JPH08183766A - Method for producing aqueous peracetic acid solution - Google Patents

Abstract

PURPOSE: To obtain an aqueous peracetic acid solution useful for a breaching agent for nylon fabrics, etc., a bactericide, an epoxidating agent, etc., without using an aqueous hydrogen peroxide solution of a high concentration and at an industrially low cost by reacting a specific amount of acetic anhydride with the aqueous hydrogen peroxide solution. CONSTITUTION: This method for producing an aqueous peracetic acid solution comprises reacting (A) an aqueous hydrogen peroxide solution with (B) acetic anhydride with an amount of a lower molarity than that of water. Furthermore, preferably the concentration of the component (A) is 50-70wt.%, and the reaction is carried out by adding the component (B) into a reaction vessel containing the component (A) and using 0.2-2.0wt. % acid catalyst such as sulfuric acid or phosphoric acid and 0.01-2.0wt.% metallic ion sequestering agent such as an aminocarboxylic acid as a stabilizer based on the total amount of the reaction mixture at 0-90 deg.C, especially 10-50 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aqueous solution of peracetic acid. The aqueous solution of peracetic acid produced by the present invention is
It is used as a bleaching agent for fibers such as nylon fabric, a low temperature polymerization catalyst for polyester type resins, a bactericidal agent, an epoxidizing agent, and an oxidizing agent for organic synthesis such as a raw material for producing polymer monomers.

[0002]

2. Description of the Related Art As a method for producing an aqueous solution of peracetic acid, a method is known in which acetic acid is added to hydrogen peroxide and reacted. In this method, in order to obtain a high-concentration aqueous solution of peracetic acid, it is necessary to use a high-concentration aqueous solution of hydrogen peroxide of about 90% by weight as hydrogen peroxide. However, it is inconvenient that a high-concentration aqueous hydrogen peroxide solution is difficult to obtain and difficult to handle.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for industrially producing an aqueous solution of peracetic acid at low cost without using a highly concentrated aqueous solution of hydrogen peroxide.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above-mentioned problems. As a result, acetic anhydride was added to an aqueous hydrogen peroxide solution containing an excess molar amount of water to cause a reaction. The inventors have found that an aqueous acetic acid solution is economically produced and completed the present invention.

The concentration of the hydrogen peroxide aqueous solution used in the present invention is not limited, but a 10 to 90 wt% hydrogen peroxide aqueous solution is preferably used, and a 30 to 80 wt% hydrogen peroxide aqueous solution is more preferable. Especially, 50-70, which is easy to obtain and easy to handle
It is preferable to use an aqueous solution of hydrogen peroxide of wt%,
As a result, a highly concentrated aqueous solution of peracetic acid of 30% by weight or more can be obtained with a high hydrogen peroxide selectivity.

A feature of the present invention is that acetic anhydride is used in place of acetic acid, and that when acetic anhydride is reacted with an aqueous solution of hydrogen peroxide, a molar amount of acetic anhydride that is less than that of water is used. In point.

That is, by using acetic anhydride instead of acetic acid, and by using acetic anhydride in an amount less than that of water when reacting acetic anhydride with an aqueous hydrogen peroxide solution, It is possible to obtain a high-concentration aqueous solution of peracetic acid without using a high-concentration aqueous solution of hydrogen peroxide.

The present invention can be implemented in a continuous mode. At that time, the mixing molar ratio of acetic anhydride and water in the hydrogen peroxide solution is 1
It is less than 0.5, preferably 0.5 to 0.99.

The present invention can also be implemented in a batch system. Particularly in a batch system, acetic anhydride is added to a reaction vessel containing an aqueous hydrogen peroxide solution with stirring so that the number of moles of acetic anhydride is always lower than the number of moles of water in the aqueous hydrogen peroxide solution. On the contrary, if hydrogen peroxide solution was added to the reaction vessel containing acetic anhydride, the number of moles of acetic anhydride in the reaction system would exceed the number of moles of water in the hydrogen peroxide solution in the initial addition. However, the selectivity of the reaction that produces peracetic acid decreases. The final mixing molar ratio of acetic anhydride and water in the hydrogen peroxide solution is less than 1, preferably 0.5 to 0.99.

The reaction temperature in the present invention is not limited,
The temperature is preferably 0 to 90 ° C, more preferably 10 to 50 ° C.
The reaction time is 1 hour or longer, preferably 2 to 48 hours.

In the present invention, it is preferable to use an acid as a catalyst. As the reaction catalyst, an acid having an acid dissociation index (pKa) of 4.6 or more can be used regardless of an organic acid, an inorganic acid, or a solid acid,
Although the amount used is not limited, it is preferable to use sulfuric acid or phosphoric acid in an amount of 0.2 to 2.0% by weight based on the total amount of the reaction mixture in view of easy handling and economy. If necessary, 0.001 of a sequestering agent such as aminocarboxylic acid, phosphoric acid, condensed phosphoric acid, or organic phosphonic acid is used as a stabilizer.
It is also preferable to add up to 1.0% by weight.

