KR102541263B1 - Method for producing freshness preservation agent of food containing water using chemically treated zeolite - Google Patents

Abstract

The present invention relates to a method for preparing a freshness-retaining agent, characterized in that it is prepared by mixing a citric acid-treated zeolite and sodium chlorite-treated zeolite, and a freshness-retaining agent prepared by the method.

Description

Method for producing freshness preservation agent of food containing water using chemically treated zeolite}

The present invention includes (1) adding an aqueous solution of citric acid to zeolite and then stirring; (2) preparing a citric acid-treated zeolite by drying the stirred mixture of step (1); (3) adding an aqueous solution of sodium chlorite (NaClO ₂ ) to the zeolite and then stirring; (4) preparing sodium chlorite-treated zeolite by drying the stirred mixture of step (3); and (5) mixing the citric acid-treated zeolite prepared in step (2) with the sodium chlorite-treated zeolite prepared in step (4). It relates to a freshness-retaining agent prepared by the method.

Foods containing a large amount of moisture, such as fruits, agricultural and marine products, refrigerated meats, and cooked foods, may suffer from quality degradation problems such as being dried depending on distribution conditions or microorganisms being generated for various reasons. As a result, problems such as deterioration in food quality and deterioration in taste occur. In addition, as various cooked foods are developed according to the increase in single-person households and distributed in a refrigerated state, the importance of maintaining the freshness of food is increasing.

In addition, most of the food manufactured and cooked at home, as well as the food manufactured for distribution, contains moisture, and the quality deterioration problem of such food may be applied. Since food is generally not added with preservatives such as food preservatives, it may be difficult to maintain long-term freshness.

On the other hand, food preservatives are sometimes mixed with food to maintain the freshness of food, but consumers' preference is low due to concerns about side effects caused by ingestion of food preservatives. Therefore, attempts to prevent mixing with food and at the same time maintain the freshness of food by adding a freshness-retaining material when manufacturing food packaging materials or by attaching a freshness-retaining agent to food preservation containers in place of food preservatives mixed with food It is being done.

Korean Patent Registration No. 1726857 describes a method for manufacturing a disinfectant for agricultural and livestock products using a hydrogen ion concentration regulator, and Korean Patent Publication No. 2020-0113123 discloses a slow-release chlorous acid or carbon dioxide release kit Although described, it is different from the method for preparing freshness-retaining agents for water-containing foods using the chemically treated zeolite of the present invention.

The present invention was devised in response to the above needs, and an object of the present invention is a food that can replace food preservatives that are mixed with food and may be ingested, and that function is realized in a space where food is packaged in a non-contact manner with food. It is to provide a freshness retention agent for.

In order to solve the above problems, the present invention is (1) adding a citric acid aqueous solution to the zeolite and then stirring; (2) preparing a citric acid-treated zeolite by drying the stirred mixture of step (1); (3) adding an aqueous solution of sodium chlorite (NaClO ₂ ) to the zeolite and then stirring; (4) preparing sodium chlorite-treated zeolite by drying the stirred mixture of step (3); and (5) mixing the citric acid-treated zeolite prepared in step (2) with the sodium chlorite-treated zeolite prepared in step (4). do.

In addition, the present invention provides a freshness-retaining agent prepared by the above method.

The present invention replaces food preservatives that are mixed with food and may be ingested, and provides a freshness retainer that can effectively maintain the freshness of food for a long period of time rather than temporarily while having a low risk of ingestion by attaching to food packaging materials or food storage containers. can

Figure 1 compares the effect of inhibiting the growth of E. coli according to the freshness maintenance agent treatment.

In order to achieve the object of the present invention, the present invention

(1) stirring after adding an aqueous solution of citric acid to zeolite;

(2) preparing a citric acid-treated zeolite by drying the stirred mixture of step (1);

(3) adding an aqueous solution of sodium chlorite (NaClO ₂ ) to the zeolite and then stirring;

(4) preparing sodium chlorite-treated zeolite by drying the stirred mixture of step (3); and

(5) Provides a method for producing a freshness-retaining agent, characterized in that it is produced by mixing the citric acid-treated zeolite prepared in step (2) and the sodium chlorite-treated zeolite prepared in step (4). .

