KR101547566B1 - A Method for Preparing Sterile Water Using the Electrolyzing and Continuous Flow Sterile Water Fish Aquaculture System Using It - Google Patents

Abstract

The present invention relates to a method for manufacturing sterilized water by electrolysis, and a running water type method for culturing fish in sterilized water using the same, more specifically, to a novel running water type method for culturing fish in sterilized water, which applies a novel sterile aquaculture system (SAS) without using antibiotics and vaccines, thus minimizing fish mortality caused by various pathogenic microorganisms. The method for culturing fish using fresh water or sea water comprises the steps of: electrolyzing fresh water or sea water to produce oxidants; destroying pathogenic viruses, bacteria, and parasites to manufacture sterilized water containing lower levels of harmful substances than a drinking water standard; and removing residual oxidants which are toxic to fish through neutralization of the sterilized water.

Description

Technical Field [0001] The present invention relates to a sterilized water producing method using electrolysis, and a method of forming a sterilized fish water using the same.

The present invention relates to a method of producing sterilized water using electrolysis and a method of producing water-sterilized water. More particularly, the present invention relates to an electrolytic method for electrolyzing fresh water or seawater in the production of fish using fresh water or sea water, And sterilizing the water produced by the harmful minerals to produce pathogenic viruses, germs and parasites. By using this, the sterilized aquatic water is neutralized by the neutralization treatment to produce residual oxidants Sterile Aquaculture System (SAS) is applied to minimize the mortality of fish by various pathogenic microorganisms without the use of antibiotics and vaccines by using it as aquaculture water after removing Residual Oxidant Lt; RTI ID = 0.0 > sterile < / RTI >

Fish farming methods include paddling, pond, or pond by ponding freshwater or seawater to the aquatic aquarium with a certain size of net in the river or sea, The water tank in the aquaculture system that is exchanged and cultured is a circulation filtration system that purifies the water in the tank through a drum filter and a biofilter while reducing the exchange rate of the fresh water per day to about 10% (Biofloc), which simultaneously decomposes and metabolizes autotrophic bacteria and other nutritional bacteria in the metabolism of RAS, residual feed, and metabolites secreted by aquaculture fish.

On the other hand, the sea has been rapidly eutrophication due to various pollutants flowing from the land, and as a result, various viruses, pathogenic bacterium and parasites propagate and deteriorate when the offshore farming environment deteriorates. have. Although there is some difference according to the statistics, it shows that the rate of mortality from fry to sale is more than 50% and weight loss rate is more than 40%.

In order to solve this problem, the methods developed for culturing only contaminated seawater and artificially cleaned seawater completely blocked are the 'circulation filtration' and 'bioflex type' mentioned above. However, this method can be applied to some species such as tilapia, eel, eel, carp, salmon, and shrimp which are not sensitive to ammonia nitrogen, nitrite nitrogen and parasites. However, most of the fish species that grow well in clean waters are at high risk, And maintenance costs, and the rate of exchange of new organisms is low, which makes it a good condition for the breeding of various protists.

Therefore, 20 ~ 30 years ago, ozone or electrolysis of fresh water or sea water produced oxidant material to kill viruses, bacteria and parasites in water, then oxidized activated carbon (eg, Cabot corporation Norit GCN 830) has been actively used as aquaculture water (Korean Patent No. 10-1264260), which requires a large quantity of water (small and medium sized fish farms with an area of 5,000 m ² , 60 tons / min. Is required) and is used in the production of drinking water (cola, etc.) in the food industry.

In addition, the aquaculture water (seawater and freshwater) contains some salts such as sodium chloride (NaCl) and sodium bromide (NaBr), and these aquaculture water contains a total residual oxidant (TRO) And various electrolytic reactions such as those listed in the following reaction scheme 1 may occur.

[Reaction Scheme 1]

NaCl → Na + + Cl-

2Cl → Cl ₂ + 2e-

Cl ₂ + H ₂ O → HCl + HOCl

HOCl - > H + + OCl-

H ₂ O → H + + OH-

Na + + OH - > NaOH

Cl ₂ + ₂ NaOH → NaOCl + NaCl + H ₂ O

HOCl + Br- < / RTI > HOBr + Cl-

HOBr → H + + OBr-

In addition, various oxydant materials generated when ozone and ozone dissolving ozone are dissolved in seawater and fresh water may cause various reactions as listed in the following reaction formula (2).

[Reaction Scheme 2]

The dissolved O ₃ → O ₂ + O

_{NaBr + O 3 → NaOBr + O} 2

_{NaCl + O 3 → NaOCl + O} 2

NH ₃ + HOBr -> NH ₂ Br + H ₂ O

NH ₂ Br + HOBr -> NHBr ₂ + H ₂ O

NHBr ₂ + HOBr - > NBr ₃ + H ₂ O

Oxidant substances such as those generated by electrolysis or ozone supply in fresh water or seawater are required to have a concentration of 0.8 ppm (0.8 mg / L) or more and a time of 1 minute or more to kill pathogenic viruses, bacteria and parasites Has been published in the literature [SUISANZOSHOKU, 49 (2), 237-241 (2001); Nippon Suisan Gakkaishi, 67 (2), 222-225 (2001); 44, No. 4, 457-463 (1996)].

Korean Patent Laid-Open Publication No. 2004-19772 discloses a method for producing a bactericidal pathogenic bactericidal solution containing acidic water and diluted alkaline water obtained by electrolyzing seawater, and a method for neutralizing the bactericidal bactericidal solution, Are mixed with each other at a stoichiometric volume ratio and neutralized. However, this is a germicidal solution used for sterilization of fish stocks in aquaculture, and is not applicable to water-based aquaculture methods that continuously treat aquaculture water.

Korean Patent Laid-Open Publication No. 2010-59089 discloses a method of disinfecting seawater by disinfecting seawater by electric potential difference and electrolysis and passing the treated seawater through a chlorine disposer to treat the seawater. And a technique for neutralizing this with hydrogen peroxide has been proposed. However, this invention is not applied specifically to the problem of toxicity of chlorine dioxide treatment and fish toxicity according to the oxidant concentration, and it is applied to outdoor shrimp farm, and the total residual oxidant (TRO) measurement is 0.5 mg / L 0.5 ppm), it is impossible to remove oxidant to less than 0.06ppm, which is the minimum concentration of fish that can be cultured. Therefore, it is not applicable to aquaculture industry. Do. In particular, the hydrogen peroxide used in the neutralization treatment requires a very long period of time for the neutralization treatment even if it is applied together with other auxiliary neutralization means, which is not applicable to the water-based culture method.

Korean Patent Registration No. 10-1064911 proposes a technique of electrolyzing seawater to sterilize ballast water, then storing the ballast water in a ballast water tank for a certain period of time, and then neutralizing the ballast water. However, It is only a technology for removing microorganisms from ship equilibrium water, and it is not applicable to the sterilization level fish culture method necessary for fish culture. In particular, the neutralization treatment in this case can not be regarded as sterilized water because it is neutralized to the marginal line where the creature does not die and survives when the ballast water is discharged, so that it can not be applied to fish.

On the other hand, in order to kill various viruses, bacteria, and parasites that cause diseases in fishes, when the oxidant concentration is 0.8 ppm, 99.9% or more of them are killed if treated for 1 minute or more, It has been reported that it exhibits a sterilizing effect.

