KR20130059376A - Surface-active acid drug for laver farming - Google Patents

Abstract

PURPOSE: A surface-active acid treatment for farming laver(seaweed) is provided to strengthen acidity by adding strong acid, to improve penetration and adsorption of an agent by mixing with a surfactant, and to quickly treat red rot of laver. CONSTITUTION: A surface-active acid treatment for farming laver is prepared by electrolyzing an electrolyte solution containing 0.5-3.5wt% of salt(NaCl) and 2.0-9.5wt% of hydrochloric acid(HCl), generating an acid electrolyte solution containing hypochlorous acid(HOCl), sodium hypochlorite(NaOCl), and hydrochloric acid(HCl), and mixing 0.5-9wt% of strong acid and 0.1-1wt% of surfactant for acid in 90-99.4wt% of the acid electrolyte solution. The strong acid contains two or more kinds among glacial acetic acid(CH_3COOH), sulfuric acid(H_2SO_4), and nitric acid(HNO_3). The surfactant contains a non-ionic surfactant, a cationic surfactant, an amphoteric surfactant, or a mixture thereof.

Description

Surface-active acid drug for laver farming

The present invention relates to a surface active acid treatment agent for aquaculture (seaweed), more specifically 0.5 to 3.5% by weight of salt (NaCl) and 2.0 to 9.5% by weight of hydrochloric acid (HCl). The electrolyte solution is electrolyzed by a membrane-free electrolytic bath to produce an acidic electrolyzed water containing hypochlorous acid (HOCl), sodium hypochlorite (NaOCl), and hydrochloric acid (HCl), and the acid is strengthened to acidity in 90 to 99.4% by weight. (Iii) 0.5 to 9% by weight and 0.1 to 1% by weight of an acidic surfactant, and the permeability and adsorption of the drug is improved by the surfactant effect compared to the conventional seaweed treatment agent for seaweed farming, Remedy of seaweed bottle and blemishes is good, and foreign matters such as ginseng are separated and dispersed by emulsification to improve washing power, and recurrence of seaweed bottle is prevented, and well-washed laver leaves improve nutrient absorption and promote the activity and growth of seaweed. The quality of It relates to a surface active acid treatment agent for seaweed (seaweed) aquaculture, characterized in that the quality of the dried seaweed is improved by washing the debris, foreign matters, miscellaneous algae, bone rot (upper seaweed), and landslides (dead seaweed).

The conventional seaweed acid treatment agent for seaweed for seaweed was found by accident in 1977 when aquaculture farmers in Chiba, Japan, tried to control seaweed bottle and blemishes by accident. In 1980, experiments at the Chiba Prefectural Fisheries Test Center showed that acid treatments were reported to be effective for the relief of diatoms and seaweeds in addition to the blue sea.

Since then, in Korea, acid treatment agents have been used to promote the growth and quality of seaweed by eliminating the miscellaneous growth of laver and gimbal and to wash the bacteria.Inorganic acid treatment agents are concerned about marine pollution. It prohibits its use by notifying the standard of use, and it is allowed to use acid treating agent mainly composed of organic acid and seawater electrolyzed water.

In order to solve this problem, 'Kim Aquaculture Organic Acid Compounds' of Korean Laid-Open Patent Publication No. 1998-069576 (October 26, 1998), 'Kim Aquaculture Organic Acid Compounds' of Republic of Korea Patent Publication No. 1998-072363 (1998.11.05), Republic of Korea 'Organic acid composition for controlling algae attachment to the laver farming net' in Korean Patent Laid-Open No. 2000-0051208 (2000.08.16), 'Oil organic acid for laver farming and the preparation method thereof' in Korean Patent No. 10-0478492 (2005.03.14) , Republic of Korea Patent Publication No. 2008-0103482 (2008.11.28) of the Republic of Korea Patent Registration No. 10-0366899 (2002.12.18) Various attempts have been made to improve the performance of acid treatment agents, such as the strong acidic electrolyzed water generator for seaweed farming.

However, the strong acidic electrolytic acid treatment agent produced by the organic acid treatment agent and the diaphragm electrolyzer manufactured by these conventional techniques is less effective than the inorganic acid treatment agent, and many fishermen are aware of the fact that it is expensive. Preferred use of treatment. In particular, the conventional seaweed acid treatment agent is administered to the gimbal by immersion for 10 to 15 seconds on the shipboard, so the infiltration time and detergency of the drug are insufficient. After the re-initiation there was a problem that the fungal pathogen is immune to the drug effect is not well exhibited the effect of the acid treatment agent. Therefore, it improves the permeability and adsorption of the drug by enhancing the surface active function compared to the conventional acid treatment agent for seaweed farming, so that the control of seaweed bottle and blemishes attached to the seaweed is well-resolved, and the foreign substances such as sesame are dispersed and emulsified by the improvement of washing power. It prevents recurrence of seaweed disease, and well-cleaned laver leaves improve nutrient absorption, promote the activity and growth of laver, and deteriorate the laver quality. It is necessary to develop a surfactant for treating seaweed (seaweed) to improve the quality of dried seaweed.