In the method for preparing the freshness retainer of the present invention, step (1) is preferably 0.1 to 10% (w / v) citric acid aqueous solution added to zeolite in a ratio of 0.8 to 1.2: 4.5 to 5.5 (w / v) After stirring for 20 to 40 minutes, more preferably, 2% (w/v) citric acid aqueous solution may be added to the zeolite at a ratio of 1:5 (w/v) and then stirred for 30 minutes.

Zeolite is an aluminum silicate hydrate mineral and is a microporous material in which pores with a diameter of several nm exist. Water molecules can be filled in the microscopic inner pores, and the water molecules contained can be evaporated and converted into water vapor. In addition, it can be used as a catalyst because it can attach various organic substances that promote chemical reactions.

Citric acid is a weak organic acid found in tangerines and lemons in nature, and is used as a sweetener and fragrance for food, and is also widely used as an eco-friendly disinfectant because of its bactericidal effect. In the present invention, since the purpose of the present invention is to gradually release chlorine dioxide gas of sodium chlorite according to the concentration of hydrogen ions, a method of adsorbing uniformly low-concentration citric acid to zeolite is preferable rather than directly using citric acid powder.

In addition, in the method for preparing freshness-retaining agent of the present invention, in the step (2), preferably, the stirred mixture is dried at 25-60 ° C. for 20-28 hours to produce citric acid-treated zeolite, more preferably may dry the stirred mixture at 37° C. for 24 hours to prepare a citric acid-treated zeolite.

In addition, in the method for preparing the freshness retainer of the present invention, the step (3) is preferably 0.1 to 10% (w / v) sodium chlorite (NaClO ₂ ) aqueous solution having a pH of 9 to 14 is added to zeolite. After addition at a ratio of 1.2: 4.5 to 5.5 (w / v), it can be stirred for 20 to 40 minutes, more preferably a 2% (w / v) sodium chlorite (NaClO ₂ ) aqueous solution with a pH of 11 in zeolite After adding in a ratio of 1:5 (w/v), it can be stirred for 30 minutes.

As described above, by treating the zeolite with sodium chlorite, the disinfection function of releasing chlorine dioxide gas can be imparted. Treatment of zeolite with sodium chlorite under the above conditions could maximize the freshness effect without affecting the flavor or taste of food when packaged together with food. In the above step, sodium chlorite that is chemically stable may be used as sodium chlorite. For example, sodium chlorite reacts chemically under conditions rich in hydrogen ions to generate chlorine dioxide (ClO ₂ ) gas, which is used as a water purification disinfectant to disinfect and remove odors. It is preferable to prepare using a stable basic sodium chlorite aqueous solution.

In order to maintain chemical stability of the sodium chlorite (NaClO ₂ ) aqueous solution, it is preferable to prepare it in a low hydrogen ion concentration range (pH 8 or higher). Sodium chlorite releases chlorine dioxide gas as the number of hydrogen ions increases, that is, chemically reacts under acidic conditions. Therefore, sodium chlorite (NaClO ₂ ) aqueous solution can be prepared after the pH reaches more than the above range using sodium hydroxide or potassium hydroxide, but is not limited thereto.

In addition, in the method for preparing freshness-retaining agent of the present invention, in step (4), the stirred mixture can be preferably dried at 25-60 ° C. for 20-28 hours to produce sodium chlorite-treated zeolite. Preferably, the stirred mixture may be dried at 37° C. for 24 hours to prepare sodium chlorite-treated zeolite.

In addition, in the method for preparing the freshness-retaining agent of the present invention, the mixing in step (5) may preferably mix citric acid-treated zeolite and sodium chlorite-treated zeolite in a weight ratio of 0.8 to 1.2: 0.8 to 1.2, and more Preferably, citric acid-treated zeolite and sodium chlorite-treated zeolite may be mixed in a weight ratio of 1:1.

The freshness retainer mixed under the above conditions activates hydrogen ions of citric acid by absorbing water vapor in the food container with zeolite. effect could be maximized.