In addition, the stability of fish against oxidant was found to be 10 min at the total residual oxidant (TRO) of 0.03 ppm at 50 min, and at 0.04 ppm at the rigid dome. Rainbow trout TRO LC50 (50% ) Was introduced at 0.008 ppm and warns that fish are in great danger to total residual oxidants. In addition, in the case of the flounder which is the most cultured in Korea, it has been reported that it is toxic at 0.01 to 0.04 ppm (mg / L), and the total residual oxidant is 0.003 ppm (mg / L) or less (Proliferation, 44, No. 4, 457-463 (1996)].

Therefore, although pathogenic microorganisms can completely kill at a concentration as low as 0.8ppm in a short time, the total residual oxidant produced by the electrolysis or ozone feeder is completely toxic to fish and can not be used for aquaculture. The reason for this is that after the sterilization using the oxidant, the technique of removing the residual oxidant has not been properly realized.

* With regard to this oxidant removal technology, the activated carbon filter known so far has been applied to various aquidents listed above for the aquaculture water which is applied to a fish farm where a large amount of water is consumed by exchanging fresh one to 20 times a day Has been used in the food industry and in some small nurseries, such as by eliminating up to 0.01 ppm of oxidants, since it is not industrialized because it requires a tremendous processing capacity and area to remove fish to levels below 0.003 ppm sufficient to propagate fish.

In this regard, in the Korean Fisheries Science Journal, 46 (5), 534 - 539 (2013), when short-term treatment of live shellfish was performed at 0.07 to 0.09 ppm (mg / Vibrio bacteria were not detected after one hour, and they were not killed when exposed for 1 week. Therefore, it is suggested that they can be used for the purpose of killing Vibrio spp. Before sale to consumers in live fish shops. However, It is absolutely impossible to do so, and there are cases where fish and shellfish are dead and are not practically used.

Thus, in the case of the conventional fish farming method, the water-based farming method of continuously supplying the aquaculture water by the sterilization method can not be applied, and it is necessary to use various antibiotics, vaccines or even 40-50% In fact, we are continuing efforts to reduce the mortality rate by cyclical filtration (RAS) and bioflactive (BioFloc) depending on the species. Therefore, it is urgent to develop a more efficient and economical new fish culture system in the fisheries industry.

On the other hand, in case of sterilization of fresh water and seawater by electrolysis apparatus or ozone in the production of sterilized aqua culture water applied in such a fish culture method, O ₂ , Cl ₂ , Br _{2 ,} O _{3 and} OH radicals are first generated and then these materials are secondarily produced as NaOCl, ClO ₂ , NaOBr, HOCl, HOBr and the like, and these materials are various organic substances existing in fresh water and seawater (OH) radicals are instantaneously generated and disappear, and CO is generated. After the ozone is generated at a potential equal to or higher than the Ozone ORP (Oxidation Reduction Potential) It has been argued that BrO ₃ - (Bromate) occurs when an overcurrent or overvoltage occurs in the system.

In addition, it was possible to produce aquaculture water free from pathogenic microorganisms by sterilizing the aquaculture water by the electrolysis method. However, the technology to remove the oxidant from the fish to the safe range and the by- Manufacture of sterile aquaculture water to contain harmful substances of human and fish harmful substances is prohibited because of high cost and can not be put into practical use for aquaculture. In order to sterilize ship ballast water and to be approved by IMO (International Maritime Organization) And it is diluted with a large amount of seawater at a high speed so that it is utilized as a technology for disinfecting equilibrium water which does not damage fishes living in the sea.

The sterilized water culture method of sterilizing the aquaculture water by electrolysis has not yet been put into practical use because the method of sterilizing by electrolysis and then removing the TRO material by activated carbon is known , And the method is being utilized for small seedling cultivation field or research use.

1. Korean Patent No. 1264260 2. Korean Patent Publication No. 2004-19772 3. Korean Patent Publication No. 2010-59089

1. SUISANZOSHOKU, 49 (2), 237-241 (2001) 2. Nippon Suisan Gakkaishi, 67 (2), 222-225 (2001) 3. Proliferation of fish, Vol. 44, No. 4, 457-463 (1996-H8) 4. Korean Journal of Fisheries Science, 46 (5), 534-536 (2013)

In the present invention, a system for treating aquaculture water capable of minimizing the mortality of fish by various pathogenic microorganisms without using antibiotics and vaccines in a system for supplying fish stock water, which utilizes an oxidant generated by an electrolysis method, And to develop a method for producing aseptic aquaculture water containing less than the water to be eaten.

In addition, while providing the above harmless sterilization aquaculture water continuously, it is possible to provide a new fish production method and system with low cost and high efficiency as compared with conventional circulation filtration (RAS) and biofloc .

The present inventors produced oxidant in the aquaculture water to sterilize the fish pest, but when the oxidant remaining in the aquaculture water is removed by a specific neutralization treatment method, the concentration of the oxidant in the aquaculture water is 0.06 ppm (mg / L) or less, Preferably not more than 0.01 ppm, more preferably not more than 0.003 ppm, so that the sterilized water in a safe state in the fish can be applied to the aquaculture system in a water-based system. Thus, the present invention has been accomplished.

Therefore, an object of the present invention is to provide a sterilized water producing method in which aquaculture water is sterilized by an electrolysis method.

It is another object of the present invention to provide a method for sterilizing fish which can sterilize aquaculture water by oxidant and then remove oxydant by a neutralizer to supply safe aquaculture water to fish safely.

Still another object of the present invention is to provide a new concept of a water-sterilized fish culture method that enables a large-scale fish culture in an eco-friendly manner while processing aquaculture water in a very economical and efficient manner.

Still another object of the present invention is to provide a sterile aquaculture system (SAS) for aquacultural fish culture as a new fishery system.

In order to solve the above-described problems, the present invention provides a method for manufacturing a semiconductor device, which comprises using a titanium metal or a niobium as a base metal and doping a metal selected from the group consisting of ruthenium, iridium, tantalum, Electrolysis method in which seawater and fresh water are electrolyzed by using a metal selected from among oxides thereof coated with 0.1 to 30 μm as an anode to adjust the voltage to 2.51 to 4.4 volts so as to produce bromate to be less than 10 ppb To provide a method for producing sterile wastewater water.

Further, the present invention provides a method for producing aquaculture water, comprising the steps of: (a) supplying fresh water or sea water and supplying it as aquaculture water; (b) an oxidant generating step of generating an oxidant by applying the electrolysis method as described above in the supplied number of the aquarium; (c) a sterilization treatment step in which oxidant remains in the aquaculture water in a continuous flow of aquaculture, thereby sterilizing the fish pests in the aquaculture water; (d) a neutralization treatment step of removing the oxidant so that the residual oxidant in the aquaculture water is 0.06 ppm or less by injecting a neutralizer into the sanitized wastewater water in the state where the water is continuously flowing; (e) supplying a sterilized aqua regenerated water to the culture water tank of the fish; And (f) a culture wastewater discharging step of discharging the culture wastewater used in the fish culture from the culture water tank.