[0012]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples. Example 1 Two 500 mL reaction vessels equipped with a stirrer were connected in series, and in the first reaction vessel, sulfuric acid in an amount of 1% by weight and ethylenediaminetetraacetic acid in an amount of 0.1% by weight of the total amount of the reaction mixture. 45.0 g / h of 60 wt% hydrogen peroxide solution with sodium added (1 mol / h of water in hydrogen peroxide solution)
Acetic anhydride at the rate of 73.4g / h (acetic anhydride 0.72mol / h)
At the same rate, and the reaction mixture was fed to the second reaction vessel to be reacted in a flow system. The temperature of the reaction mixture in the reaction vessel was kept at 40 ° C.

The product solution in a steady state is diluted with cold water,
Unreacted hydrogen peroxide is measured by titration with a 1 / 10N potassium permanganate aqueous solution in the presence of sulfuric acid at 4 ° C or lower, and then potassium iodide powder is added and released while keeping the temperature at 4 ° C or lower. Peracetic acid was measured by titrating iodine with a 1/10 N aqueous sodium thiosulfate solution. The concentration of peracetic acid in the product solution was 37.5% by weight, and the yield of peracetic acid based on hydrogen peroxide was 73.6%.

Comparative Example 1 45.0 g / h of a 60% by weight aqueous hydrogen peroxide solution containing 1% by weight of sulfuric acid and 0.1% by weight of sodium ethylenediaminetetraacetate in an amount of 45.0 g / h (aqueous hydrogen peroxide solution) was added. Acetic anhydride at a rate of 1 mol / h in
Example 1 was repeated except that the addition was carried out simultaneously at a rate of 1 g / h (acetic anhydride 1.39 mol / h). The concentration of peracetic acid in the product solution in the steady state was 19.1% by weight, and the yield of peracetic acid based on hydrogen peroxide was 58.9%.

Example 2 45.0 g of a 60% by weight aqueous hydrogen peroxide solution containing 1% by weight of sulfuric acid and 0.1% by weight of sodium ethylenediamine tetraacetate in an amount of 1% by weight of the total amount of the reaction mixture (water in an aqueous solution of hydrogen peroxide). Acetic anhydride 73.4 in a reactor containing 1 mol)
Under stirring, g (0.72 mol of acetic anhydride) was added dropwise at 40 ° C over 1 hour, and stirring was continued at 40 ° C for 24 hours. The concentration of peracetic acid in the obtained reaction solution was 39.0% by weight, and the yield of peracetic acid based on hydrogen peroxide was 76.0%.

Comparative Example 2 To a reactor containing 73.4 g of acetic anhydride (0.72 mol of acetic anhydride) was added sulfuric acid in an amount of 1% by weight and sodium ethylenediaminetetraacetate in an amount of 0.1% by weight of the total amount of the reaction mixture. Example 2 was repeated except that 45.0 g of a weight% aqueous hydrogen peroxide solution (1 mol of water in the aqueous hydrogen peroxide solution) was added dropwise. The concentration of peracetic acid was 24.0% by weight, and the yield of peracetic acid based on hydrogen peroxide was 47.1%.

Comparative Example 3 45.0 g of 60% by weight aqueous hydrogen peroxide solution containing 1% by weight of sulfuric acid and 0.1% by weight of sodium ethylenediaminetetraacetate in an amount of 15.0% by weight of the total amount of the reaction mixture. 86.4 g of acetic acid in a reactor containing 1 mol)
Example 2 was repeated except that (1.44 mol of acetic acid) was added dropwise. The concentration of peracetic acid was 28.7% by weight, and the yield of peracetic acid based on hydrogen peroxide was 62.4%.

[0018]

According to the present invention, a relatively high concentration aqueous solution of peracetic acid can be obtained with a high reaction selectivity without using a high concentration aqueous solution of hydrogen peroxide which is difficult to handle.

Claims (3)

[Claims] 1. A method for producing an aqueous solution of peracetic acid from acetic anhydride and an aqueous solution of hydrogen peroxide, wherein when the acetic anhydride is reacted with the aqueous solution of hydrogen peroxide, a molar amount of acetic anhydride that is less than the molar number of water is used. A method for producing an aqueous solution of peracetic acid, comprising: 2. The method according to claim 1, wherein an aqueous solution of hydrogen peroxide having a concentration of 50 to 70% by weight is used to produce an aqueous solution of peracetic acid of 30% by weight or more. 3. The method according to claim 1, wherein acetic anhydride is added to a reaction vessel containing an aqueous hydrogen peroxide solution.