KR20230033843A - method for in-cite preparation of peroxy carboxylic acid using formic acid - Google Patents

Abstract

The present invention relates to a method for on-site production of carboxylic acid peroxide using formic acid, and more specifically, to a producing method that can produce carboxylic acid peroxide immediately on-site by separately preparing first liquid containing carboxylic acid and second liquid containing hydrogen peroxide and reacting the same at the site where the carboxylic acid peroxide is to be used by simply shaking by hand. The method for on-site production of carboxylic acid peroxide using formic acid of the present invention comprises: a first liquid preparation step of obtaining first liquid containing carboxylic acid and an acid catalyst; a second liquid preparation step of obtaining second liquid containing hydrogen peroxide; a mixing step of adding the first liquid and the second liquid to a reaction vessel and mixing the same; and a handshaking step of sealing the reaction vessel and shaking the reaction vessel by hand at room temperature to react the first liquid and the second liquid to produce carboxylic acid peroxide.

Description

Method for in-cite preparation of peroxy carboxylic acid using formic acid}

The present invention relates to an on-site production method of carboxylic acid peroxide using formic acid, and more specifically, a first liquid containing formic acid and a second liquid containing hydrogen peroxide are separately prepared and a simple operation of shaking by hand at the site where the carboxylic acid peroxide is to be used It relates to a manufacturing method capable of immediately preparing peroxide carboxylic acid on site by reacting only with the present invention.

Peroxyformic acid and peracetic acid are typical low molecular weight peroxycarboxylic acids. Both substances are strong oxidizers, and have a wide range of biocidal abilities such as sterilization, bactericidal, bactericidal, bactericidal, sporicidal, etc., and have environmentally friendly characteristics that do not generate by-products after disinfection and metabolize to carbon dioxide, oxygen, and water to disappear. It is also used in deodorization, bleaching, cleaning, food preservation, water treatment, and chemical reaction processes.

Peroxyformic acid and peracetic acid are reversible reactions as shown in the chemical reaction formula (1) (2) below, and after mixing formic acid and acetic acid with hydrogen peroxide in the presence of an acid catalyst, stirring at 30 ~ 60 ℃ for more than 12 hours, and hydrolysis reaction chemical equilibrium is reached, and the product is a liquid-phase four-component equilibrium mixture in which reactants and products exist at the same time due to the nature of the reversible reaction.

Acid catalysts used at this time include homogeneous catalysts such as salts and inorganic acids such as sulfuric acid, phosphoric acid, hydrofluoric acid, and nitric acid, and heterogeneous catalysts such as cation exchange resins and solid acid catalysts.

Like most peroxides, peroxoformic acid and peracetic acid have thermodynamically unstable molecular structures to the extent that metathesis proceeds even at low temperatures. Therefore, the equilibrium state changes depending on the elapsed time after manufacture, transportation, and storage, so the concentration is variable. can

In addition, since the metathesis characteristics of peroxyformic acid or peracetic acid are enhanced by various factors such as heat, metal, light, and impact, the concentration continuously decreases after reaching the maximum concentration in chemical equilibrium. The rate of concentration decrease is much faster in peroxyformic acid than in peracetic acid. Therefore, in the course of transportation, storage, and use, there are problems such as a decrease in the concentration of peroxidized components, swelling of the storage container, and leakage, which act as an obstacle to commercialization despite excellent physical properties such as strong oxidizing power, non-residue, and eco-friendliness.

In particular, since peroxyformic acid is more unstable than peracetic acid, it has been commercialized only in limited fields, and it is preferable to use it within about 12 hours after production. Peracetic acid products also have increased explosiveness, instability, and reactivity at a concentration of 15% or more, so the product concentration is usually adjusted to the range of 10 to 15% to reduce explosiveness and inflammability to minimize the risk. Therefore, stabilizers such as quinoline, etidronic acid, and dipicolinic acid are sometimes used in products, but they do not completely solve the stability problem.

In this way, in order to overcome the short shelf life, instability and danger when dealing with unstable chemicals such as peroxyformic acid and peracetic acid, on-site manufacturing technology that can be easily manufactured in high yield with simple operation at the site and at the point of use is very useful. do.