In addition, the present invention provides a water supply system comprising: a water supply unit for supplying fresh water or sea water to aquaculture water; An oxidant generating unit provided with oxidant generating means and generating an oxidant by the electrolysis method in the supplied aqua regia; A sterilizing treatment section including an aquaculture treatment chamber for allowing the oxidant to remain in the aquarium while the aquaculture-producing aquaculture water is supplied and the aquatic bacteria in the aquaculture water are sterilized; It has a neutralization agent input unit for neutralizer input during the movement of sterilized aquaculture water. It also contains a aquaculture water transfer chamber to keep the remaining aquaduct in the aquaculture water down to 0.06ppm or less by neutralization, A neutralization processing unit; A sterilization water supply unit for supplying the sterilized aqua regenerated water to the aquaculture water tank; And a culture wastewater discharge unit for discharging the culture wastewater used from the culture water tank.

The present invention relates to a neutralization treatment method using a neutralizing agent which is safe for fishes after neutralization treatment by electrolysis at a low cost and a high efficiency method using electrolysis under specific conditions, It is possible to effectively sterilize aquaculture water, thereby enabling continuous sterilization treatment.

That is, after killing various pathogenic microorganisms in aquaculture, the present invention substantially completely removes harmful residual oxidant substances in fishes to 0.06ppm or less, preferably 0.01ppm or less, more preferably 0.003ppm or less, By continuously supplying sterilized water to the aquaculture tank, it is a highly practical technology that can dramatically reduce mortality caused by harmful microbes such as various pathogenic microorganisms.

The aquaculture method and the sterilization system according to the present invention can produce aquaculture fish in a mass production manner without any antibiotics. In addition, the increase of consumption of aquaculture fish not only contributes to income increase of the aquaculture industry, but also enables fish farming in economical environment without being affected by natural disasters such as typhoons and spread of pathogenic microorganisms, It is expected to be possible.

Particularly, in the present invention, the electrolysis method can be carried out in a specific voltage range to produce sterilized water, thereby minimizing harmful substances such as bromates. Therefore, the application of the aquaculture system, There is a possible effect.

FIG. 1 is a process diagram illustrating a method of producing a water-sterilized fish according to the present invention.
FIG. 2 is a schematic view showing an example of a typical sterile water fish aquarium system including a sterilizing treatment unit and a neutralization treatment unit including a plurality of chambers as an embodiment of the water-based sterilization system for fish culture according to the present invention.
3A and 3B are views showing, as one specific example, the constitution of the sterilization processing part and the neutralization processing part which are the main parts in the sterilization system according to the present invention, 3 is a diagram schematically showing the planar structure of the eight chambers constituting the sterilization treatment section and the neutralization treatment section.

Hereinafter, the present invention will be described in more detail as an embodiment.

The present invention relates to a sterilizing system (SAS) which applies a new concept of a sterilization system (SAS) to sterilize and neutralize a large quantity of aquaculture water while continuously supplying the aquaculture water, And a method of fish culture. The method for cultivating a water-based fish according to the present invention is essentially applied to a system for sterilization of fish, and the method for cultivating the water-sterilized water according to the present invention can be explained by a process diagram as shown in FIG.

The present invention is characterized by a water-based sterilized water culture method which can be constituted so that the water supply step, the oxidant generation step, the sterilization treatment step, the neutralization treatment step, the sterilization water supply step, do.

In the present invention, the aquaculture water supply step (a) is a step of collecting fresh water or sea water and supplying it as aquaculture water.

In this step (a), freshwater is constantly collected from the place where fresh water is continuously supplied, or seawater is continuously collected from the sea and supplied as ponds by pumping or natural spillage. According to a preferred embodiment of the present invention, water can be collected using a long pipe or the like in a lake or a sea, and the water can be collected from the water using a pump or the like. The number of the aquaculture aquaculture contains various harmful fishes, so 40 ~ 50% of the aquaculture aquaculture occurs when applied as aquaculture. Therefore, in order to sterilize various fish harmful bacteria contained in the initial culture water, it is sent to the next step (b) of oxidant generation so as to create a sterilization treatment environment.

The step (b) is a step of generating an oxidant in the supplied culture water, wherein the oxidant is generated by using electrolysis as a means for generating an oxidant in the culture water.

In the present invention, the term 'oxidant' refers to a substance having a function to kill pathogenic microorganisms such as viruses, bacteria and parasites. According to the present invention, the oxidant includes, for example, NaOBr, NaOCl, NaClO ₂ , HOCl , HClO _{2 ,} HOBr, Cl ₂ , Br ₂ , OH Radical, O ₃ , NH ₂ Br, NHBr _{2 ,} NBr ₃ And the like. However, when the fresh water or seawater is subjected to electrolytic treatment, about 5 to 20 kinds of various bactericidal substances are produced depending on the quality of the initial cultivation water, and many oxidative substances are generated from these substances. Therefore, in the present invention, It is called Oxidant.

Therefore, the oxidants produced from such aquaculture can not be regarded as a simple oxidizing agent. It is a highly active and insecure material, which can be completely isolated and quantitatively disinfected if it is left in the atmosphere for a long time.

According to the present invention, the aquaculture produced by electrolysis (TRO, Total Residual Oxidant) is used.

According to the present invention, electrolysis is performed under specific conditions in application to an electrolysis method for generating such oxidants. In the present invention, it is very important to produce sterilized water by using an electrolysis method.

The method for producing sterilized water using the electrolysis method according to the present invention will be described in detail as follows.

In general, electrolysis of seawater or freshwater for fish culture can produce oxidants, and sterilized water can be produced using these oxidants. In relation to this, a method of generating less THMs, HANs, HAAs, Bromates, and CO, which are known to be harmful to humans and harmful to fish, is described in Aquaculture 264 (2007) 119-129 at 1.8-2.5 Volt 2 Liter / min flow rate Electrolysis of the aquaculture water produces 0.5-0.3 ppm (mg / L) of TRO, which is enough to sterilize the aquaculture water and produce THMs, HANs and HAAs below the water standard. There is a performance study. However, there is no report that bromate, known as a human carcinogen, is produced below the water standard.

The method of manufacturing sterilized water according to a preferred embodiment of the present invention is a method of producing sterilized water containing harmful substances containing such bromate at a water level or lower.

Trichloromethane, Dichlorobromomethane, Dibromochloro-methane, Tribromomethane, 1,2,3-Trichloropropane and 1,2-dichloroethane are known to be included in the sterilized water by electrolysis. HANs (Halogennated acetonitriles) include Monochloroacetonitrile, Monobromoacetonitrile, Trichloroacetonitrile, Dichloroacetonitrile, Bromochloroacetonitrile, Dibromoacetonitrile, Tribromoacetonitrile, Bromodichloroacetonitrile, Dibromochloroacetonitrile and the like are known, HAAs (Halogenated acetic acid) is Monochloroacetic acid, Monobromoacetic acid, Dichloroacetic acid, Dalapon, Trichloroaceticacid, Bromochloroacetic acid, Dibromoacetic acid, Bromodichloroacetic acid, Chlorodibromoacetic acid, and tribromoacetic acid. Other substances include chloropicrin.

