KR101568275B1 - High salt agent for laver farming - Google Patents

Abstract

The present invention relates to a high salt agent for a high salt agent for laver farming, reducing use of a hydrochloric acid which an inorganic acid, and replacing the hydrochloric acid by salt and the like to reduce use of an inorganic acid, thereby not only enabling environmentally friendly farming, but also improving quality of laver by using only a small amount of high salt agent.

Description

{High salt agent for laver farming}

The present invention relates to a high-salt treatment agent for Kimyang, which can reduce the use of hydrochloric acid, which is an inorganic acid, and replace it with an additive such as salt, thereby reducing the amount of inorganic acid used to make it environmentally friendly. And a high salt treatment agent for Kim Yong Sik.

Based on the development of artificial harvesting technology, Kim Yang Sik has continued to grow quantitatively through advancement of fishing grounds and mechanization of processing, and Kim has been established as a foreign food acquisition and national health food by activating the fishing village economy. However, growth is limited due to instability and quality deterioration in recent years, slowing consumption due to unhealthy acid processing, rising labor costs, and sluggish exports.

In the meantime, the use of inorganic acid treatment agents in the aquaculture farms was accompanied by nutritional problems on the ecosystem, and the consumption of kimchi was reduced due to the degradation of the kimchi image, which is a natural food. And the like.

In other words, existing active treatments including inorganic acid such as salt and apple have been used for a long time due to advantages such as diatomaceous and fungus removal, It is reasonable to avoid using these chemicals and inorganic acids in the future.

Therefore, in 1994, the Ministry of Agriculture and Forestry declared the use standards of the Kimyang valley acid treatment agent, which prescribes the acid treatment chemicals, the supply procedure and the proper use standards. In 1995, The use of inorganic acid in the treatment agent, that is, the content of chlorine, sulfuric acid and nitrogen ion was adjusted from 5.0 wt% to 9.5 wt% or less.

However, the active treatment agent having a low content of inorganic acid is not excellent in efficacy, and thus it is difficult to completely replace the existing active treatment agent.

Accordingly, in order to maintain and preserve the marine ecosystem and the environment by minimizing the use of animal medicines and the like, without using chemically synthesized substances harmful to the human body, Applicants have been presenting entrusted examination business reports of the Mokpo Regional Maritime Affairs and Fisheries Office, , A high salt treatment technology was developed to produce high quality steaming even with less active treatment agent including inorganic acid.

Disclosure of Invention Technical Problem [7] The present invention provides a high salt treatment agent for Kimyangsik which can improve the quality of kimchi by using only a small amount of high salt treatment agent that minimizes the amount of inorganic acid used and can reduce the cost burden of the fishermen. .

In order to achieve the above object, the present invention provides a method for producing a water-based acid solution, which comprises 40 to 50% by weight of water, 10 to 15% by weight of a phosphoric acid aqueous solution of 85% by weight, 10 to 15% by weight of salt, And 30 wt%, based on the total weight of the composition. At this time, the water preferably includes seawater.

The high salt treatment agent may further comprise 1 to 5% by weight of an aqueous solution of calcium chloride or 0.1 to 2% by weight of hypochlorous acid, and the concentration of the hypochlorous acid water is preferably 50 to 200 ppm.

The chlorine ion content in the high salt treatment agent is preferably 14 to 18% by weight, and the high salt treatment agent may be diluted to 5 to 40 times.

The present invention minimizes the amount of inorganic acid which is the main component of the active treatment agent and increases the content of chlorine ion through other additives such as salt without using citric acid at all, And a high salt treatment agent for Kim Yong Sik which shows a high effect on the improvement of quality of Kim.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the invention as disclosed to those skilled in the art. It does not mean that the category is limited.

Throughout this specification, when an element is referred to as "including" an element, it is understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise. In addition, each step may be performed differently from the stated order unless explicitly stated in the context in the specific order.