Substances for which on-site manufacturing is applied include hypochlorous acid for use as a disinfectant and bleach. This requires an on-site system including electrolyzer, storage tank, power supply, raw material or raw water supply, and agitation equipment. The actual use concentration of peroxycarboxylic acid is 0.001% to 0.3%, which requires dilution with water at the site of use, and can be said to be included in field manufacturing in a broad sense.

As described above, carboxylic acid peroxide has excellent performance such as disinfection, bleaching, and deodorization, but is disadvantageous in storage and distribution due to the instability of the material itself, which is an obstacle to commercialization. However, there is a high demand for technology that can be produced by simple operation without using equipment with an agitation function. In addition, since the perboxylic acid prepared on site is diluted according to the purpose of use and used within several hours, it is necessary to obtain a high concentration of perboxylic acid at the time of on-site preparation.

Republic of Korea Patent No. 10-1325236: Manufacturing method of peroxide

As a result of research to solve the above problems, the present invention, unlike other carboxylic acids, during experiments related to peroxycarboxylic acid, formic acid undergoes a hydrolysis reaction with hydrogen peroxide under an acid catalyst and simply shaking by hand at room temperature (handshaking), resulting in formic acid peroxide found out that this was created. Then, the effect of handshaking time, comparison with the conventional thermosynthetic method, mixing effect with other carboxylic acids, application of the Le Chatelier principle using absorbents, etc. were tested step by step. As a result of the experiment, when formic acid was mixed with acetic acid, propionic acid, lactic acid, citric acid, etc., it was confirmed that the concentration increase effect was about 10% higher than the theoretical concentration. In addition, it was confirmed that the concentration of peroxycarboxylic acid was increased during on-site production by suppressing participation in the reverse reaction by absorbing water in the product with an absorbent using the characteristic that the perhydrolysis reaction is a reversible reaction.

The present invention was created based on these research results, and solved the solution stability problem by dividing and storing formic acid or a mixture of a carboxylic acid containing formic acid and an acid catalyst as a first liquid and hydrogen peroxide as a second liquid. , On-site production of peroxycarboxylic acid using formic acid, which can maximize the peracid concentration by mixing it on-site and generating peroxyformic acid or peroxycarboxylic acid with a simple handshaking operation at room temperature, and additionally adding an absorbent to participate in the reaction. Its purpose is to provide a method.

To achieve the above object, the in situ preparation method of carboxylic acid peroxide using formic acid of the present invention includes a first liquid preparation step of obtaining a first liquid containing carboxylic acid and an acid catalyst; a second liquid preparation step of obtaining a second liquid containing hydrogen peroxide; a mixing step of mixing the first liquid and the second liquid by introducing them into a reaction container; and a handshaking step of generating perboxylic acid by reacting the first liquid with the second liquid by shaking the reaction vessel by hand at room temperature after sealing the reaction vessel, wherein the carboxylic acid includes formic acid.

The carboxylic acid further includes at least one selected from acetic acid, propionic acid, lactic acid, and citric acid.

The carboxylic acid is mixed with the formic acid and the acetic acid in a weight ratio of 1:0.33 to 3.

In order to increase the concentration of the carboxylic acid peroxide produced through the handshaking step, an absorbent capable of absorbing water is added to the first liquid in the first liquid preparation step.

In order to increase the concentration of the carboxylic acid peroxide produced through the handshaking step, an absorbent is added to the reaction vessel in the mixing step.

After the handshaking step, the contents of the reaction vessel are allowed to stand for 1 to 3 hours.

According to the present invention, peroxyformic acid and peroxycarboxylic acid, which have been difficult to commercialize due to their instability, can be prepared at a desired time and place on site, and high-concentration carboxylic acid can be obtained with a simple operation.

In addition, the present invention is a two-component type in which reactants are divided into two types and the solution stability problem is completely solved, thereby enhancing applicability to various fields such as sterilization, disinfection, bleaching, cleaning, water treatment, deodorization, and space disinfection.

