric acid as a catalyst,
A method for producing glycolic acid in one step by reacting formaldehyde, water and carbon monoxide under high pressure (for example, U.S. Pat. Glycolic acid is produced in one step by reacting formaldehyde, water and carbon monoxide under normal pressure (for example, U.S. Pat. No. 3,754,028 and U.S. Pat. No. 3,911).
oo No. 3, and % Shiroan No. 51-13719) method. These methods have problems such as requiring complicated operations to separate glycolic acid from the reaction solution and requiring an acid-resistant reactor because the catalyst is a strong acid solution. , the i7 could not be called an industrially superior method.

Additionally, there is a method known as the Carpentry Trial Method or the Soma Method (Japanese Unexamined Patent Publication No. 57-46934), in which the synthesis of glycolic acid such as formaldehyde (formaldehyde≠) using a sulfuric acid catalyst, which conventionally required high pressure, was It is noteworthy that by adding Vζ more silver salt to the system, it is possible to reduce the reaction pressure to normal pressure. However, this method still suffers from the drawbacks of using concentrated sulfuric acid, and is also a two-step reaction, requiring large stoichiometric amounts of copper and silver, making it difficult to industrialize. Contains elements that may be a hindrance.

As a method to avoid the drawbacks of these methods, a method has recently been proposed for the production of glycolic acid derivatives using ion exchange resins, acidic clays, and strongly acidic insoluble solids such as zeolites as catalysts (Japanese Patent Publication No. 53-37332).
No.) and a method using a heteropolyacid as a catalyst (Japanese Unexamined Patent Publication No. 5
No. 6-79638 and No. 57-32236) are known. However, in these methods, a strongly acidic ion exchange resin with low heat resistance is used, and the reaction temperature must be strictly maintained. Furthermore, the strongly acidic ion exchange resin has serious problems such as deterioration in an organic solvent in a relatively short period of time, making it unsuitable for industrial production. When using zeolite as a catalyst, the natural mordenite used itself has low catalytic activity and short life, making it unsuitable for use as a practical catalyst. There is.

The present inventors have repeatedly searched for solid catalysts for the production of hydroxycarboxylic acids that have high catalytic activity, heat resistance, easy handling, and long lifetime, and have discovered the structure of crystalline aluminosilicate. We have obtained new knowledge that the catalytic activity is completely different depending on the type, and the life is significantly different depending on the type, and we have already applied for a patent (patent application No. S6-143622).

As a result of further intensive studies on this method, the present inventors have found that the yield of the product, the glycolic acid derivative, can be improved by further coexisting a transition metal compound such as copper in the reaction system. Moreover, we have obtained a new finding that the reaction pressure can be lowered, and based on this new finding, we have arrived at the present invention.

The object of the present invention is to use crystalline aluminosilicate, which is a strongly acidic solid acid melting medium that has high catalytic activity, high heat resistance, easy handling and reaction operation, and has a long life, to The object of the present invention is to provide a method for producing acid derivatives industrially and more advantageously at relatively low pressure.

That is, the present invention provides a method for producing a hydroxycarboxylic acid derivative by reacting an aliphatic aldehyde and carbon monoxide in the presence of a reaction medium.
,3','R,R'' ±O,3° ,23.2°±
0.3-', 23.7°±0.3″ and 24.4°±
This is a method for producing a hydroxycarboxylic acid derivative, characterized in that a crystalline aluminosilicate having an X-ray diffraction angle of 0.3° and a transition metal coexist in a reaction system.

In the present invention, the reaction type can be any of 71 types, such as seed type, winter type, continuous type, and batch type. can also be adopted.

The crystalline aluminosilicate used in the present invention has high activity for producing hydroxycarboxylic acid derivatives, and has 4.
Not only the type but also the industrially advantageous continuous type can provide a satisfactory reaction rate.

The crystalline aluminosilicate used in the present invention means a composition containing at least sulfuric acid, oxygen, and aluminum and having a specific cage structure, and may further contain other elements. Note that the aluminum content of the crystalline aluminosilicate may be as small as an impurity.

As other elements, Group I metals such as boron are also suitable.

The crystalline aluminosilicate used in the present invention is xM
+ In the diffraction diagram, the X-ray diffraction angle (2θ) is at least 7.
9°±0.3L', R,R°±0.3°, 23.2
°±0.3°, 23.7Ll±0.3° and 24.
Any composition may be used as long as it exhibits diffraction peaks in each of the five regions of 4°±0.3°, and other peaks within this range may be maintained.