The high salt treatment agent of the present invention comprises 40 to 50 wt% of water, 10 to 15 wt% of a phosphoric acid aqueous solution having a concentration of 85 wt%, 10 to 15 wt% of a salt and 25 to 30 wt% of an aqueous hydrochloric acid solution having a concentration of 35 wt% .

The phosphoric acid aqueous solution is preferably a source of phosphorus (P) which is a core element constituting a protoplasm of a cell, and its content is preferably 10 to 15% by weight. When the content is less than 10% by weight, %, It is uneconomical because there is practically no difference in effect.

The salt acts as a source of chlorine ions having a sterilizing effect. Conventionally, hydrochloric acid has been mainly used as a source of chlorine ions, but the present invention is characterized in that salt is used in place of hydrochloric acid to reduce the amount of inorganic acid used. That is, the salt is used to increase the content of chlorine ion while reducing the amount of inorganic acid. When used together with hydrochloric acid, the salt can maximize the effect while reducing the amount of hydrochloric acid used.

The content of the salt is preferably 10 to 15% by weight. If the content is less than 10% by weight, it is difficult to obtain a desired effect due to insufficient chlorine ions. If the content exceeds 15% by weight, the organic acid salt- And the like. As the type of the salt, all kinds of salt such as sun salt and mechanical salt can be used, and the kind of the salt is not limited.

The content of the hydrochloric acid aqueous solution is preferably 25 to 30% by weight as the supply source of chlorine ions. If the content is less than 25% by weight, the effect of adding hydrochloric acid is insignificant. If the content is more than 30% by weight, The effect of reduction can be reduced.

Conventional drinking water, industrial water, etc. may be used as the water, but it is preferable that seawater containing chlorine ions, sodium ions, etc. be used as an example.

The high salt treatment agent may further comprise 1 to 5% by weight of an aqueous solution of calcium chloride and 0.1 to 2% by weight of hypochlorous acid to improve the culture efficiency. At this time, the concentration of the hypochlorous acid water is preferably 50 to 200 ppm.

When the content of calcium is less than 1% by weight, the effect of adding calcium is insufficient. When the content of calcium is more than 5% by weight, There is no difference in effect, which is uneconomical.

The calcium chloride aqueous solution is preferably an aqueous calcium chloride solution having a concentration of 35% by weight. The calcium chloride aqueous solution may be prepared by various industrially applicable methods, but preferably an aqueous calcium chloride solution prepared from shellfish such as oyster shells, barnyardgrass, clam, etc. is preferably used.

In detail, first, the shellfish are crushed into powder form, and then the hydrochloric acid aqueous solution is added to the crushed shellfish powder to elute the metals contained in the shellfish into hydrochloride form. For rapid reaction, the shellfishes are pulverized into an appropriate size to be undifferentiated, preferably 20-100 mesh shellfish powder.

The hydrochloric acid aqueous solution used for the hydrochloric acid elution is preferably an aqueous hydrochloric acid solution of 30 to 35 wt%, preferably 3 to 10 times the weight of the shellfish. If the amount of the hydrochloric acid aqueous solution is less than 3 times, precipitation of calcium chloride causes gelation, which makes agitation and reaction difficult. If it exceeds 10 times, it may be difficult to recover excess hydrochloric acid.

When the reaction between the shellfish and hydrochloric acid is terminated, the solid phase silicon dioxide is separated from the reaction product in which the hydrochloride is mixed by using a filter to separate the silicon dioxide contained in the reaction product. Filtration can be carried out using various solid-liquid separators such as pressure filters, centrifuges, belt presses, and fibrous filters.

Thereafter, the silicon dioxide is separated and calcium oxide (CaO) is added to the egg filtrate to precipitate hydrochlorides except for the calcium chloride in the hydroxide form. Thereafter, the precipitated hydroxides can be separated by centrifugation or the like to finally obtain a calcium chloride solution. The excess hydrochloric acid contained in the filtrate can be increased in the yield of calcium chloride by adding calcium oxide rather than separating it. At this time, by adjusting the pH to between 6 and 8 by the amount of calcium oxide, the separation efficiency can be increased by using the difference in solubility.