In addition, since the present invention does not use a separate manufacturing facility and does not require the use of a stabilizer, the manufacturing cost is very low compared to the conventional heating synthesis method and has the advantage of not burdening the environment.

1 is a block diagram showing an in situ production method of carboxylic acid peroxide according to an embodiment of the present invention;
2 is a block diagram showing an in situ production method of carboxylic acid peroxide according to another example of the present invention;
3 is a block diagram showing an in situ preparation method of carboxylic acid peroxide according to another example of the present invention.

Hereinafter, a method for preparing peroxycarboxylic acid in situ using formic acid according to a preferred embodiment of the present invention will be described.

Referring to FIG. 1, the in situ production method of carboxylic acid peroxide according to an embodiment of the present invention includes a first liquid preparation step of obtaining a first liquid containing carboxylic acid and an acid catalyst, and a second liquid containing hydrogen peroxide. A two-liquid preparation step, a mixing step in which the first and second liquids are put into a reaction vessel and mixed, and the reaction vessel is sealed and the reaction vessel is shaken by hand at room temperature to react the first liquid and the second liquid to peroxidize and a handshaking step to generate the carboxylic acid. Let's look at each step in detail.

1. First liquid preparation step

In the first liquid preparation step, a first liquid containing a carboxylic acid and an acid catalyst is obtained.

A carboxylic acid is an organic acid having a carboxyl group (-COOH), and an aliphatic carboxylic acid is suitable. Examples of such aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, lactic acid, and citric acid. A solution of 1 to 10 molar concentration (mol/L) of the carboxylic acid may be used.

In the present invention, as the carboxylic acid, formic acid is used alone or in the form of a mixture of formic acid and other types of carboxylic acids. For example, a carboxylic acid in which at least one selected from acetic acid, propionic acid, lactic acid, and citric acid is mixed with formic acid may be used.

In the present invention, unlike other carboxylic acids, it has been experimentally proven that formic acid is hydrolyzed with hydrogen peroxide under an acid catalyst and simply shaken by hand at room temperature (handshaking) to produce peroxyformic acid. Therefore, it is preferable to use only formic acid as the carboxylic acid or to use a mixture of other types of carboxylic acids together with formic acid.

More preferably, formic acid and acetic acid are mixed and used. In this case, there is a synergistic effect of increasing the peracid concentration. Formic acid and acetic acid may be mixed in a weight ratio of 1:0.33 to 3.

Inorganic acids are used as acid catalysts. As suitable inorganic acids, sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, hydrofluoric acid, pyrophosphoric acid and the like can be used. Inorganic acids may be used alone or in combination of two or more.

A first liquid is obtained by mixing a carboxylic acid and an acid catalyst. The addition amount of the acid catalyst is appropriately 3 to 10% of the weight of the first liquid.

The above-described first liquid may be stored or stored in a form contained in a first container.

2. 2nd liquid preparation step

Next, a second liquid containing hydrogen peroxide is obtained.

The second liquid is hydrogen peroxide alone. Therefore, the hydrogen peroxide solution itself is the second liquid. A solution of 1 to 10 molar concentration (mol/L) of hydrogen peroxide may be used.

The above-described second liquid may be stored or stored in a form contained in a second container.

3. Mixing step

Next, the first liquid and the second liquid are put into a reaction vessel and mixed. Mixing is performed at the site where the percarboxylic acid is to be used. The mixing ratio of the first liquid and the second liquid is such that the carboxylic acid and hydrogen peroxide are equimolar according to the stoichiometric ratio.

In the present invention, the problem of solution stability is completely solved because the reactants are divided into two types, the first liquid and the second liquid, and then mixed on site.

For mixing, the first liquid contained in the first container and the second liquid contained in the second container may be poured into a reaction container and mixed.

4. Handshaking Phase

Next, a handshaking step of shaking the reaction vessel by hand is performed so that the mixed first liquid and second liquid can react.

To this end, after sealing the reaction vessel, the reaction vessel is shaken by hand to react the first liquid and the second liquid. The shaking time can be within the range of 10 seconds to 10 minutes. Preferably it is 1 to 5 minutes.