In addition, when zeolite is treated with citric acid and sodium chlorite at the same time, acidification proceeds in advance due to citric acid, and chlorine dioxide gas is already released, which incapacitates the performance as a freshness retainer. .

In the case of fermented food (kimchi, soybean paste, etc.), which is a traditional Korean food containing a lot of moisture, the freshness retainer of the present invention is highly dependent on the amount of hydrogen ions discharged during acidification during the fermentation process and the amount of water vapor present in the space within the food container. The rate and amount of chlorine dioxide gas release from sodium chlorite can be determined by Therefore, in fermented foods containing a lot of moisture, hydrogen ions in citric acid as well as hydrogen ions in the water vapor and food can be activated to promote the release of chlorine dioxide gas from sodium chlorite. However, sodium chlorite in freshness-retaining agents in dried foods or cooking dry ingredients that do not contain moisture is stably present and does not emit or emit very small amounts of chlorine dioxide gas. Therefore, the freshness-retaining agent of the present invention is preferably used for water-containing foods. Types of the water-containing food may include cheonggukjang, soybean paste, ssamjang, red pepper paste, soy sauce, and kimchi, but are not limited thereto.

The method for producing the freshness-retaining agent of the present invention is more specifically

(1) adding 0.1 to 10% (w/v) citric acid aqueous solution to zeolite at a ratio of 0.8 to 1.2:4.5 to 5.5 (w/v) and stirring for 20 to 40 minutes;

(2) preparing a citric acid-treated zeolite by drying the stirred mixture of step (1) at 25 to 60° C. for 20 to 28 hours;

(3) adding 0.1 to 10% (w/v) sodium chlorite (NaClO ₂ ) aqueous solution to zeolite at a ratio of 0.8 to 1.2:4.5 to 5.5 (w/v) and then stirring for 20 to 40 minutes;

(4) preparing sodium chlorite-treated zeolite by drying the stirred mixture of step (3) at 25 to 60° C. for 20 to 28 hours; and

(5) mixing the citric acid-treated zeolite prepared in step (2) and the sodium chlorite-treated zeolite prepared in step (4) in a weight ratio of 0.8 to 1.2: 0.8 to 1.2,

more specifically

(1) adding 2% (w/v) citric acid aqueous solution to zeolite at a ratio of 1:5 (w/v) and then stirring for 30 minutes;

(2) preparing a citric acid-treated zeolite by drying the stirred mixture of step (1) at 37° C. for 24 hours;

(3) adding a 2% (w/v) aqueous solution of sodium chlorite (NaClO ₂ ) to the zeolite at a ratio of 1:5 (w/v) and stirring for 30 minutes;

(4) drying the stirred mixture of step (3) at 37° C. for 24 hours to prepare sodium chlorite-treated zeolite; and

(5) mixing the citric acid-treated zeolite prepared in step (2) and the sodium chlorite-treated zeolite prepared in step (4) in a weight ratio of 1:1.

The present invention also provides a freshness-retaining agent prepared by the above method.

In order to attach the freshness-retaining agent to food packaging materials or food storage containers without being mixed with food, it may be put into a pouch made of a breathable film and sealed. The material of the breathable film may not be particularly limited, and may be composed of various resins. For example, the breathable film may be made of a resin of polyethylene terephthalate (PET), casting polypropylene (CPP), oriented polypropylene (OPP), linear low density polyethylene (LLDPE), polypropylene (PP), or polyethylene (PE). And they can be composed of one layer or multiple layers.

Hereinafter, production examples and examples of the present invention will be described in detail. However, the following Preparation Examples and Examples are only to illustrate the present invention, and the content of the present invention is not limited to the following Preparation Examples and Examples.

Preparation Example 1. Freshness maintaining agent (zeolite/citric acid-zeolite/sodium chlorite)

Citric acid-treated zeolite was prepared by adding 0.5 L of a 2% (w/v) citric acid aqueous solution to 100 g of zeolite powder, stirring the mixture for 30 minutes, and drying the mixture at 37° C. for 24 hours.

