JPH03294243A - Production of organic carboxylic acid ester - Google Patents

Abstract

PURPOSE:To produce the title compound useful as a raw material for solvent and various kinds of spices extremely industrially and advantageously from an organic carboxylic acid and an alcohol or an olefin by using clay minerals containing a zirconium compound as a catalyst. CONSTITUTION:In producing a carboxylic acid ester from an organic carboxylic acid and an alcohol or an olefin, clay minerals (especially preferably montmorillonite) containing a zirconium compound (e.g. zirconium oxide or zirconium hydroxide) are used as a catalyst and the reaction is carried out. By this method, a reactor is not corroded with the organic carboxylic acid ester and the organic carboxylic acid ester can be obtained at high esterification rate. The prepared organic carboxylic acid ester is readily recovered.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing an organic carboxylic acid ester.

[Prior Art and Problems to be Solved by the Invention] Organic carboxylic acid esters are widely used as organic solvents and as raw materials for various fragrances.

As a method for producing this type of organic carboxylic acid ester, a method is known in which an organic carboxylic acid and an alcohol are reacted in the presence of a sulfuric acid catalyst (see Japanese Patent Publications No. 45-14529 and Japanese Patent Publication No. 48-30257). ). However, this method uses sulfuric acid, which is a corrosive liquid, as a catalyst, so it not only tends to corrode the metal reactor, but also has the disadvantage that it is not easy to recover the organic carboxylic acid ester product.

Also, Japanese Patent Publication No. 61-21543 and U.S. Patent Nos. 3 and 7
No. 76.947 discloses a method for producing an organic carboxylic acid ester by reacting an organic carboxylic acid and an alcohol using an ion exchange resin as a catalyst. This method has an advantage over the method using a sulfuric acid catalyst in that it is easier to recover the organic carboxylic acid ester product, but the ion exchange resin used as a catalyst is expensive and the ion exchange resin contains There is a drawback that sulfone groups and the like leak out during the reaction and tend to corrode the metal reactor.

Furthermore, Japanese Patent Publication No. 64-4815 describes a method for producing organic carboxylic acid esters from organic carboxylic acids and alcohols or olefins using hydrogen ion-exchanged bentonite obtained by contacting sodium bentonite with mineral acids as a catalyst. It has been disclosed and also
Publication No. 060 discloses that polyvalent cation (chromium, aluminum, cobalt, nickel, iron, copper, or vanadium ions) exchanged bentonite obtained by cation-exchanging the sodium ions of sodium bentonite is used as a catalyst to produce an organic carboxylic acid. A method for producing an organic carboxylic acid ester from an alcohol or an olefin is disclosed. The methods described in these patent publications have the advantage that the product organic carboxylic acid ester can be easily recovered and the catalyst is cheaper than the above-mentioned ion exchange resin catalyst, but the activity of the catalyst used is The drawback is that the esterification rate is extremely low.

Therefore, it is an object of the present invention to overcome the drawbacks of the conventional methods described above, to be able to obtain organic carboxylic acid esters at a high esterification rate without corroding the metal reactor, and to The object of the present invention is to provide an extremely industrial method for producing an organic carboxylic acid ester, which allows the ester to be easily recovered.

[Means for Solving the Problems] The present inventors have discovered that when a clay mineral incorporating a zirconium compound is used as a catalyst when producing an organic carboxylic acid ester from an organic carboxylic acid and an alcohol or an olefin, (1) Unlike when using conventional esterification catalysts such as sulfuric acid or ion exchange resins, there is no corrosion of the metal reactor. (11) Using conventional esterification catalysts such as hydrogen ion exchange bentonite or polyvalent cation exchange bentonite The esterification rate is significantly higher than when using sulfuric acid, which is a conventional esterification catalyst, and the recovery of the reaction product is easy. I found it.

The present invention has been made based on the above findings, and the method for producing an organic carboxylic acid ester of the present invention involves reacting an organic carboxylic acid with an alcohol or an olefin in the presence of a clay mineral incorporating a zirconium compound. It is characterized by

The raw materials used in the method for producing an organic carboxylic acid ester of the present invention are an organic carboxylic acid and an alcohol or an olefin.