The handshaking is carried out by holding the reaction vessel by hand and shaking it up and down repeatedly. The shaking frequency may be 50 to 150 times per minute.

Handshaking takes place at room temperature. The room temperature here is the temperature at the site where the peroxycarboxylic acid is to be used. Room temperature may be less than 30 °C, preferably 15 to 25 °C.

Through handshaking, carboxylic acid in the first liquid and hydrogen peroxide in the second liquid react as follows under an acid catalyst to produce carboxylic acid peroxide.

Carboxylic Acid + Hydrogen Peroxide ↔ Carboxylic Peroxide + Water

As described above, according to the present invention, a hydrolysis reaction of carboxylic acid and hydrogen peroxide can be performed by simply shaking hands (handshaking) at room temperature to produce carboxylic acid peroxide.

On the other hand, in the present invention, the concentration of peroxycarboxylic acid can be increased by breaking the equilibrium state of the reversible reaction by using an absorbent capable of absorbing water.

Taking the reaction of producing peroxyformic acid and peracetic acid as an example, it is a reversible reaction as shown in the chemical equation (1) (2) below. Chemical equilibrium is reached after a certain period of time when the hydrolysis reaction is carried out, and the product is a liquid phase four-component equilibrium mixture in which reactants and products exist at the same time due to the nature of the reversible reaction.

Therefore, if the concentration of water in the product is lowered using Le Chatelier's principle, the reaction rate is increased and the equilibrium state is shifted to the product side, thereby increasing the concentration of the finally produced peracid.

Le Chatelier's principle is a theory that a new equilibrium is reached in the direction of minimizing the change when the concentration, pressure, temperature, etc. of a substance related to the equilibrium is changed in a system in equilibrium where a reversible reaction occurs. In other words, if a part of the product involved in the reverse reaction is removed, the reverse reaction is suppressed and the forward reaction prevails, shifting the equilibrium to the product side.

A conventional superabsorbent polymer hydrogel may be used as an absorbent for lowering the concentration of product water. Super absorbent polymer hydrogel, also called super absorbent polymer, is a material that has a structure in which hydrophilic polymers are loosely cross-linked in three dimensions and can absorb and swell hundreds to thousands of times its own weight in water. Such a superabsorbent polymer hydrogel has a very fast absorption rate of water, but a very slow absorption rate of organic/inorganic solvents, oil, and ionic substances. Therefore, in the case of an aqueous solution containing organic/inorganic solvents, oil, ionic substances, etc., water is first absorbed and then penetrates between the absorbed water molecules by diffusion.

As the superabsorbent polymer hydrogel, a polyacrylic acid-based water-absorbent resin using acrylic acid and/or a salt thereof as a monomer may be used. For example, crosslinked sodium polyacrylate can be used. These polyacrylic acid-based absorbent resins are the most industrially used absorbents because they have high absorbency and fast absorption rate and are stable against heat and light.

As shown in FIG. 2, the absorbent described above may be added to the first liquid obtained in the first liquid preparation step. In this case, it is advantageous when reacting with the second liquid immediately after obtaining the first liquid to produce peroxycarboxylic acid.

And, as shown in FIG. 3, an absorbent may be added in the mixing step. At this time, it may be added to the first liquid immediately before mixing or added to the reaction vessel in which the first liquid and the second liquid are mixed.

In the case of adding an absorbent in the mixing step, it is advantageous when the first liquid and the second liquid are stored separately for a certain period of time and then mixed without immediately mixing the first liquid and the second liquid.

As described above, the present invention can greatly increase the concentration of carboxylic acid peroxide during on-site manufacturing by suppressing participation in the reverse reaction by absorbing water in the product with an absorbent using the characteristic that the hydrolysis reaction is a reversible reaction.

When reacting by adding an absorbent, it is preferable to allow the contents of the reaction vessel, that is, a four-component equilibrium mixed solution of a reactant and a product, to stand for 1 to 3 hours after the handshaking step. During the standing time, the absorbent absorbs water, which is a product, and lowers the concentration of water, thereby increasing the forward reaction rate. Accordingly, by shifting the equilibrium state to the product side, the finally produced peracid concentration can be further increased.