The obtained calcium chloride solution may be used as it is, but the calcium chloride may be concentrated and crystallized by performing a crystallization step, and then the calcium chloride solution may be prepared into an aqueous solution. The crystallization is carried out by heating the calcium chloride solution at 80 to 100 ° C. and concentrating the solution to a specific gravity of 1.55 to 1.8. Thereafter, the concentrated calcium chloride solution is introduced into the cooling vessel where the cooling water is circulated externally. And calcium chloride crystals can be obtained.

Meanwhile, the calcium chloride aqueous solution is prepared by adding a woody plant or herbaceous plant material to an aqueous calcium chloride solution and stirring the calcium chloride aqueous solution so as to further contain various minerals such as magnesium and potassium to enhance the texture and nutrition of the kim, By separating, various minerals contained in plants can be utilized.

The woody plant or herbaceous plant may be a variety of plants, but it is preferable to use Fagopyrum esculentum moench. It has been reported that the mung bean contains 0.227% of phosphorus, 0.62% of nitrogen, 5.38% of potassium, 3.03% of calcium, 0.384% of magnesium, 154.4 ppm of iron, 20.0 ppm of manganese, 28.79 ppm of zinc and 17.34 ppm of boron, Magnesium, phosphorus, and the like, rather than the mineral component contained in the ash combusted.

The calcium chloride aqueous solution further containing various minerals extracted from the woody plant or herbal plant material is also effective for anticancer activity, for example, for improving the quality and quality of kimchi. The woody plant or herbaceous plant material is preferably added in an amount of 1 to 30 g per 100 mL of the aqueous solution of calcium chloride. The aqueous solution of the calcium chloride to which the ash is added is sufficiently stirred and then allowed to stand at 3 to 25 캜 for 4 to 10 hours to precipitate impurities. It is preferable to use them separately.

On the other hand, the hypochlorous acid water is added to improve the germicidal effect and to minimize the generation of parasitic diatoms and the like. When the content of hypochlorous acid water is less than 0.1 wt%, it is difficult to obtain a desired effect and more than 2 wt% The productivity of the Kim style can be reduced.

The hypochlorous acid water may be produced by various methods, but preferably by electrolysis of seawater. In one embodiment, the hypochlorous acid water can be produced by electrolyzing seawater using an electrolytic cell in which a stick-shaped negative electrode is inserted into a cylindrical positive electrode. At this time, it is preferable that an anion exchange membrane supported by the mesh net support is fixedly installed between the positive electrode and the negative electrode.

When sodium chloride-containing seawater flows into the periphery of the negative electrode of the electrolytic cell, chloride ions generated in the negative electrode selectively pass through the anion exchange membrane to the positive electrode, and in the positive electrode, hypochlorous acid is generated from the chloride ion passing through the anion- can do.

By using an anion exchange membrane supported by a mesh net support rather than a general porous polymer membrane, purity and production efficiency of hypochlorous acid water can be enhanced, and diffusion of ions in the vicinity of the diaphragm to the opposite side can be minimized .

The anion exchange membrane may be prepared by coating an anion exchange resin composition comprising an anion exchange resin, a binder resin, a cross-linking agent, and a solvent on a nonwoven fabric, followed by drying.

The anion exchange resin may be a resin component having a quaternary ammonium salt group such as quaternary butyl ammonium hydroxide, quaternary butyl ammonium acetate, quaternary ethyl ammonium hydroxide, quaternary ethyl ammonium acetate, etc. The binder resin component A styrene-acrylate-glycidyl methacrylate terpolymer, a polyvinyl alcohol-vinyl acetate copolymer, an acrylic acid-acrylate copolymer, and the like can be used. The crosslinking agent of the present invention may be a compound such as diacryl pentaerythritol, triacryl pentaerythritol, or hexaacryl pentaerythritol, or a di (meth) acrylate monomer, but is not limited thereto no.