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In order to solve the above problems, an electrolyte solution containing 0.5 to 3.5% by weight of salt (NaCl) and 2.0 to 9.5% by weight of hydrochloric acid (HCl) is electrolyzed by a membrane-free electrolytic cell to form hypochlorous acid (HOCl), An acidic electrolyzed water containing sodium hypochlorite (NaOCl) and hydrochloric acid (HCl) is produced. The acidic electrolyzed water is 90 to 99.4% by weight, and 0.5 to 9% by weight of strong acid for strengthening acidity, and 0.1 to 1 acidic surfactant. As a result of mixing the weight percent, the acid treatment agent with enhanced surface active function is enhanced by the penetration and adsorption of the drug into the pathogens attached to the gimbal (dog bottle, blemishes, granulosa cells, etc.) It is possible to prevent recurrence of cramps by improving the decomposition and washing function of the strong adhesion material such as ginseng, etc., and well-washed laver leaves can be expected to promote the activity and growth of laver by improving nutrient absorption ability.

Referring to the configuration and operation of the present invention in detail as follows.

In the present invention, an electrolytic solution containing 0.5 to 3.5% by weight of salt (NaCl) and 2.0 to 9.5% by weight of hydrochloric acid (HCl) is electrolyzed by a membrane-free electrolytic cell to dissolve hypochlorous acid (HOCl), sodium hypochlorite (NaOCl), and hydrochloric acid. An acidic electrolyzed water containing (HCl) was produced, and 0.5 to 9% by weight of acidic reinforcing strong acid having a pH of 0.3 or less, and 0.1 to 1% by weight of an acidic surfactant were mixed with 90 to 99.4% by weight of this acidic electrolyzed water. It is.

The acidity reinforcing strong acid having a pH of 0.3 or less is glacial acetic acid (CH ₃ COOH) or sulfuric acid (H ₂ SO ₄ ) or nitric acid (HNO ₃ ) having a concentration of 98% or more, or a mixture of two or more thereof.

On the other hand, the above-mentioned acid-based surfactants are nonionic surfactants (polyethylene glycol type and polyhydric alcohol type, etc.), cationic surfactants (such as amine salt type and ammonium salt type) and amphoteric surfactants (such as amino acid type and betaine type) or these Use at least two of them in mixture.

Here, the acidic electrolyzed water electrolyzed in a membrane-free electrolytic bath using an electrolyte solution containing 0.5 to 3.5 wt% of salt (NaCl) and 2.0 to 9.5 wt% of hydrochloric acid (HCl) is

Salt (NaCl) electrolyte solution

Sodium hypochlorite (NaOCl) is produced by the reaction formula NaCl + H 2 O + 2e → NaOCl + H 2,

Hydrochloric acid (HCl) electrolyte solution

2HCl → 2H + 2Cl

2Cl → Cl ₂ + 2e

The _{Cl 2 + H 2 O → HOCl} + HCl The hypochlorous acid (HOCl) and hydrochloric acid (HCl) by the reaction scheme the acidic electrolytic water to be produced.

Sodium hypochlorite (NaOCl) contained in these acidic electrolyzed waters has less bactericidal power than hypochlorous acid (HOCl), but it kills cells of miscellaneous algae (eg, green, diatom) that damages seaweed. It is a useful ingredient.

In addition, hypochlorous acid (HOCl) produced together has a broad spectrum disinfection effect with superior sterilizing power than sodium hypochlorite (NaOCl), hypochlorite ion ((OCl-), chlorine dioxide (ClO2), and hydrochloric acid (HCl). It is a useful ingredient to combat seaweed germs of seaweed, and hypochlorous acid (HOCl) kills not only normal bacteria but also fungi and viruses, especially spore-forming bacteria that require high pressure and high temperature treatment. For example, Bacillus is a bacterium that is difficult to sterilize even with alcohol, but only glutalaldehyde and hypochlorous acid, which can be used only in hospitals and not in food, can be sterilized. There are various types of things such as green spot disease, mold (redness disease), viral (hinge disease), spore-forming bacteria (diatomaceous disease), and unknown cause (squatting disease). Therefore, hypochlorite (HOCl), which has an excellent bactericidal power and a broad spectrum bactericidal effect, is the most useful ingredient in combating pathogens.