The organic carboxylic acid that is the raw material for the former has 1 to 1 carbon atoms.
18 carboxylic acids are preferred, examples of which include the following.

(a) lower saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, (b) valeric acid, caproic acid, enanthic acid, caprylic acid,
Intermediate saturated fatty acids such as pelargonic acid, capric acid, undecylic acid, lauric acid (C) tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid,
Higher saturated fatty acids such as stearic acid (d) Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid (e) Unsaturated fatty acids such as acrylic acid, methacrylic acid, and crotonic acid (f) Benzoic acid, As the raw material for the reaction with the organic carboxylic acid and aromatic acid such as phthalic acid, alcohol or olefin is used as described above.

The alcohol is preferably an alcohol having 1 to 20 carbon atoms, examples of which include methanol, ethanol, propatools, butanols, pentanols, hexanols, heptatools, octatools, nonanols, and decanols. , undecanols, dodecanols, etc.

Further, as the olefin, an olefin having 2 to 20 carbon atoms is preferable, and examples thereof include ethylene, propylene,
Examples include butenes, pentenes, hexenes, and cyclohexene.

In the method for producing an organic carboxylic acid ester of the present invention, the organic carboxylic acid and alcohol or olefin are reacted in the presence of a clay mineral incorporating a zirconium compound.

A clay mineral incorporating a zirconium compound, which is used as a catalyst, is prepared, for example, through the following steps (a) to (b).

(a) Water is added to zirconium chloride, sulfate or alkoxide and mixed to form a polycation represented by the formula % formula %], and aged at a temperature of room temperature to 100°C for 0 hours to several weeks to produce the above Stabilize the polycation (Here, the ripening time of 0 hours means that no ripening is required. The same applies hereinafter).

(b) Next, add clay minerals in powder or slurry form,
After stirring for 5 minutes to several weeks at a temperature of room temperature to 100°C to insert the polycation between the layers of the clay mineral, the polycation is filtered and washed with water, alcohol, etc.
After stabilizing the pillars (polycations) by aging them at a temperature of 00° C. for 0 hours to several weeks, they are filtered, freeze-dried, or washed with alcohol and then air-dried to obtain clay minerals incorporating zirconium compounds.

Incorporated zirconium compounds include zirconium oxide, zirconium hydroxide, partially dehydrated zirconium hydroxide, and mixtures thereof.

In addition, clay minerals include montmorillonite, saponite, bentonite, beidellite, anthropotronite, porconscoreite, sauconite, stevensite,
Although phyllosilicate minerals and the like are used, it is particularly preferable to use montmorillonite.

When the clay mineral incorporating the zirconium compound obtained as described above is used as a catalyst, the amount is 0.001 to 2 kg per 1 kg of raw materials (organic carboxylic acid and alcohol or olefin) in the case of a batch reaction. It is preferable to do so. The reason for this is that if the CL is less than 1 kg, the effect as a catalyst is small, while if it exceeds 2 kg, no improvement in the esterification rate can be expected, which is uneconomical. Particularly preferred amount of catalyst is 0.03 to 0.05 kg
It is.

Further, in the case of a continuous reaction, the amount of catalyst is preferably 0.01 to 50/hr in terms of WH8V (weight hourly space velocity).

The reason for this is that if it is less than 0.01/hr, the effect as a catalyst will be small, while if it exceeds 50/hr, no improvement in the esterification rate can be expected, which is uneconomical. A particularly preferable amount of catalyst is 0.1 to 10/hr.

In order to shape the catalyst into a desired shape, an inorganic binder such as kaolin, silica, alumina, etc. can be used as the binder. Preferably, the amount of binder is less than 80% by weight relative to the catalyst.

The catalyst is prepared in such a way that the contact area between the raw material organic carboxylic acid and the alcohol or olefin is large, for example,
Those having a surface area of 00 to 800 rrl'/g are preferred. The shape of the catalyst is not particularly limited, but shapes such as powder, beads, and pellets are preferred. Also, the catalyst do
. 1 (interlayer distance) is preferably 14 to 28 people.