However, in relation to the technology that generates less THMs, HAAs and HANs when sterilization of seawater and fresh water by electrolysis, Journal of Environmental Protection 2010. 1. 456 - 465 suggests that the oxidative components The concentration of Trichloromethane (Chloroform), Bromodichloromethane, Dibromochloromethane, and Tribromomethane (Bromoform) in the THMs over time was controlled by adjusting the concentration of residual chlorine to 1 to 4 ppm with NaOCl On the other hand, when sterilizing seawater by electrolysis, the concentration of human and fish toxic substances is reported to be higher than that of electrolysis of ship ballast water according to the Journal of the Korean Society for Marine Environment and Energy, Vol.16 No 2 88-101, May 2013 The emission concentrations of the harmful substances of various fishes, which are generated when sterilized by disassembly and discharged, are analyzed as shown in Table 1 below.

Ingredients Concentration after electrolysis Before electrolysis, Eating water standard (Korea) Bromate (ug / L) 51.1 - 10 THMs (ug / L) 1,2-Dichloroethane 0.36 - 20 Dibromomethane 0.23 - Dichlorobromomethane - - 30 Dibromochloromethane 1.12 - 100 Trichloromethane 2.08 1.74 80 Tribromomethane 42.2 0.28 HAAs Monochloroacetic acid 25.8 2.31 Dalapon 0.67 - Trichloroacetic acid 2.82 - Tribromoacetic acid 6.37 - Monobromoacetic acid 1.17 - Dibromoacetic acid 9.26 - HANs Dibromoacetonitrile 12.7 - 100

In the present invention, as a method capable of producing sterilized water while introducing seawater and fresh water into an electrolysis tank, it is necessary to maintain a condition such that the TRO concentration is 0.1 to 7 ppm, which is a sterilizable concentration, and at the same time, The present invention relates to an electrolytic method and a process for producing the same.

According to the present invention, an electrolytic apparatus for sterilizing aquaculture water generally produces less harmful substances by electrolyzing the electrolyzed water at a rate of 2.5 volts or less, but if the electrolytic apparatus is below 2.5 volts, the current density flowing through the electrode plates And the TRO concentration of 0.1 to 7 ppm is preferably 0.5 to 7 ppm for a yield of about 3,600 m 3 / h on the basis of a typical water surface area of 5000 m 2, as well as a low economic efficiency. - It is not possible to sterilize by 3.0ppm TRO.

Therefore, according to the present invention, electrolysis is preferably performed at 2.5-4.4 volts, more preferably 3.0-4.2 volts, depending on the content of sodium bromate (NaBr) in seawater and fresh water, It is a desirable electrolysis condition to sterilize Bromate to below water standard and to minimize mortality.

According to the present invention, electrolytic treatment was performed on seawater at a condition of 3.5 V to produce oxidant content of 1 ppm TRO, sterilized, and analyzed for components contained in the sterilized water.

Ingredients Number of forms after electrolysis
([Mu] g / L) Before electrolysis,
([Mu] g / L) Eating water standard (Korea)
([Mu] g / L) Total Trihalomethane (/ / L) 23.7 2.02 100 Trichloromethae (Chloroform) nd nd 80 Dichloroacetonitrile 0.18 nd 90 Trichloroacetonitrile nd nd 4 Total Haloacetic acid 7.84 nd 100

According to a preferred embodiment of the present invention, the electrode for electrolysis is made of titanium metal or niobium as a base metal, and in the case of an anode, ruthenium, iridium, tantalum ) And platinum, or a metal selected from the group consisting of oxides thereof is coated in a thickness of 0.1 to 30 μm to electrolyze seawater and fresh water.

In particular, according to a preferred embodiment of the present invention, it is preferable to adjust the voltage to 2.51-4.4 volts at the time of electrolysis. In this case, the bromate is produced to 10 ppb or less. If the voltage is less than 2.51 volts at the time of electrolysis, the amount of oxidant generated is too low to lower the sterilizing effect, which is unpreventable and can not be practically used. If the voltage is more than 4.4 volts, the content of bromate in the sterilized water is not less than the reference value.

Accordingly, the present invention includes a method of producing sterile water in which bromate is produced at a content below a standard value by using an electrolysis method under the above-described conditions.

In addition, the present invention includes a method of culturing fishes in a water-based method using sterilized water produced by the electrolysis method as described above.

According to a preferred embodiment of the present invention, in the oxidant production step, the oxidant is preferably produced to be 0.1 to 7.0 ppm based on the total residual oxidant (TRO) amount in the culture water. In the oxidant generation step, the generation of such oxidants creates an environment capable of disinfecting various fish harmful bacteria in aquaculture water. If the total residual oxidant in the aquaculture is less than 0.1 ppm, it is difficult to kill various pathogenic microorganisms such as viruses, bacteria and parasites which are harmful microbes of fish. In case of exceeding 7.0 ppm, the process of removing the oxidant by neutralization (Trihalomethane, halogenated acetonitriles, halogenated acetic acid, etc.) may be generated, and it is preferable to produce oxides within the above range. The residual amount of such oxidants can be appropriately adjusted within the above range in consideration of the quality of the aquaculture water, the species of the fish and the aquaculture environment, and it can be produced at a concentration of 0.1 to 7.0 ppm with respect to the whole aquaculture water, It is also possible to generate a sterilization environment by diluting the water to a concentration of 0.1 to 7.0 ppm with respect to the total number of aquaculture by generating a high concentration of 1.0 to 700 ppm in a part of the yield.

Next, the number of forms in which the oxidant is generated is sent to the sterilization treatment step (c).

The step (c) is a sterilization treatment step for sterilizing the fishes in the aquaculture water while oxidant is available in the aquaculture water. At this stage, the oxidizing agent is contacted or bound to the harmful microorganisms contained in the aquaculture water during the time when the culture water flows down or up by the difference in height between the sterilizing water tank and the ground. At this time, the aquaculture water continues to flow to the next stage during the sterilization treatment process and maintains the water flow state.

In the present invention, the term 'harmful microorganism of fish' means to include all pathogenic bacteria and microorganisms which directly or indirectly affect diseases of various fishes, such as viruses, bacteria and parasites, pathogenic microorganisms, and the like.

In general, in order to kill harmful microorganisms such as pathogenic viruses, bacteria and parasites in the sterilization method of the aquaculture water, ultraviolet (UV) irradiation is performed to feed the aquaculture water how to cases of farms that, one day replace the 1-24 rotating saemul been reviewed, handling the huge volume of the tank form an area 4,960m ² (1,500 square meters) based on approximately 60 tons per minute (3,600 ton / hour) and Facility Fee It is not easy to use it because it is too expensive to be put into practical use, and there is a major drawback that ultraviolet rays are not irradiated to water and the bactericidal effect is remarkably lowered when a large amount of suspended or suspended matter is contained in aquaculture water. Can be used, but not in most fish farms.

However, in the above-described sterilization treatment step according to the present invention, the oxidant, which is a bactericidal substance, is contained in the culture water, and the mechanism for immediately killing the harmful microbes by contacting with the fish harmful bacteria is adopted. And the facility cost and maintenance cost are lower than that of the ultraviolet ray sterilization. Especially, the oxidant remaining in the aquaculture water has enough sterilization and insecticidal effect even at a very low concentration of about 0.5 ~ 1 ppm, The effect is very good.

However, since the oxidants remaining in the aquaculture water for sterilizing these fish harmful bacteria are not only killed the harmful microorganisms of fish but also cause the dead fishes and shellfish to be killed, after the sterilization treatment step, It is impossible to use. Therefore, after the neutralization treatment step for removal of residual oxidant, it must be supplied to the aquaculture tank in which the fish are cultured as sterilized water.