In addition, hypochlorous acid (HOCl) is environmentally friendly and pollution-free compared to other acid treatment agents. When it comes into contact with bacteria or organic matter, it is reduced to water (H ₂ O) immediately after sterilization so that there is no burden on waste water treatment.

On the other hand, hypochlorous acid (HOCl) is changed to hypochlorous ion (OCl-) at high pH, but the efficiency is lowered, but hypochlorous acid (HOCl) is not changed to hypochlorous ion (OCl-) at low pH. ) Is prepared by mixing an acidic electrolyzed water with a pH of 5 or less and a strong acid (强酸 -glacial acetic acid [CH3COOH], sulfuric acid [H ₂ SO _4] , nitric acid [HNO ₃ ] or a mixture of two or more thereof) having an acidity of pH 0.3 or less. It is desirable to bring the acidity of the finished drug to pH 0.5 or below.

On the other hand, hypochlorous acid (HOCl) is mixed with an acidic surfactant to improve the penetration and adsorption of the drug to increase the action capacity of the drug effect and shorten the treatment time, so sterilization effect is 10 to 20 times stronger.

Table 1 below shows hypochlorous acid water (pH4.38, redox potential 1368mV, effective chlorine concentration 22ppm) containing a surfactant (0.5 wt% of nonionic surfactant having a hydrophilic lipophilic balance (HLB) of 14.6). The results of the bactericidal effect test at 20 ℃ were measured for the control group (tap water, sodium hypochlorite water, hypochlorite water).

[Table 1] Hypochlorite water bactericidal effect test results containing a surfactant

As shown in Table 1, hypochlorous acid (HOCl), when mixed with a surfactant, has a strong drug effect and a short treatment time resulting in a sterilizing effect.

Therefore, in the present invention, the acidity reinforcement was mixed with acidic electrolyzed water containing hypochlorous acid (HOCl) to improve acidity and to improve the efficacy by adding an acidic nonionic surfactant that works well in acidity. .

Since the acid treatment agent of the present invention is acidic, it is not preferable to use an anionic surfactant which acts in neutral and alkaline water and does not exert a surfactant effect in acidic conditions. The pH in the solution will affect the dissociation of the surfactant. If the solution is acidic due to high pH, if the amount of hydrogen ions in the solution is high, the degree of dissociation in the solution and the anionic surfactant in which the anion moiety is hydrophilic is lowered in the solution. The fact that the degree of dissociation of the surfactant is lowered means that the surfactant effect is reduced. That is, it is preferable that surfactant used for this invention uses surfactant which acts surfactant effect in acidity. The acid treatment agent has a strong acidity, because if the surfactant does not play a role in the acid can not expect the effect.

On the other hand, acidic surfactants acting in the acidic region include nonionic surfactants (polyethylene glycol type and polyhydric alcohol type, etc.), cationic surfactants (amine type and ammonium salt type, etc.) and amphoteric surfactants (amino acid type and betaine type, etc.). ), It is preferable to use them individually or to mix two or more of them.

The content of the acidic surfactant used in the present invention is 0.1 to 1% by weight. When 0.1% by weight or less is used, the effect of infiltration, adsorption, and cleaning of the drug is insignificant due to low surfactant effect, and 1% by weight. If more than% is used, it will be excessive and the fall of laver from laver will increase and manufacturing cost will be high.

Meanwhile, in the present invention, the salt (NaCl) content of the electrolyte solution is suitably 1 to 3.5% by weight. If the salt content is less than 1% sodium hypochlorite (NaOCl) is produced too little, if more than 3.5% is generated too much, there is a problem that increases the dead cells of the seaweed during administration.

When the hydrochloric acid (HCl) content is less than 2% by weight, hypochlorous acid (HOCl) is generated too little, and when it is more than 9.5% by weight, overcurrent flows in the electrolytic cell, resulting in high energy consumption and easy oxidation of the electrode, which shortens the life of the electrolytic cell. HCl) is most suitable in the state containing 2 to 9.5% by weight.

The present invention adds a strong acid for acidity reinforcement to acidic electrolyzed water containing sodium hypochlorite, hypochlorous acid, and hydrochloric acid to enhance acidity, and then mixes a surfactant acting in acid, thereby improving the penetration and adsorption of drugs. The medicinal effect acts rapidly on seaweed disease and blemishes of the seaweed, and it is possible to prevent the recurrence of seaweed disease by separating and washing the pathogens, such as the host of seaweed germ bacterium, after the administration, and to prevent the recurrence of seaweed disease. As it is well washed, the nutrient absorption of the laver leaves progresses actively, so the activity and growth of laver can be promoted. And using the present invention, there is no need to separately carry out the acid treatment work and the hump removal work, and can be carried out together with the remedy of the bottle and bleeding during the acid treatment work to reduce the labor force and cost of fishermen, thus produced The seaweed has many features and benefits such as the quality of dry seaweed, foreign matter, miscellaneous algae, bone algae, spoiled seaweed (dead seaweed), and landslide (dead seaweed), which improves the quality of dried seaweed.