Hereinafter, the present invention will be described through examples. However, the following examples are intended to specifically explain the present invention, and the scope of the present invention is not limited to the following examples.

<Measurement of peracid concentration>

The concentration of peroxy acid is B.D. Sully, P.L. Williams, Analyst 87 (1962) 653-657 and G.S. Cavallini, S.X.De Campos, J.Beber De Souza, C.M. De Sousa Vidal, Int. J. Environ. Anal. Chem. 93 (2013) 906-918, and measured according to the method described. A more detailed explanation is as follows.

Phosphate buffer saline (PBS) having a composition of 0.14 mol monobasic sodium phosphate (NaH ₂ PO ₄ ), 0.34 mol monobasic potassium phosphate (KH ₂ PO ₄ ), and 0.003 mol ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) After preparing, pH = 5.5 with 1.0 mol sulfuric acid (H ₂ SO ₄ ) solution. Take 1.0 mL of the sample, dilute it 250 times with purified water, sample 25 mL, and add 10 mL of phosphate buffer solution and 50 mL of purified water. 600 μg of (2900 units/mg) bovine catalase was added thereto and stirred for 5 minutes to quench hydrogen peroxide in the sample solution. Then, 15 mL of 12 normal sulfuric acid (H ₂ SO ₄ ) solution and 2.5 g of potassium iodide (KI) were added, stirred in a dark room for 20 minutes, stirred again with 50 mL of purified water, and then 0.1 mol sodium persulfate (Na ₂ S ₂ O ₃ ) solution until it becomes pale yellow. Then, when 2 mL of diluted starch solution is added, the color darkens to blue-brown. At this time, titration is continued with 0.1 mol sodium thiosulfate (Na ₂ S ₂ O ₃ ) solution until it becomes transparent again. The peracid concentration (wt%) was calculated using the amount of 0.1 mol sodium thiosulfate solution consumed for titration.

<Manufacture of absorbent material>

According to Le Chatelier's principle, an absorbent to be used to increase the concentration of carboxylic acid peroxide was prepared as follows.

The degree of neutralization of acrylic acid was set to 40% with sodium hydroxide. And the acrylamide / acrylic acid molar ratio was 0.51, N, N'-methylenebisacrylamide / (acrylamide + acrylic acid) weight ratio was 0.2wt%, ammonium persulfate / ( Acrylamide + acrylic acid) weight ratio was set to 1.0wt%, and gelation was performed at 70 ° C. for 3 hours under a nitrogen flow. Then, it was washed with purified water, dried at room temperature, and classified into the same size for use.

<Example 1: Synthesis of handshaking peroxyformic acid according to reactant concentration>

The molar ratio of formic acid and hydrogen peroxide, which are reactants of perhydrolysis, was used in equimolar amounts according to the stoichiometric ratio. In addition, sulfuric acid was used as an acid catalyst, but the amount used was 5% based on the weight of formic acid. Hand-shaking was determined by putting the first and second liquids in a bottle, locking the lid, and then shaking the bottle up and down with a hand at a frequency of 120 times for 1 minute.

Formic acid in the range of 1 to 8 mol, hydrogen peroxide in the range of 1 to 8 mol, and sulfuric acid in the concentration of 95 wt% were prepared respectively. After preparing the first solution by mixing 100mL of formic acid and sulfuric acid, preparing 100mL of hydrogen peroxide as the second solution, put the first and second solutions in a 500mL reaction vessel (plastic bottle), lock the lid, and shake hands for 5 minutes. After standing still, the peracid concentration was measured. The measured peracid concentration (wt%) was divided by the formic acid content (wt%) in the reactant and the optimal concentration range of the reactant was determined from the yield calculated as a percentage, and the results are shown in Table 1 below.

division formic acid concentration 1M 2M 3M 4M 5M 6M 7M 8M Peracid concentration (wt%) 2.38 3.54 7.22 12.58 19.85 23.14 25.37 26.88 Formic acid content (wt%) 4.603 9.206 13.809 18.412 23.015 27.618 32.221 36.824 transference number(%) 51.74 38.45 52.28 68.33 86.3 83.79 78.74 73.00

Referring to Table 1, as the molarity of formic acid increases, the concentration of peracid produced also increases, but the concentration increase rate increases up to 5 mol concentration, but thereafter it shows a tendency to decrease somewhat.