According to the present invention, the total residual oxidant (TRO) can be measured in order to measure the degree of residual oxidant suitable for the sterilization treatment step or the subsequent step. The commonly known oxidative measurement method is a physical measurement method using a chemical method and a device using color development reagents and electrodes such as N, N-diethyl-p-phenylenediamine (DPD), and tolidine Can be used.

As an example of the chemical measurement method, about 50 ml of a sample is adjusted to pH 6 by adding 1 N sulfuric acid, and then 5 ml of a 1% KI solution is added. Thereafter, 1% starch solution solution is added to the solution to make blue appear. Titrate the solution with 0.001 N sodium thiosulfate solution to the end point. The total residual oxidant concentration is calculated according to the following equation (1).

[Equation 1]

Total Residual Oxidant (ppm = mg / L) = aF x 1000 / x x 0.024 (0.03456)

In this case,

a: Amount (ml)

F: 0.001 N sodium thiosulfate solution Factor

X: Seawater sample (ml)

0.024: Ozone (O ₃ ) amount corresponding to 0.001 N sodium thiosulfate solution

0.03546: Cl amount corresponding to 0.001 N sodium thiosulfate solution

(Multiplied by ₂ if indicated by Cl ₂ )

.

However, when the above-described chemical measurement method is used in the measurement of the residual amount of oxidant, measurement is not performed well when the oxidant concentration is as low as 0.5 ppm or less.

For example, HACH Pocket Colorimeter II can be used as a color measurement method for measuring the residual amount of oxidant, for example, as a portable device. This can be measured only when the oxidant concentration is 0.02 ppm or more. Total Residual Oxidant (TRO) produced by the electrolysis was measured and then the factor of 0.68 (O ₃ 48 / Cl ₂ 71).

As another example, a precision instrument can be used. For example, AW400 (Residual Chlorine monitor, ABB Limited (USA)) or Mico 2000 (SIEMENS) instrument can be used. The sensitivity is 0.001 ppm. The residual chlorine oxides, and the total residual ozone. Therefore, it is necessary to understand the sum of the analyzed values as a TRO analysis value, but there is a defect that many errors occur in seawater.

As another example of the method for measuring the residual amount of oxidant, ES05310.2a and IS07393-2 (1985) OT-method, DPD-method, etc., It can also be measured.

As described above, the sterilization process for the harmful microorganisms contained in the aquaculture water using the oxidant remaining in the aquaculture water can be carried out smoothly while the aquaculture water moves in the aquaculture water transfer chamber. In this case, the sterilization treatment time in the sterilization treatment step is such that all the harmful microbes contained in the aquaculture water are killed, which can be determined depending on the condition of the aquaculture and the residual amount of the oxidant, but preferably 1 to 32 minutes Preferably about 4 minutes to 8 minutes. If the sterilization treatment is carried out for less than 1 minute, it is necessary to generate a high concentration of residual oxidant, and in order to safely neutralize and remove the oxidant generated at a high concentration, various substances which are expensive and harmful to fish (trihalomethane, halogenated acetonitrilees, Etc.). In addition, when the sterilization treatment step is performed for a long period of time, for example, more than 32 minutes, it is convenient to remove the oxidant by sterilizing the oxidant residue for a long period of time by lowering the residual concentration of the oxidant, If the sterilization time is too long, harmful substances may be produced. If the sterilization time is too long, it may be harmful to the fish.

As described above, the aquatic wastewater which has undergone the sterilization treatment step is sterilized but the residual oxidant must be removed. Therefore, in the present invention, the sterilized aquaculture water is sent to the neutralization step (d) for the removal of the oxidant.

In the neutralization treatment step (d), a neutralizer is added to the sanitized wastewater to remove the residual oxidant. In this step, the oxydant remains in a trace amount or substantially all of the oxidant is removed, Of water quality.

According to the present invention, in the neutralization treatment step, a neutralizing agent is added. The neutralization treatment of the present invention is a method capable of removing oxidant at low cost and high efficiency.

In general, in the case of the conventional activated carbon used as a method for removing oxidant, the water containing oxidants at a concentration of 0.1 to 7.0 ppm (mg / L) Although 60 ton / min is supplied to fish farms, it is necessary to use large size or several activated carbon filtration tanks to remove oxidant to below 0.003 ppm suitable for fish culture. However, activated carbon can not be removed immediately until 0.003 ppm and only 0.01 ppm is removed . Of course, it is possible to remove up to 0.003 ppm when the activated carbon is subjected to various stages or when the oxidant is low in 0.01 ppm in the aquaculture water, but this is not applicable in the fish farm, and it is not possible to use the small seedling cultivation field, It can only be used for practical purposes.

However, in the case of the present invention, it is possible to remove the residual oxidant through a neutralization treatment using a neutralization treatment method using a neutralizer which is safe to fish at a concentration below a certain level using a minimum amount of neutralization agent.

According to a preferred embodiment of the present invention, in addition to the neutralizing agent addition, aeration, neutralization accelerator or both may be additionally used in the neutralization step. By using these means, it is possible to further shorten the neutralization time or to sufficiently remove the oxidant, neutralize the oxidant by a low-cost, high-efficiency method, to reduce the oxidant residue to 0.06 ppm or less, preferably 0.01 ppm or less Can be removed to 0.003 ppm or less, and thus can be widely used.

According to a preferred embodiment of the present invention, the step (c) is preferably carried out for 1 to 28 minutes, more preferably 4 to 12 minutes. The sterilization treatment time in the sterilization treatment step can be determined in consideration of the quality of the aquaculture water, the initial residual amount of oxidant, and the like. This sterilization treatment step means the time before the neutralization treatment step is performed, and the sterilization process can be continued for a while by some remaining oxidant even in the neutralization treatment step.

According to a preferred embodiment of the present invention, in the neutralization treatment step, the addition amount of the neutralizing agent is preferably such that the amount of the oxidant remaining in the aquaculture water and the neutralizing agent is slightly greater than the equivalent amount of the neutralizing agent, It is preferably added in an equivalent amount of not more than 2 times. Because the neutralizing agent is not used for neutralization if the neutralizing agent is added too much, the remaining neutralizing agent can damage the fish. Therefore, the neutralizing agent itself or the substance generated after neutralization uses the extremely limited range of substances that should not be harmful to the fish at all It is because it must.

Therefore, according to a preferred embodiment of the present invention, it is preferable to use at least one neutralizing agent selected from sodium thiosulfate, sodium dithionate, ascorbic acid and cysteine as the neutralizing agent used in the neutralization step. In the present invention, at least one selected from the group consisting of sulfur dioxide, sodium sulfite, acidic sodium sulfite and hydrogen peroxide may be used as the neutralizing agent in addition to the above components. According to the present invention, when a neutralizing agent other than the general neutralizing agent is used, it takes a long time for the neutralization treatment or it is difficult to neutralize the residual oxidant to 0.06 ppm or less, more preferably 0.01 ppm or less, without further neutralization treatment. In addition, when the neutralization treatment time is long, a lot of chambers for neutralization treatment are required, and a lot of space or equipment for neutralization treatment is required, or it is very uneconomical and excessive use of neutralizing agent is required, And other harmful problems arise.