When reacting an organic carboxylic acid with an alcohol or an olefin using the above catalyst, the reaction temperature is preferably 50 to 200°C, although it depends on the type of raw materials.

The reaction pressure is preferably 0 to 300 kg/cjG, particularly preferably 10 to 150 kg/cjG. The reaction method may be a batch method, a semi-continuous method, or a continuous method.

When a highly viscous substance or a solid substance is used as a raw material, particularly an organic carboxylic acid, the reaction can proceed smoothly by using a diluent that dissolves the raw material and does not react with the raw material. Such diluents include 1
．． Examples include 4-dioxane. However, even when a highly viscous or solid organic carboxylic acid is used as the raw material, the above-mentioned diluent is not necessary when a low viscosity alcohol is used as the other raw material alcohol. Furthermore, it goes without saying that the above-mentioned diluent is not required even when a low-viscosity organic carboxylic acid and a low-viscosity alcohol are used as raw materials.

According to the method for producing an organic carboxylic acid of the present invention, since the clay mineral incorporating a zirconium compound, which is the catalyst used, has high catalytic activity, it is possible to obtain an organic carboxylic acid ester in a high yield at a high esterification rate. can. Further, even when a metal reactor is used as the reactor, corrosion does not occur in the reactor.

The obtained organic carboxylic acid ester is recovered as follows. That is, after the reaction is completed, the clay mineral catalyst incorporating the zirconium compound is removed by filtration, and the filtrate is dehydrated and directly distilled to isolate the organic carboxylic acid ester product. In this manner, the organic carboxylic acid ester product can be recovered with extremely simple operations.

[Example] The present invention will be further described below with reference to catalyst preparation examples and examples.

Catalyst Preparation Example 1 (Preparation Example of Montmorillonite Catalyst Incorporating Zirconium Compound) 2 g of ZrOCl2 '8H2032 was dissolved in 11 pure water. After sufficient stirring, 10 g of sodium montmorillonite was added as a powder at 80° C., and the mixture was stirred and mixed for 1.5 hours to fully disperse the mixture. Thereafter, the solution was filtered, washed with pure water and alcohol, and then air-dried and fired at 120° C. for 15 hours. The surface area of the montmorillonite catalyst incorporating the obtained zirconium compound (denoted as Zr-montmorillonite (A) in Table 1) is 216g/m.
g, average d0°1 was 16.6 people.

Catalyst Preparation Example 2 (Preparation Example of Montmorillonite Catalyst Incorporating Zirconium Compound) Catalyst Preparation Example 1 except that the calcination was performed at 150°C for 2 hours.
A montmorillonite catalyst incorporating a zirconium compound (denoted as Zr-montmorillonite (B) in Table 1) was obtained in the same manner as above. The surface area of the obtained catalyst is 250
rrr/g, average d. There were 15 office workers.

Catalyst Preparation Example 3 (Preparation Example of Hydrogen Ion Exchange Montmorillonite Catalyst) 2 g of sodium montmorillonite was added as a powder to 200 ml of INNH4Ci aqueous solution, and the mixture was stirred and mixed day and night to be sufficiently dispersed. The solution was then filtered, washed with pure water and alcohol, air-dried at 120°C, and
It was calcined at 0° C. (in a nitrogen stream) to obtain a hydrogen ion exchange montmorillonite catalyst (denoted as H-montmorillonite in Table 1).

Catalyst Preparation Example 4 (Preparation Example of Aluminum Ion Exchange Montmorillonite Catalyst) 20121 g of A I C13.6H was dissolved in 11 of pure water, and 40 g of granular NaOH was added. The resulting aluminum oxide was dissolved at 100°C, and after the liquid became transparent, it was cooled to room temperature. To this solution was added 100 g of sodium montmorillonite as a powder, and the mixture was stirred and mixed for 10 minutes to sufficiently disperse the mixture. After this, the mixture was allowed to stand at room temperature for 10 hours. Then, the solution was filtered, washed with pure water and alcohol, and then air-dried at 120°C to obtain an aluminum ion-exchanged montmorillonite catalyst (denoted as AI-montmorillonite in Table 1).