More specifically, the anion exchange membrane may be prepared by mixing an anion exchange resin, a binder resin, a crosslinking agent and a solvent to prepare a composition liquid having a solid content of 20 to 50% by weight, impregnating the composition liquid with a nonwoven fabric, The coated nonwoven fabric may be dried at room temperature and then heat-treated at 100 to 150 ° C.

Meanwhile, the high salt treatment agent of the present invention may further include an aqueous sulfuric acid solution to further improve sterilizing power and culture efficiency. The sulfur aqueous solution may be a sulfur aqueous solution having a concentration of 35% by weight, and the content thereof is preferably 1 to 5% by weight. If the content of the aqueous sulfuric acid solution is less than 1% by weight, it is difficult to obtain a desired effect. If the content of the aqueous sulfuric acid solution exceeds 5% by weight, on the other hand,

Various types of the sulfuric acid solution may be used, but preferably sulfuric acid pretreated to reduce toxicity can be used. As for the pretreatment method of sulfur, yellow soil, sulfur, molasses and water are first mixed and aged at 30 to 35 ° C for 6 to 8 days. Then, water and sodium hydroxide are added to the aged sulfur again, and the mixture is heated and stirred to dissolve the sulfur sufficiently in water. Then, solid matters such as yellow loess are precipitated from the solution in which the sulfur component is dissolved. At this time, it is preferable to mix the yellow clay and the sulfur in a ratio of 1: 1, and the mixture ratio of the yellow clay, sulfur, molasses and water is preferably adjusted to 60 to 70%. Such pretreated sulfur has a germicidal effect but is less toxic and environmentally friendly.

In order to increase the productivity of Kimyangmyun, to minimize the parasites and attached diatoms, and to sufficiently achieve the control effect against pests and the like, the high salt treatment agent of the present invention having the above composition preferably has a chloride ion content of 14 to 18% by weight . At this time, the content of sodium ions in the high salt treatment agent is preferably 1 to 5% by weight.

Hereinafter, the present invention will be described with reference to various experimental examples. However, the following Production Examples and Experimental Examples are intended to illustrate the present invention specifically, and do not limit the scope of the present invention.

[Experimental Example 1]

A high salt treating agent was prepared in a different composition and composition as shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 sea water 47% 45% 40% 45% 45% 40% 40% Aqueous solution of phosphoric acid
(85%) 13% 12% 14% 12% 12% 14% 14% Salt 13% 12% 14% 12% 12% 14% 11% Hydrochloric acid aqueous solution
(35%) 27% 27% 25% 27% 27% 27.5% 25% Calcium chloride
Aqueous solution (35%) 3% 2.5% 3.99% 1.5% 2.5% 2.5% Hypochlorous acid water
(100 ppm) One % 1.5% 0.01% 2.5% 1.5% 1.5% Sulfuric aqueous solution
(35%) - 3% - - 0.5% 6% Sum 100 100 100 100 100 100 100

In the case of Example 1, the content of chlorine ion and sodium ion in the high salt treatment agent was examined and it was measured to include 16.25% of chloride ion and 3.13% of sodium ion.

[Experimental Example 2]

When the high salt treatment agents of the above Examples and Comparative Examples were treated with Kim and Paula, the cell ratio was measured.

Kim, used in this study, used sea anchovy cultivated in Songpyeong fishing village located in Pyeongho - ri, Jeonnam - namdo, South Korea.