In the present invention, both sodium thiosulfate and sodium dithionate which are used as the neutralizing agent are applicable to anhydrides and hydrates. In addition, the neutralizing agent may be prepared by adding an aqueous solution into sterilized water after the sterilization treatment step is completed.

The neutralizing agent used in the present invention means a substance used for eliminating the toxicity of the residual oxidant contained in the aquaculture water. Since the neutralizing agent also shows toxicity to fish, it is necessary to minimize the amount of the neutralizing agent used. In other words, the neutralizing agent neutralizing the oxidant should be safe for the fish, and the material produced after neutralization must be safe for the fish. However, since the wastewater discharged into the sea and the river does not hinder the environment, COD, and BOD of the product.

Therefore, according to the present invention, it is preferable to use the neutralizing agent as described above, and to minimize the amount of the neutralizing agent used. According to a preferred embodiment of the present invention, the amount of the netralizer used is required to be at least equal to the ratio of equivalent equivalent to the total remaining amount of oxidant (TRO), and equal to or less than twice the equivalent amount. After the neutralization treatment step, it is converted into a safe neutral salt which does not adversely affect the fish, so that the oxidant is completely removed or a trace amount of the neutralized water is obtained, and the residual amount of the neutralizing agent after the neutralization treatment is sterilized to a level not harmful to the fish.

In one embodiment, when the oxydant is generated in the form number, there are 5 to 20 kinds of oxidants in the form number. Among the oxidants, for example, sodium hypochlorite (NaOCl), sodium hypochlorite (NaOBr ) And O ₃ And so on. In this case, the reaction of the neutralizing agent with respect to the component of oxidant present in the culture water in the neutralization treatment step is neutralized through a reaction mechanism as shown in the following reaction formula 3, whereby the residual oxidant in the sterilized water is removed You can. An example of the reaction can be illustrated by the following reaction formula (3).

[Reaction Scheme 3]

NaOCl (oxidant) + H ₂ O ₂ (oxidizing neutralizer) → NaCl + H ₂ O + O ₂ ↑

NaOBr (oxidant) + H ₂ O ₂ (oxidizing neutralizer) → NaBr + H ₂ O + O ₂ ↑

Zn (metal promoting neutralizer) + NaOCl (oxidant) → ZnO + NaCl

NaHSO ₃ (reducing neutralizer) + NaOCl (oxidant) → NaCl + NaHSO ₄

NaOCl _{(oxidant) + Na 2 S 2 O 3} ( neutral salt-type _{neutralizer) + 2NaOH → NaCl + 2Na 2} SO 4 + H 2 O

O ₃ (oxidant) + 3 SO ₂ (gas neutralizer) + 3H ₂ O → 3H ₂ SO ₄

2Na ₂ S ₂ O ₄ (neutral salt type neutralizing agent) + H ₂ O -> Na ₂ S ₂ O ₃ + 2NaHSO ₃

As shown in the above reaction formula, according to the present invention, it is possible to sterilize the residual oxidant present in the aquaculture water by neutralizing with the neutralizing agent, , There is substantially no residual oxidant harmful to the fish in the state where all of the fish harmful bacteria are killed and the neutralization agent is not remained or remains in a trace amount and does not affect the fish at all, As shown in FIG.

According to the present invention, in order to minimize the use amount of the neutralizing agent in the neutralization treatment step, an environment for using less of the neutralizing agent can be additionally provided.

To this end, during the neutralization process, a neutralization accelerator, which is a metallic neutralization component, may be added to the mobile chamber while the sterilized water is moved during the neutralization process. According to a preferred embodiment of the present invention, as the neutralization accelerator which can be additionally used in the neutralization treatment step, for example, one or more selected from transition metals and metals belonging to Group IVA may be preferably used, more preferably Group IIIB, VIIIB At least one metal selected from Group IVB, Group IB, Group VIB and Group IVA can be used, and most preferably at least one metal selected from the group consisting of zinc, iron, copper, chromium and tin, And neutralization treatment for removal of oxidant can be preferably performed. Wherein the neutralization promoter is selected from the group consisting of mesh drawing, powder, porous or non-porous granule, porous pellet, cylindrical block, or plate The neutralization accelerator may be added in one or more forms, which may facilitate the neutralization reaction in the aquaculture water and allow the reaction to occur more readily.

Also, according to a preferred embodiment of the present invention, the neutralization step (d) may further include an aeration step of removing the oxidant by injecting air. In this case, the air injecting means applied to the aeration step for injecting air may be typically performed through a blower and a compressor, but the present invention is not limited thereto. If the aeration step for air injection is additionally applied in the neutralization step, the neutralization reaction can be promoted as well as the neutralization accelerator to further improve the removal rate of the oxidant, and the neutralization accelerator can be activated And can be moved and floated. According to the present invention, in place of the aeration, the neutralization promoter may be suspended in the aquaculture water through agitation, or agitation may be performed simultaneously with the aeration.

According to a preferred embodiment of the present invention, in the neutralization step, the addition of the neutralization accelerator of the metal component and the aeration step may be additionally performed at the same time. In this case, when the air is injected from the lower part by the aeration step, the neutralization promoter of the metal component, which is further charged in the chamber through the sterilization treatment step and in the state where the neutralizing agent is introduced, is suspended in the water in the chamber and actively moved So that a highly desirable neutralization treatment is possible.

According to the present invention, it is relatively easy to remove the oxidant remaining in the sterilized aquaculture water by the above-described method until the residual amount of the oxidant in the aquaculture is 0.06 ppm, preferably 0.01 ppm, when the neutralization treatment is carried out using the neutralizing agent Do. However, it may not be easy to remove the residual amount of oxidant in the aquaculture water to 0.005 ppm, more preferably 0.003 ppm. In this case, in order to remove a large amount of aquaculture water in a short time to remove the residual amount of oxidant to 0.003 ppm or less, it is necessary to remove sodium thiosulfate, sodium dithionite, ascorbic acid, cysteine, sulfuric acid gas, sodium sulfite, acidic sodium sulfite and hydrogen peroxide At least one neutralizing agent selected from the group consisting of Particularly, in order to shorten the neutralization treatment time, when the neutralization accelerator is further added as a catalyst component at the same time as the addition of the specific neutralizing agent and the aeration step, the rate of progress of the neutralization reaction, that is, It will accelerate. For example, it is possible to remove up to 0.003 ppm or less of oxydant remaining in a large number of aquaculture water at a rate of 60 ton per minute or less within a maximum of 1 hour.

Meanwhile, according to a preferred embodiment of the present invention, the sterilization treatment step (c) and the neutralization treatment step (d) can be carried out continuously in the process of continuously moving the form water. According to a preferred embodiment of the present invention, steps (c) and (d) for sterilization treatment and neutralization treatment for such aquaculture water can be performed in a plurality of chambers partitioned by, for example, (C) and the neutralization step (d) of the step (d) can be sequentially performed in each of the chambers partitioned in the flow direction in one direction, have.