<Example 2: Synthesis of peroxyformic acid according to handshaking time>

In order to determine the optimal handshaking time, peroxyformic acid was synthesized by varying the handshaking time in the range of 10 seconds to 10 minutes, and then the peracid concentration was measured and shown in Table 2 below. The formic acid used was at a 5 molar concentration, and the experimental procedure was the same as in Example 1.

Referring to Table 2 below, it is determined that the equilibrium concentration is reached when handshaking is performed for at least 1 minute.

division handshaking time 10 seconds 30 seconds 1 min 2 minutes 5 minutes 10 minutes Peracid concentration (wt%) 7.66 16.52 19.85 20.86 21.13 19.45

<Example 3: Comparison of handshaking and heating synthesis in peroxycarboxylic acid synthesis>

In order to confirm that handshaking synthesis can be applied to other low molecular weight carboxylic acids in addition to formic acid, and to compare the performances of handshaking according to the present invention and conventional thermal synthesis, acetic acid, propionic acid, lactic acid, and citric acid were compared.

The reactant concentrations were all 5 molar concentrations except for citric acid, which was 3 molar concentrations, and the handshaking experiment procedure was the same as in Example 3. In the warming synthesis experiment, formic acid was heated to 30°C and acetic acid, propionic acid, lactic acid, and citric acid were heated to 50°C, maintained for 6 hours, and then cooled to room temperature to measure peracid concentration.

Referring to Table 3 below, when compared with warming synthesis, the hydrolysis reaction of the handshaking method proceeded almost insignificantly for carboxylic acids other than formic acid. In the case of handshaking, peracid concentration was the highest in formic acid among carboxylic acids. In general, the higher the molecular weight, the lower the reactivity. In the case of handshaking, formic acid showed results almost similar to those of thermal synthesis.

division Peracid concentration (wt%) formic acid acetic acid propionic acid lactic acid citric acid handshaking synthesis 19.85 3.28 2.11 1.46 0.31 Heated synthesis 23.7 18.5 19.1 18.3 5.42

<Example 4: Handshaking Synthesis of Carboxylic Acid Peroxide for Mixed Solution of Formic Acid-Carboxylic Acid>

Table 4 shows the results of applying the handshaking synthesis method to the formic acid-carboxylic acid mixed solution in order to alleviate the disadvantages of corrosion and instability due to the strong reactivity of peroxyformic acid.

The reactant concentrations are all 5 molar concentrations except for citric acid, which is 3 molar concentrations, and the handshaking experiment procedure is the Example except that the weight ratio of formic acid:carboxylic acid is set to 75:25, 50:50, and 25:75 when preparing the first liquid. Same as 1.

In Table 4 below, the numerical values in parentheses are the theoretical peracid concentrations expected when formic acid and each carboxylic acid are mixed in their respective ratios based on the peracid concentrations in the case of a single component.

Referring to Table 4 below, as a result of the experiment, peracid concentrations were high in all formic acid-carboxylic acid mixed solutions and in all weight ratios. In particular, in the case of acetic acid, the weight ratio was 14% higher than the theoretical value at 50:50 and 25% higher than the theoretical value at 25:75. This is presumed to be due to the active intermolecular radical transfer of various intermediates (radicals) generated during the hydrolysis of formic acid to the acetic acid molecules.

Formic Acid:Carboxylic Acid
Mixing ratio (% by weight) Peracid concentration (wt%) acetic acid propionic acid lactic acid citric acid 100:0 19.85 19.85 19.85 19.85 75:25 16.12
(15.71) 16.37
(15.42) 15.63
(15.26) 15.69
(15.00) 50:50 13.25
(11.57) 12.33
(10.99) 11.34
(10.66) 11.25
(10.09) 25:75 9.25
(7.42) 7.58
(6.54) 6.52
(6.06) 6.31
(5.19) 0:100 3.28 2.11 1.46 0.31

<Example 5: Handshaking Carboxylic Acid Synthesis for Formic Acid-Carboxylic Acid Mixed Solution>

Through the above examples, unlike other carboxylic acids, formic acid generates peracid through hydrolysis reaction by handshaking at room temperature, and has an effect of increasing the peracid concentration (synergy) with respect to formic acid-carboxylic acid mixed solution. In particular, formic acid-acetic acid mixture In the case of the solution, it was confirmed that the enhancement effect was the highest.