After immersing for 30 seconds in the high salt treatment agent diluted 10, 20 and 40 times, the changes of before and after treatment were compared and investigated. After the above-mentioned acid treatment test, the cells were stained with erythrhosin and observed with a microscope. The results are shown in Table 2 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Kim Blue Kim Blue Kim Blue Kim Blue Kim Blue Kim Blue Kim Blue 10 times 3.43 50.24 4.05 65.90 4.95 73.57 3.57 51.27 11.02 77.89 3.97 63.25 10.59 75.29 20 times 3.09 48.26 3.85 63.50 4.63 70.28 3.15 49.20 10.47 75.23 3.57 61.78 10.11 73.88 40 times 2.57 45.89 3.50 60.97 4.07 68.27 2.87 45.54 10.01 73.14 3.45 59.36 09.75 71.20

(Percentage of cells of Kim and Paral,%)

As can be seen from the above table, it was found that the cell ratio of Paeonia japonica was highest in Example 3. In Comparative Example 1 and Comparative Example 3, the effect of increasing the cell percentage was insufficient by adding hypochlorous acid water and aqueous sulfuric acid solution. In Comparative Example 2 and Comparative Example 4, .

The photosynthetic activity was measured immediately after the immersion and 72 hours after the immersion in the high salt treatment agent diluted 20-fold for 30 seconds, and the results are shown in Table 3 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Kim Blue Kim Blue Kim Blue Kim Blue Kim Blue Kim Blue Kim Blue Immediately after immersion 0.61 0.65 0.57 0.62 0.51 0.60 0.59 0.57 0.49 0.55 0.54 0.65 0.45 0.60 After 72 hours 0.80 0.31 0.78 0.29 0.75 0.25 0.81 0.35 0.37 0.25 0.79 0.30 0.30 0.27

(Photosynthetic activity of Fusarium oxysporum, Fv / Fm)

As can be seen from the above table, in Examples 1 to 3, the photosynthetic activity was slightly lowered immediately after the acid treatment but then recovered thereafter, whereas the photosynthetic activity was recovered even after the passage of time I did not. In addition, in the case of Comparative Examples 2 and 4, it was confirmed that photosynthetic activity was not restored in both the kimchi and the persimmon.

On the other hand, the dropout rate of diatomic diatomaceae was investigated in a high salt treatment agent diluted to 10, 20 and 40 times, and the results are shown in Table 4 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 10 times 72.27 78.25 82.36 71.27 79.54 77.02 83.12 20 times 71.18 75.89 79.98 70.56 76.67 74.80 79.95 40 times 65.58 71.45 75.11 65.12 72.56 71.32 75.57

(Percentage of sticking structure dropout,%)

As can be seen from the above table, the lower the dilution concentration, the higher the dropout rate of the attached diatoms was, and the dropout rate was the highest in Example 3 and Comparative Example 4.

The embodiments of the present invention described above should not be construed as limiting the technical idea of the present invention. The scope of protection of the present invention is limited only by the matters described in the claims, and those skilled in the art will be able to modify the technical idea of the present invention in various forms. Accordingly, such improvements and modifications will fall within the scope of the present invention if they are apparent to those skilled in the art.

Claims (7)

10 to 15% by weight of an aqueous phosphoric acid solution having a concentration of 85% by weight, 10 to 15% by weight of a salt, 25 to 30% by weight of an aqueous hydrochloric acid solution having a concentration of 35% by weight, an aqueous calcium chloride solution having a concentration of 35% And 0.1 to 2% by weight of hypochlorous acid water at a concentration of 50 to 200 ppm, wherein the water comprises seawater,
The content of chlorine ions in the high salt treatment agent is 14 to 18% by weight,
The calcium chloride aqueous solution is prepared by adding an aqueous hydrochloric acid solution to the crushed shellfish powder to elute the metals contained in the shellfish in hydrochloride form and separating the solid phase silicon dioxide from the reaction product in which the hydrochloride salt is mixed using a filter, And calcium oxide (CaO) is added to the filtrate to precipitate hydrochlorides except for calcium chloride in the form of hydroxide to separate and remove the precipitated hydroxides.
Wherein the hydrochloric acid aqueous solution used for eluting the hydrochloride is prepared by mixing 30 to 35% by weight of hydrochloric acid aqueous solution at a weight ratio of 3 to 10 times with respect to the shell water. delete delete delete delete delete The method according to claim 1,
Which is diluted 5 to 40 times.