According to the present invention, the chamber in which the sterilization treatment step is performed and the chamber in which the neutralization treatment step is performed may each be constituted by a plurality of chambers. Preferably, the chambers are formed so as to pass through the upper and lower ends of the chambers, After the sterilizing treatment step is carried out in the course of the continuous movement of the cultivating water, the cultivating water can be passed through the neutralization treatment step while moving up and down in the same manner. That is, the number of forms in which the oxidant is generated moves the culture water downward in the first chamber while passing through the first chamber and the second chamber, and the culture water moved to the lower chamber of the second chamber through the lower chamber of the first chamber, And the neutralizing agent is injected at the upper end portion of the second chamber between the second chamber and the third chamber so that the third chamber and a plurality of subsequent chambers, for example, the fourth chamber to the eighth chamber, It is possible to perform the neutralization treatment step while the culture water moves up and down as in the second chamber. When the culture water is constructed so that a plurality of chambers pass through and move up and down while the culture water passes through the disinfection treatment stage and the neutralization treatment stage, the water-based sterilized fish culture method according to the present invention is preferably used even in a relatively small space And can be advantageously used in the contact state of the oxidant in the sterilization treatment step and in the neutralization treatment step in the neutralization treatment step.

During this sterilization and neutralization step, the number of chambers through which aquaculture water passes can be determined by the water quality of the aquaculture, the amount of oxidant produced, the conditions of the sterilization and neutralization stages, the area or local environment in which the aquaculture is performed, The size of fish farms, the supply volume of aquaculture water, and the like. Preferably, the total number of the chambers for the sterilization treatment step and the neutralization treatment step is 2 to 8, more preferably 4 to 6, in view of sterilization efficiency, neutralization efficiency, and neutralization time.

According to the present invention, the oxidant remaining in the culture water is removed in the neutralization treatment stage as described above. During the neutralization treatment stage, a considerable amount of oxidant remains in the culture water at the initial stage of the neutralization treatment. The oxidant residual amount is reduced. Therefore, since the residual amount of the oxidant in the culture water is large at the initial stage of the neutralization treatment step, the sterilization treatment step has already been carried out for the number of the culture, but the sterilization treatment can be partially continued in the neutralization treatment step. However, in the latter stage of the neutralization treatment step, since the oxidant is almost removed and the harmful microorganisms of the fish are almost killed, the sterilization treatment does not occur substantially.

As described above, according to the preferred embodiment of the present invention, the sterilization treatment step and the neutralization treatment step are continuously performed, and the sterilization treatment of the aquaculture water can be performed very efficiently even in the point that the sterilization treatment is continued at the initial stage of the neutralization treatment step.

According to the present invention, sterilized water after sterilization treatment can be supplied to aquaculture tank immediately after the sterilization step, in which the amount of oxidant remaining in the sterilized water is at least 0.06 ppm, preferably 0.01 ppm or less, more preferably 0.005 ppm or less, and most preferably 0.003 ppm or less, which is suitable for fish culture. Most preferably, no oxidant is detected. The residual amount of the neutralizing agent should preferably be substantially no, and should be at least 1 ppm or less, more preferably 0.5 ppm or less.

According to an embodiment of the present invention, for example, when the structure of the aquarium water treatment tank for performing the sterilization treatment step and the neutralization treatment step is divided into a total of eight chambers, a form containing a low concentration oxidant of 0.1 to 0.7 ppm In the case where the water is intended to be sterilized for a long period of time, a sterilization treatment step is carried out while passing through the five chambers of the fifth chamber of the first chamber, for example, the oxidant produced in the first chamber, The sterilizing process proceeds while the sterilizing action is performed in the aquaculture water itself. And the sterilized water having been subjected to the sterilization treatment step up to the fifth chamber is moved to the sixth chamber while the neutralizing agent is injected at the upper end of the fifth chamber and the neutralization process is performed while moving the three chambers from the sixth chamber to the eighth chamber The neutralization step can be carried out.

According to the present invention, the sterilization treatment time and the neutralization treatment time can also be adjusted and designed in accordance with the number and size of the chambers formed with the partition walls in the water treatment water tank. For example, when pumping water of 60 m ³ / min in an onshore aquaculture farm with a water surface area of 5,000 m ² , while generating 0.7 ppm of oxidant continuously and setting the sterilization time to 4 minutes, If the volume of each chamber is 6 m, 5 m, and 8 m in height, the flow rate of the flow through each chamber is 4 minutes. Therefore, the sterilization process time is automatically 4 minutes. In this case, The time can be estimated as 4 minutes x 7 chambers = 28 minutes. On the other hand, the underwater form incoming 30m ³ / min In the absence of sterilization need to use a ground water, the size of the chamber because if only the remaining 30m ³ / min instead of underground water sterilized horizontally 6m, vertical 5m, height 8m The sterilization treatment time is 8 minutes, and the neutralization treatment time is 8 × 7 = 56 minutes.

The neutralization treatment time is very important as well as the kind of the neutralizer in the neutralization treatment step. The time for the neutralization treatment in accordance with the concentration of the oxidant is at least 0.06 ppm or less, preferably 0.01 ppm or less. In the present invention, it is preferable to remove the residual amount of oxidant to 0.06 ppm or less within 1 to 16 minutes of the neutralization treatment time. If the neutralization treatment is performed for a long period of time, that is, if the neutralization treatment chamber is, for example, 7 or more, the neutralization treatment is very uneconomical due to the space and time required for the neutralization treatment. There is a difficult problem.

That is, according to the present invention, since the infectious concentrations of pathogenic microorganisms such as pathogenic bacteria and scutchica are different depending on the area and water quality, the concentration of oxidant and the disinfection time using the concentration of the oxidant in the aquaculture water You can also set it. Accordingly, as described above, the chamber for performing the sterilization treatment step in various forms and the size and number of chambers for performing the neutralization treatment step can be configured.

In one embodiment according to the present invention, the number of sterilized aquaculture water that is passed through the neutralization treatment step a plurality of times is determined by the type of neutralizing agent used and the neutralization time so that the total residual oxidant is almost zero or 0.06 ppm or less, And 99% or more of the total residual oxidant concentration of the sterilized aqua regime is mostly removed and neutralized to 99.9% or more. Therefore, the neutralization treatment step according to the present invention facilitates removal of the oxidant by a low-cost and high-efficiency method You can do it.

According to the present invention, the sterilized water that has undergone the neutralization process as described above is supplied to the fish farm in earnest through the sterilized water supply step (e) supplied to the aquaculture tank where the fish is produced.

In this case, only the sterilization mode may be supplied to the aquaculture tank alone, or the ground water without other harmful bacteria may be mixed and supplied to the aquaculture tank. The sterilized water according to the present invention supplied to the aquaculture tank can be very useful environment for the fish culture since the harmful microbes of the fish are sterilized, .

According to the present invention, since the method of continuously supplying the sterilized aquaculture water supplied to the aquaculture tank and continuously discharging the sterilized aquaculture aqua is preferably applied, the sterilized aquaculture form supplied in the aquaculture tank does not stay long, It is possible that the aquaculture tank will always be filled with high quality water.

According to the present invention, the sterilized aquaculture water supplied to the aquaculture tank is subjected to a wastewater discharge step (f) for discharging the aquaculture wastewater used in the aquaculture from the aquaculture tank. As such, the sterilized aquaculture water is continuously supplied, and after being used for aquaculture, the wastewater is continuously discharged on the other hand. The aquaculture wastewater discharged as such is environmentally friendly wastewater as sterilized water, and even if released into the environment, does not adversely affect the environment.