The following describes the preferred embodiment of the present invention and the effects on the seaweed and miscellaneous algae (green) to verify its action and effects, the seaweed germ control effect of the seaweed, the washing effect of seaweed, the growth effect of seaweed and the environment The test and investigation will be described together.

First of all, the experiment period was from October 2011 to April 2012, and the experiment site was conducted in a seaweed farm in the fish farm of Songan, Haenam-gun, and the indoor experiment was conducted by the Korea Maritime Development Institute. Was done through.

The surface active acid treatment agent of the present invention used in this test was electrolyzed in a membrane-free electrolytic bath with an electrolyte solution containing 96.5% by weight of purified water, 1.0% by weight of salt (NaCl) and 3.5% by weight of hydrochloric acid (HCl). For acidity reinforcement in which acidic electrolyzed water (acid treating agent) containing chloric acid is formed and glacial acetic acid (CH3COOH), sulfuric acid (H ₂ SO ₄ ) and nitric acid (HNO ₃ ) are mixed in a weight ratio of 1: 10: 4. 4.5% by weight of strong acid is mixed with 0.5% by weight of a nonionic surfactant having a polyoxyethylene alkyl ether (RO (CH 2 CH 2 O) m H) and a hydrophilic lipophilic balance (HLB) of 14.6 Was prepared.

As the control acid treatment agent 1 used in this test, an organic acid activity treatment agent was mixed with 15 wt% citric acid, 9.0 wt% hydrochloric acid, and 75 wt% purified water recommended by the National Institute of Fisheries and Algae. In addition, the control acid treatment agent 2 used a seawater electrolytic acid treatment agent in which 1.5 wt% of hydrochloric acid (HCl) was mixed with seawater electrolysis solution having a pH of 2.5, generated by electrolyzing seawater having a salinity of 2.0 in a diaphragm electrolyzer according to the governmental notice. .

In the field experiment, dilute the seawater dilution ratios of the surfactant treatment agent, control acid treatment agent 1, and control acid treatment agent 2 to 25 times, and the soaking time during dosing was treated with 10, 15 seconds before and immediately after treatment and after 72 hours. The change after 1 week was observed. In the laboratory experiment, the seawater dilution ratio of the test group was increased to 25 times, and the immersion time was treated at 10 and 15 seconds to compare the changes before and after the treatment and after 72 hours.

In the field experiments and laboratory experiments, the samples of seaweed and greenery were treated according to the test groups as described above, stained with erythrosine (Erytrhrosin), observed 4 cells under a microscope, and the ratios were obtained. Table 3 shows.

[Table 2] Seaweed and green dead cell rate in field experiments (unit%)

[Table 3] Seaweed and green dead cell rate (unit%) of laboratory experiment

As can be seen in Table 2 and Table 3, the mortality rate of laver and green seaweed was different depending on the elapsed time and immersion time, and the mortality of laver and green seaweed decreased slightly after 72 hours than immediately after treatment. In each experimental group, it was found that the mortality rate increased with a long immersion time.

In addition, compared to the control acid treatment agent 1 and the control acid treatment agent 2, the surface active acid treatment agent of the present invention was found to have a significantly lower cell death rate and a higher cell death rate of green seaweed. It can be seen that the activity maintaining effect and the effect of extinguishing the green sea are excellent.

Next, the dropping rate of the diatoms adhered immediately after the treatment with the acid treatment agent was investigated and the results are shown in Table 4 below.

[Table 4] Dropping Rate of Ginseng and Attached Diatoms (Unit%)

As can be seen in Table 4, the control acid treatment agent 2 showed higher pickling and sedimentation diatom dropout rate than the control acid treatment agent 1, and the pickling and sticking diatom dropping rate of the surfactant treatment agent of the present invention was higher than that of the control acid treatment agent 2. Higher. This indicates that the surfactant treatment agent has a significantly better penetration, adsorption, and cleaning effect than the control group, and has a high rate of dropping out of the sesame and attached diatoms.

Next, photosynthetic activity was measured by light induction analysis on the control acid treatment agent 1 and the control acid treatment agent 2, and the laver and laver leaves administered with the surfactant treatment agent of the present invention, and the results are shown in Table 5 below. .