After adding 0.5 L of a 2% (w/v) sodium chlorite (NaClO ₂ ) aqueous solution (adjusted to pH 11) to 100 g of zeolite powder, the mixture stirred for 30 minutes was dried at 37°C for 24 hours to obtain sodium chlorite. A treated zeolite was prepared.

The prepared citric acid-treated zeolite and the prepared sodium chlorite-treated zeolite were mixed in a weight ratio of 1:1.

Comparative Example 1. Freshness retaining agent (zeolite/citric acid)

Citric acid-treated zeolite was prepared by adding 0.5 L of a 5% (w/v) citric acid aqueous solution to 100 g of zeolite powder, stirring the mixture for 30 minutes, and drying the mixture at 37° C. for 24 hours.

Comparative Example 2. Freshness retaining agent (zeolite/sodium chlorite)

100 g of zeolite powder was added to 0.5 L of 2% (w/v) sodium chlorite (NaClO ₂ ) aqueous solution (pH 11), stirred for 30 minutes, and dried at 37 ° C for 24 hours to prepare zeolite adsorbed with sodium chlorite. did

Comparative Example 3. Freshness retaining agent (zeolite/citric acid-zeolite/sodium chlorite)

Citric acid-treated zeolite was prepared by adding 0.5 L of 0.05% (w/v) citric acid aqueous solution to 100 g of zeolite powder, stirring the mixture for 30 minutes, and drying the mixture at 37° C. for 24 hours.

After adding 0.5 L of 12% (w/v) sodium chlorite (NaClO ₂ ) aqueous solution (pH 11) to 100 g of zeolite powder, the mixture stirred for 30 minutes was dried at 37°C for 24 hours to obtain sodium chlorite-treated zeolite. was manufactured.

The prepared citric acid-treated zeolite and the prepared sodium chlorite-treated zeolite were mixed in a weight ratio of 1:1.

Comparative Example 4. Freshness retaining agent (zeolite/citric acid-zeolite/sodium chlorite)

Citric acid-treated zeolite was prepared by adding 0.5 L of a 12% (w/v) citric acid aqueous solution to 100 g of zeolite powder, stirring the mixture for 30 minutes, and drying the mixture at 37° C. for 24 hours.

After adding 0.5 L of 0.05% (w/v) sodium chlorite (NaClO ₂ ) aqueous solution (pH 11) to 100 g of zeolite powder and stirring for 30 minutes, the mixture was dried at 37°C for 24 hours to obtain sodium chlorite-treated zeolite. was manufactured.

The prepared citric acid-treated zeolite and the prepared sodium chlorite-treated zeolite were mixed in a weight ratio of 1:1.

Comparative Example 5. Freshness retaining agent (zeolite/citric acid/sodium chlorite)

200 g of zeolite powder, 10 g of citric acid and 10 g of sodium chlorite (NaClO ₂ ) were mixed.

Example 1. E. coli growth evaluation

1 g each of the freshness-retaining agents prepared in Preparation Example 1 and Comparative Examples 1 and 2 was put into a Tyvek pouch, sterilized with ethylene oxide gas, and E. coli growth was observed for 24 hours, and then it was confirmed whether the growth of the bacteria was inhibited. The concentration of E. coli was treated at 2×10 ⁷ CFU/plate.

As a result, the growth of Escherichia coli occurred normally in the untreated control group, and the growth of Escherichia coli was hardly inhibited in Comparative Example 1. On the other hand, in Comparative Example 2, E. coli was inhibited to some extent, and in Preparation Example 1, it could be seen that the growth of E. coli was almost completely inhibited (FIG. 1). Therefore, it is determined that it is preferable to prepare a freshness-retaining agent using both citric acid-treated zeolite and sodium chlorite-treated zeolite.