Catalyst Preparation Example 5 (Preparation Example of Chromium Ion-Exchanged Montmorillonite Catalyst) 1 g of Cr(NO3) 3'' 9H2040 was dissolved in pure water 11. After stirring thoroughly, it was aged at 100°C for 2 hours and cooled to room temperature. 5 g of sodium montmorillonite was added as a powder to this solution, and stirred and mixed for 10 minutes to fully disperse the solution.After this, it was left standing at room temperature for 10 hours.Then, the solution was filtered, and diluted with pure water and alcohol. After washing, air drying at 120°C and converting the chromium ion-exchanged montmorillonite catalyst (C in Table 1).
r-montmorillonite) was obtained.

Example 1 A 100 ml flask was charged with 2.7 g of acetic acid, 9.9 g of n-butanol, and montmorillonite catalyst (Zr-montmorillonite (A)) Ig incorporating the zirconium compound obtained in Preparation Example 1, and heated to 50°C. and acetic acid and n
- Butyl acetate was obtained by reacting with butanol. Samples were taken periodically and the amount of produced ester was determined by gas chromatography. In the graph showing the relationship between reaction time and butyl acetate concentration, the initial slope was taken as the butyl acetate production rate. The results are shown in Table 1.

Example 2 A montmorillonite catalyst incorporating the zirconium compound obtained in Preparation Example 2 (Zr-montmorillonite) was used as a catalyst.
The reaction was carried out under the same conditions as in Example 1 except that B)) was used, and the butyl acetate production rate was determined. The results are shown in Table 1.

Comparative Example 1 Example 1 except that the catalyst was replaced with the hydrogen ion-exchanged montmorillonite (H-montmorillonite) obtained in Preparation Example 3.
The reaction was carried out under the same conditions as above, and the butyl acetate production rate was determined. The results are shown in Table 1.

Comparative Example 2 A reaction was carried out under the same conditions as in Example 1, except that the catalyst was changed to the aluminum ion-exchanged montmorillonite (CA1-montmorillonite) obtained in Preparation Example 4, and the butyl acetate production rate was determined. The results are shown in Table 1.

Comparative Example 3 A reaction was carried out under the same conditions as in Example 1, except that the catalyst was changed to chromium ion-exchanged montmorillonite (Cr-montmorillonite) obtained in Preparation Example 5, and the butyl acetate production rate was determined. The results are shown in Table 1.

Comparative Example 4 The catalyst was ion exchange resin Nafion H (manufactured by DuPont, N
The reaction was carried out under the same conditions as in Example 1 except that R50) was used, and the butyl acetate production rate was determined. The results are shown in Table 1.

(Left below) Table 1 shows that in Examples 1 and 2 using a montmorillonite catalyst incorporating a zirconium compound, the butyl acetate production rate was approximately 25% higher than in Comparative Examples 1 to 3 using a conventional montmorillonite catalyst. It has been revealed that this is extremely high, approximately 500 times. It was also revealed that the butyl acetate production rate was approximately twice that of Comparative Example 4 using Nafion H, which is an expensive ion exchange resin. Furthermore, in Examples 1 and 2, it was confirmed that the product, butyl acetate, could be recovered extremely easily after the reaction was completed. Furthermore, no corrosion was observed when a metal reactor such as 5US316 was used as the reactor.

[Effects of the Invention] As described above, according to the present invention, an organic carboxylic acid ester can be obtained at a high esterification rate without corroding the reactor, and the obtained organic carboxylic acid ester can be easily processed. A highly industrial method for producing organic carboxylic acid esters that can be recovered has been provided.

Claims (2)

[Claims] (1) A method for producing an organic carboxylic acid ester, which comprises reacting an organic carboxylic acid with an alcohol or an olefin in the presence of a clay mineral incorporating a zirconium compound. (2) Claim (1) wherein the clay mineral is montmorillonite.
).