The X-ray diffraction pattern of this crystalline aluminosilicate was obtained by measuring copper using α radiation using a standard powder diffraction method.

Representative examples of such crystalline aluminosilicate include FZ-1 (Japanese Patent Publication No. 56-1520) and ZSM-5 (Japanese Patent Publication No. 53-11'1521).
Examples include ZSM group zeolites represented by No. The X-ray diffraction patterns of FZ-1 and ZSM-5 are as follows. That is, J”Z
-I Z S 4-57.9 7.9
6 R, RFl, Fl4 17.7 23.10 23.2 24. UU 23.7 24.45 23 , 9 24 , 4 The crystalline aluminosilicate used in the present invention acts as an acidic catalyst in the reaction system.

The crystalline aluminosilicate is then subjected to various activation treatments. For example, FZ-1 type crystalline aluminosilicate is fired, refluxed with an aqueous hydrochloric acid solution, dried, and further ion-exchanged by a conventional method, or fired again without ion-exchange to activate it. Also ZS
After firing, the M group zeolite is activated by refluxing it with an aqueous ammonium chloride solution, followed by drying and firing.

The transition metal used in the present invention may be a transition metal compound that reacts with carbon oxide under pressure with carbon oxide to provide a soluble compound in the reaction solution.

In practice, group IB metals such as copper and silver, ta!
4 iron, cobalt, nickel, ruthenium.

Group I metals such as rhodium, palladium and platinum, and IYA, VA, VIA and A group metals such as titanium, vanadium, chromium, manganese, molybdenum, tungsten and zirconium, also known as early transition metals, are commonly used. I can do it. Compounds of these metals include organic acid salts such as sulfates and benzoates, halides such as butyrates, chlorides, and bromides, hydroxides, and oxides, as well as ammine complexes, vermilion cyano complexes, Aqua complexes, and so-called unirna-type complexes such as ethylenediamine complexes, as well as acetylacetonates and alkoxides.

As cyclobentadiend, an organometallic compound having particles of tertiary phosphorus, arsenic, bipyridyl, etc., or a compound in the form of a mixture of oxine acetylacetonate, n, etc. is used.

Among these, salts and halides of copper and silver are preferably used in practice.

(1) Impregnating and adhering a transition metal to the activated crystalline aluminosilicate for use; (11) ionizing the transition metal to the crystalline aluminosilicate; Crystalline aluminosilicate (Japanese Patent Application No. 109869/1986) containing a transition metal obtained by the presence of a transition metal during hydrothermal synthesis is used. 4 silicate and transition metal
~ It does not prevent it from being embodied, supplied, and used.

The aliphatic aldehyde used in the present invention can be used regardless of the number of carbon atoms and functional groups as long as it can be dissolved and dispersed in the reaction medium. Usually, formaldehyde, acetaldehyde, propionaldehyde, etc. are used, and formaldehyde is preferably used. When formaldehyde is used as the aliphatic aldehyde, paraformaldehyde, α-polyoxymethylene, trioxane, tetraoxane and formalin can also be used as raw materials in addition to formaldehyde. However, in the case of formalin, the formaldehyde content is 3
It is preferable to use 7% or more.

The carbon monoxide used in the present invention is not only high-purity carbon oxide, but also carbon monoxide mixed with nitrogen, hydrogen, carbon dioxide, etc. that do not affect this reaction.

The reaction medium used in the present invention is not particularly limited, but typically includes, for example, carboxylic acids such as acetic acid and propionic acid, halogenated hydrocarbons such as dichloromethane, esters of ethyl acetate, methanol, and ethanol. Alcohol etc. are used. Carboxylic acids such as acetic acid and propionic acid are practically preferred.

When producing a hydroxycarboxylic acid as the target substance, water must be present as a reaction medium in the reaction system at the initial stage of the reaction. The water contained in the raw material aldehyde and the reaction medium acts as water as the reaction medium, but it can be replenished if water is insufficient.

The hydroxycarboxylic acid derivatives produced in the present invention are represented by the general formula % (wherein R is a hydrogen atom or an alkyl group, R1 is a hydroxy group or an alkoxy group, and l (2 is a hydroxy group or an acyloxy group). It is a compound that

R is determined by the type of aliphatic aldehyde used as the raw material. For example, when formaldehyde is used, it is hydrogen, and when acetaldehyde is used, it is methyl.