Example 2. Disk diffusion antibacterial test

For the freshness retainers of Preparation Example 1 and Comparative Examples 3 to 5, the antibacterial activity was verified by a commonly used disk diffusion method. Escherichia coli ( E. coli ) And Bacillus cereus ( B. cereus ) The medium used for the culture was LB medium. Each bacterium was inoculated by obtaining 2-3 colonies (0.8×10 ⁸ CFU/mL). The diluted freshness-retaining agent was dissolved in distilled water, and 10 μl of each was applied to a sterilized paper disk (8 mm in diameter). After the distilled water was completely dried, it was placed on a plate medium and maintained at 35 ° C. After 24 hours, the transparency (clear zone) around the paper disk was measured to investigate the antibacterial activity.

Antibacterial effect of freshness retainer Kind of Freshness Retaining Agent Inhibition zone (mm) Escherichia coli ( E. coli ) Bacillus cereus ( B. cereus ) Preparation Example 1 6.2 5.8 Comparative Example 3 6.0 5.8 Comparative Example 4 3.3 3.4 Comparative Example 5 6.0 5.3

As a result, it was found that the freshness-retaining agents of all experimental groups except for Comparative Example 4 had high antibacterial activity in both Escherichia coli ( E. coli ) and Bacillus cereus ( B. cereus ) strains. This proves that the antibacterial function acts strongly as the concentration of chlorine dioxide increases.

Example 3. Comparison of browning and off-flavor of traditional foods

1 g each freshness-retaining agent prepared by the methods of Preparation Example 1 and Comparative Examples was sealed and placed in a bag made of a breathable film exclusively for the freshness-retaining agent, and each of the sealed bags was attached to the inner top of the packaging container for Cheonggukjang. and packed. After being packaged and left at room temperature for 10 days, 30 sensory test agents were asked to compare the degree of browning and off-flavor of Cheonggukjang. A lower score was given as the degree of browning progressed, and a lower score was given as the off-flavor and fermented odor were severe, and it was evaluated using a 7-point scale.

Comparison of browning and off-flavor of traditional foods Kind of Freshness Retaining Agent degree of browning off-flavor Preparation Example 1 5.8 6.2 Comparative Example 1 2.0 1.6 Comparative Example 2 5.2 5.4 Comparative Example 3 5.5 5.8 Comparative Example 4 3.0 2.8 Comparative Example 5 4.6 4.4

As a result, it was judged that the freshness of the Cheonggukjang was maintained for a long time by effectively suppressing the off-odor while hardly browning in the Cheonggukjang packaged using the freshness-retaining agent of Preparation Example 1. Cheonggukjang packaged using the freshness retainer of Comparative Example 3 had almost no fermentation odor, but there was a lot of chlorine dioxide gas smell, so it was rather repulsive. It was found that the fermentation proceeded quickly and the fermentation odor was generated, resulting in a decrease in the freshness effect. Cheonggukjang packaged using the freshness-retaining agent of Comparative Example 2 showed the second highest freshness effect after Comparative Example 3 among Comparative Examples. In the case of manufacturing by simply mixing the materials as in Comparative Example 5, the emission of chlorine dioxide gas occurred explosively and there was a temporary effect, but the results observed for a long period of time confirmed that the freshness maintenance effect was not high.

Claims (4)

(1) adding 0.1 to 10% (w/v) citric acid aqueous solution to zeolite at a ratio of 0.8 to 1.2:4.5 to 5.5 (w/v) and stirring for 20 to 40 minutes;
(2) drying the stirred mixture of step (1) at 25 to 60° C. for 20 to 28 hours to prepare citric acid-treated zeolite;
(3) 20 to 40 minutes after adding 0.1 to 10% (w/v) sodium chlorite (NaClO ₂ ) aqueous solution with a pH of 9 to 14 to the zeolite at a ratio of 0.8 to 1.2:4.5 to 5.5 (w/v) Stirring while;
(4) preparing sodium chlorite-treated zeolite by drying the stirred mixture of step (3) at 25 to 60° C. for 20 to 28 hours; and
(5) mixing the citric acid-treated zeolite prepared in step (2) and the sodium chlorite-treated zeolite prepared in step (4) in a weight ratio of 0.8 to 1.2: 0.8 to 1.2. To, Bacillus cereus ( Bacillus cereus ) Method for producing a freshness retainer with enhanced antibacterial activity. delete delete delete

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