[Table 5] Measurement of photosynthetic activity of laver and seaweed in the field experiment (average)

In general, photosynthetic activity of laver showed a value of 0.500 to 0.650. In contrast, in the field experiments, as shown in Table 5, each group was lowered immediately after treatment, and then gradually recovered after 72 hours.

In addition, the photosynthetic activity of the green seaweed showed a value of 0.650 to 0.820. In contrast, in the field experiments, the experimental groups tended to be slightly lowered immediately after treatment, and then recovered after 72 hours.

In particular, as shown in Table 5, the surface active acid treatment agent of the present invention showed a higher photosynthetic activity of laver and lower photosynthetic activity of laver than the control acid treating agent 1 and the control acid treating agent 2, so that the activity of laver was good. It was shown that the effect of extinguishing the green sea was well exhibited.

Next, by selecting the gimbal whose laver leaves were grown to the same size (34 ± 1mm), the growth value of laver immediately after the administration of the surface active acid treatment agent, the control acid treatment agent 1 and the control acid treatment agent 2, and after one week was examined. The results are shown in Table 6 below.

[Table 6] Result of measurement of growth value of seaweed (unit mm)

As can be seen in Table 6, the growth value of seaweed, which was the same as immediately before dosing, was measured one week after the administration, and the surface active acid treatment agent of the present invention showed that the growth value of seaweed was larger than that of the control acid treatment agent 1 and the control acid treatment agent 2. appear. That is, the surface active acid treatment agent of the present invention is well separated by multiplying and foreign matter so that the laver leaves are washed, the absorption of nutrients is maximized, the growth of laver is judged to have progressed rapidly.

On the other hand, the sodium hydroxide (purity 99.0%) required to collect waste liquid (diluted 25 times with seawater) after use of the surface active acid treatment agent according to the present invention and neutralize 1 liter was found to be 5.65 to 6.01 g.

In addition, the hydrogen ion concentration (pH), dissolved oxygen (DO), and salt concentration were investigated in accordance with the marine environmental process test method in order to understand the effect of the surface active acid treatment agent on the water quality of the seawater. As a result, the pH range was 8.10∼6.90 in the coastal water and 7.53∼8.32 in the fishery during the test period, and the pH was not changed after the treatment with 7.98∼8.13 after the treatment with the surface active acid treatment agent. During the test period, dissolved oxygen (DO) ranged from 4.9 to 7.1 in coastal waters and 8.3 to 8.9 in test fishing grounds. The water quality was 8.0 to 8.4 mg / l before and after the treatment with the surface-active acid treatment agent. . And during the test period, salinity concentration was 30.1∼34.1 ‰.

On the other hand, the surface active acid treatment agent for seaweed (a seaweed) aquaculture of the present invention can be used in other seaweeds, such as steaming or moxibustion, to rescue seaweed diseases and pirates, and it can be expected that an effect that helps the activity and growth of seaweeds can be expected. It was.

And it is possible to fully consider the acid treatment work by adding agricultural fertilizer or nutrient for the purpose of promoting the growth of seaweed to the surfactant treatment agent of the present invention, in the case of adding the agricultural fertilizer or nutrient to the surfactant treatment agent of the present invention There may be physico-chemical changes to the active ingredients, and there is a concern that marine pollution may occur due to eutrophication of seaweed farms after use, so if you want to do acid treatment with agricultural fertilizers or nutrients, the minimum amount that does not harm seaweed and sea It is preferable to add to use.

As described above, the present invention has been described with reference to the above embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made without departing from the scope and spirit of the present invention. .

Claims (3)

Electrolyte solution containing 0.5 to 3.5% by weight of salt (NaCl) and 2.0 to 9.5% by weight of hydrochloric acid (HCl) was electrolyzed by a membrane-free electrolytic bath to dissolve hypochlorous acid (HOCl), sodium hypochlorite (NaOCl), and hydrochloric acid (HCl). And acidic electrolyzed water containing 0.5 to 9% by weight of acidic reinforcing acid having a pH of 0.3 or less, and 0.1 to 1% by weight of an acidic surfactant. Surfactant for Seaweed (Algae) Aquaculture. According to claim 1, Acidity reinforcement strong acid (强酸) is glacial acetic acid (CH3COOH) or sulfuric acid (H ₂ SO ₄ ) or nitric acid (HNO ₃ ) or seaweed characterized in that two or more of them are mixed (algae) Aquatic acid treatment agent for aquaculture. The seaweed according to claim 1 or 2, wherein the acidic surfactant is a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, or a mixture of two or more of them. A) surface active acid treatment agent.