Therefore, in the synthesis of carboxylic acid peroxide by handshaking with a formic acid-acetic acid mixture having a weight ratio of 25:75, the absorbent is added to the four-component equilibrium mixed solution to absorb and swell the product water, thereby lowering the reverse reaction rate and increasing the forward reaction rate to achieve an equilibrium state. It was tested whether the finally produced peracid concentration could be further increased by moving the mixture to the side.

The experiment was conducted in the same manner as in Example 1 after adding an absorbent of 10% of the weight of the first solution to the formic acid alone and the formic acid-acetic acid mixed solution having a weight ratio of 25:75. After handshaking and standing for a certain time (5 minutes to 12 hours), the peracid concentration was measured.

Referring to Table 5 below, in the case of formic acid alone, at 1 hour, in the case of formic acid-acetic acid mixed solution, a significant peracid concentration increase effect of 20 to 30% was shown in the interval between 1 hour and 3 hours. However, after 3 hours in the case of formic acid, and after 6 hours in the case of formic acid-acetic acid mixed solution, the crosslinked bonds constituting the gel of the absorbent are dismantled by the action of the generated peracid, changing to a sol phase, and the peracid concentration rapidly decreases. phenomenon was observed. Therefore, in the case of using the absorbent in the handshaking carboxylic acid synthesis, it was confirmed that the maximum peracid production yield could be obtained only when the absorbent was allowed to stand for 1 hour in the case of formic acid and 3 hours in the case of formic acid-acetic acid mixed solution.

Classification (Absorbent) Peracid concentration over time (wt%) 5 minutes 30 minutes 1 hours 3 hours 6 hours 12 hours formic acid not used 19.85 19.11 20.57 21.98 19.46 18.53 Used 18.62 19.28 22.63 20.41 16.24 13.47 Formic acid-acetic acid (25:75) not used 9.25 8.98 10.79 10.33 10.58 10.12 Used 9.44 10.74 12.62 13.02 10.14 7.65

In the above, the present invention has been described with reference to one embodiment, but this is only exemplary, and those skilled in the art will understand that various modifications and equivalent embodiments are possible therefrom. Therefore, the true protection scope of the present invention should be determined only by the attached claims.

Claims (6)

a first liquid preparation step of obtaining a first liquid containing a carboxylic acid and an acid catalyst;
a second liquid preparation step of obtaining a second liquid containing hydrogen peroxide;
a mixing step of mixing the first liquid and the second liquid by introducing them into a reaction container;
A handshaking step of sealing the reaction vessel and then shaking the reaction vessel by hand at room temperature to react the first liquid and the second liquid to produce carboxylic acid peroxide;
The in situ preparation method of peroxycarboxylic acid using formic acid, characterized in that the carboxylic acid comprises formic acid. The method of claim 1, wherein the carboxylic acid further comprises at least one selected from acetic acid, propionic acid, lactic acid, and citric acid. 3. The method of claim 2, wherein the carboxylic acid is a mixture of the formic acid and the acetic acid in a weight ratio of 1:0.33 to 3. The formic acid according to claim 1, characterized in that an absorbent capable of absorbing water is added to the first liquid in the first liquid preparation step to increase the concentration of the peroxycarboxylic acid produced through the handshaking step. In situ production method of peroxycarboxylic acid using The method of claim 1, wherein an absorbent is added to the reaction vessel in the mixing step to increase the concentration of the carboxylic acid peroxide produced through the handshaking step. [6] The method according to claim 4 or 5, wherein the contents of the reaction vessel are allowed to stand for 1 to 3 hours after the handshaking step.

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