R1 and R2 vary depending on the type of raw material aliphatic aldehyde and reaction medium. That is, when water is used, R
Both 1 and R2 are hydroxy groups, but when alcohol is used, RI and R2 become hydroxy groups or alkoxy groups. For example, when methanol is used, RI: methoxy group; or acyloxy group R2 becomes an acyloxy group or a hydroxy group.For example, when acetic acid is used, RI
: hydroxy group, R2: acetoxy group, R1: acetoxy group, R2: hydroxy group, or both R'+R2 are acetoxy groups. When using 16 propionic acid, R1:
Hydroxy group, R2: probionoxy group or I (1:
Propionoxy group, R2: hydroxy group or R1, R
Both of them become globionoxy groups.

The composition and amount of the hydrocarboxylic acid derivatives produced from the raw material aliphatic aldehyde and the reaction medium vary depending on the reaction conditions. Table 1 lists specific examples of the hydroxycarboxylic acid derivatives that are usually produced, although it cannot be said in general. Shown below.

Table 1 Thus, the components of the reaction medium are also the reactants.

Conditions such as temperature and pressure in the reaction of the present invention may be conventional methods.

For example, the reaction temperature is usually 10() to 300°C,
A temperature range of 180° C. to 250° C. is preferable for exhibiting high activity of the catalyst.

The reaction pressure may be normal pressure as long as the amount of carbon monoxide required for the reaction is supplied, but it is preferably 100 kg/CTfL.
The above is preferable.

In the present invention, the crystalline aluminosilicate used can be mechanically separated and recovered without substantial loss after the reaction, so it is possible to maintain effective contact with the raw material aliphatic aldehyde.
It is preferable to use as much catalyst as possible. However, in the present invention, the catalyst can exhibit sufficient activity in an amount corresponding to a low hydrogen ion concentration of about 0.5 mmol per mole of aliphatic aldehyde. Such high activity is very advantageous when conducting a continuous reaction.

The amount of transition metal compound used in the present invention may be any amount that can entrain carbon monoxide in the gas phase to the active site of the crystalline aluminosilicate. 1 to 100 in molar ratio to equivalent weight
0, preferably 50 to 200.

Unlike conventional methods, the reaction type may be not only a seed type but also a tower type, continuous type, batch type, etc.

In the present invention, the crystalline aluminosilicate used has high heat resistance, so handling and reaction operations are easy, and the catalytic activity is high, so hydroxycarboxylic acid derivatives can be obtained with good space-time yield even at low pressure. Moreover, it is not affected by solvents and can maintain high catalytic activity for a long period of time, so it can be used for a long period of time. Furthermore, since crystalline aluminosilicate can be easily separated and recovered from the reaction solution, it can be recycled and reused.

The present invention will be explained in more detail with reference to Examples.

Example 1 Trioxane 8.58F1. Acetic acid 20. li' and activated ZSM- with a silica/alumina ratio of about 50.
5 Crystalline aluminosilicate (X-ray pattern is Z
2g (same as the X-ray pattern of SM-5) and 0.4g of cupric acetate hydrate, and 150kg/carbon oxide.
d to maintain the temperature inside the reactor at 200°C.
A time reaction was performed.

The products in the reaction product liquid A were identified and quantified using gas chromatography. As a result, the conversion rate of formaldehyde was 9
6% f, and acetoxyacetic acid was obtained as a product in a yield of 88% (selectivity 92%) based on formaldehyde.

In addition, methyl glycolate has a yield of 0.3% (selectivity 0.3%), methyl acetoxyacetate has a yield of 4.5% (selectivity 5%), and acetic acid acetoxyacetic anhydride has a yield of 0.9%. (
It was obtained with a selectivity of 0.9%).

Comparative Example 1 The same procedure as in Example 1 was carried out except that cupric acetate hydrate was not added to the system, and the formaldehyde conversion rate was 56%.
The formaldehyde-based yields of acetoxyacetic acid, methyl acetoxyacetate, and acetate-acetoxyacetic anhydride are 51% (selectivity 91%), 3.1'1% (selectivity 7%), and 0.5% (selectivity), respectively. rate of 0.9%).

Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that no crystalline aluminosilicate was added to the system. No reaction occurred at all and no hydroxycarboxylic acid derivative was detected in the reaction solution.

Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Substitute Kazuyoshi Nagano

Claims (1)

[Claims] A method for producing a hydroxycarboxylic acid by reacting an aliphatic aldehyde and carbon monoxide in the presence of a reaction medium, comprising at least 7.9°±O03°+8.8°±0.3
°, 23.2°±0.3°. 23.7°±0.3° and 24°4°±O,3°X
A method for producing a hydroxycarboxylic acid derivative, characterized in that a crystalline aluminosilicate having a linear diffraction angle and a transition metal coexist in a reaction system.