Meanwhile, the present invention includes a sterilization system of fish for applying the above-described water-based sterilization method.

The preferred embodiment of the water-based sterile water fish culture system according to the present invention can be applied to the structure as shown in FIG. 2 and FIGS. Fig. 2 schematically shows an embodiment of a water-based sterile fish culture system according to the present invention. This sterile aquaculture system (SAS) will be described in detail as one embodiment.

2, the water-based sterilized water culture system according to the present invention includes a water supply unit 100; An oxidant generator 200; A sterilizing treatment section 300 including a culture water moving chamber; A neutralization processing unit 400 including a culture water moving chamber; A sterilization type water supply unit 600 for supplying sterilized water to the aquarium 500; And a culture wastewater discharge unit 700.

According to the present invention, the aquaculture water supply unit 100 may be constructed by connecting the aquaculture water transport pipe to fresh water or freshwater receiving area where seawater is located to collect fresh water or seawater. The water supply unit 100 may include a pump for supplying water.

The water collected by the water supply unit 100 is transferred to the oxidant generator 200. The oxidant generating unit 200 preferably includes a aquaculture water pretreatment water tank, and has an oxidant generating means 210 in the water tank, and is configured to generate an oxidant from the supplied aqua regia. At this time, an electrolytic apparatus may be used as the oxidant generating means.

The number of forms in which the oxidant is generated from the oxidant generating means in the oxidant generating section 200 is transferred to the sterilization processing section 300 by means of the number-of-products moving means (for example, a pump) in a state where the oxidant is generated. The sterilization treatment unit 300 includes a culture water transfer chamber that allows the oxidant to remain in the culture water while sterilization water is supplied and flow, thereby sterilizing harmful bacteria in the culture water.

According to the most typical embodiment of the present invention, the sterilizing unit 300 may have a total of eight chamber structures, for example, as shown in FIGS. 3A and 3B.

FIG. 3A is a diagram showing a configuration of the sterilization processing unit 300 and the neutralization processing unit 400, which are the main parts in the sterilization system according to the present invention, as one specific example. 3A shows the eight water chambers constituting the disinfection processing unit 300 and the neutralization processing unit 400 and the aquaculture water moving path for moving the chambers. Arrows in FIG. 3B denote sterilizing unit 300 and neutralization unit 400 ) To illustrate the planar structure of the eight chambers that make up the chamber.

3a and 3b, the sterilization treatment section 300 may include one or more aquatic movement chambers, for example, two aquatic movement chambers 310, 320, for example, so that the aquarium can be moved while the aquaculture water is continuously supplied. The oxidant-containing aquaculture water supplied from the oxidant generator 200 is oxidized during the movement of the first chamber 310 and the second chamber 320, which are the aquarium water moving chambers of the sterilizing treatment unit 300, It is contacted with the harmful microorganisms existing in the aquaculture water and sterilized. The culture water transfer chambers 310 and 320 of the sterilization treatment unit may have a single chamber or a plurality of chambers.

The sterilized aquaculture water in the sterilization treatment unit 300 is transferred to the neutralization treatment unit 400 to neutralize residual oxidant components to remove oxidant in the aquaculture water. The neutralization treatment unit 400 according to the present invention has a neutralizer injection unit 401 for inputting a neutralizer during the movement of the sterilized wastewater, and the residual aids in the aquaculture water are neutralized To be removed by the water-moving chamber.

The neutralization treatment unit 400 has a plurality of aqua regime chambers 430, 440, 450, 460, 470, 480 in the same or similar manner as the sterilization treatment unit 300, preferably in the same manner. Each of the culture water movement chambers in the neutralization processing unit 400 is regularly configured from the third chamber 430 to the eighth chamber 480. Therefore, sterilization processing is performed in the first chamber 310 and the second chamber 320, which are the sterilization processing units 300, and then the sterilized processed water is continuously flowed in the same manner in the same manner, Neutralization processing is performed while passing through the third chamber 430 to the eighth chamber 480. [

According to a preferred embodiment of the present invention, one or more neutralization accelerators 402 selected from the above transition metals or Group IVA metals may be introduced into each chamber of the neutralization processor 400. The neutralization accelerator 402 may be applied in such a form that the neutralization can be promoted by widening the contact area with the water of the culture such as granular, powdery, porous or non-porous granules, plate-like, porous pellets, . This neutralization accelerator can be added to all the chambers of the neutralization treatment unit 400 or to some chambers, which can help neutralize the oxidants remaining in the aquaculture water.

Also, according to a preferred embodiment of the present invention, the aeration apparatus 403 may be installed in each chamber of the neutralization processing unit 400. In particular, the aeration apparatus 403 may be applied together with the neutralization promoter to float the neutralization promoter in the neutralization chamber to smoothly neutralize the neutralization agent, and may be separately applied to activate the neutralization treatment. In addition, in the chamber of the neutralization processing unit 400, an agitator (not shown) for agitating the aquaculture water or the neutralization accelerator may be installed to activate the neutralization treatment. As a concrete example, there are a blower for generating bubbles to improve the reaction efficiency of each chamber, a compressor for stirring the culture water with the force of the air to shorten the reaction time by contacting the material in the culture water well, Further comprising at least one reaction enhancing device selected from the group consisting of a mixer for increasing the contact time between the neutralizing agent and the oxidant in the aquaculture water by physical force, and a circulating pump for allowing the aquaculture water to flow while rotating several times .

According to the present invention, each of the chambers from the first chamber 310 to the eighth chamber 480 has a partition between the chambers for separating the respective chambers. 3A and 3B, the partition wall between the first chamber 310 and the second chamber 320 is opened at a predetermined width at a lower end thereof, and the second chamber 320 And the third chamber 430 is formed such that the upper end thereof has a predetermined width. Therefore, in the first chamber 310, the culture water moves from the upper end to the lower end. In the second chamber 320, the culture water flowing in from the lower end of the first chamber moves to the upper end. In the third chamber 430, And then flows to the lower end portion while flowing. Accordingly, the water is moved in a water flow manner in which the water flows continuously up and down to the eighth chamber 480 while flowing continuously from the upper end of the first chamber 310 to the downward flow.

As described above, the aquatic-containing aquaculture water is oxidized during the movement from the first chamber 310 to the eighth chamber 480 and during movement in the first chamber 310 and the second chamber 320, The neutralizing agent supplied from the neutralizing agent supply device 401 at the upper end of the second chamber 320 flows from the second chamber 320 to the third chamber 430 through the sterilization process, Water is supplied to the upper portion of the third chamber 430 while the neutralization process is started. The sterilized wastewater is thus neutralized during the movement from the third chamber 430 to the eighth chamber 480. During this process, the oxidant remaining in the aquaculture water is gradually removed, and when the eighth chamber 480 is reached, the neutralization treatment is completed so that the abundance of the oxidant in the aquaculture water does not substantially remain, or at least 0.06 ppm or less, preferably 0.003 ppm or less And is sent to the aquarium 500 where the fish is processed.

According to the present invention, the sterilization water supply unit 600 for supplying the sterilized aqua regenerated water sterilized and neutralized from the eighth chamber 480 located at the distal end of the neutralization treatment unit 400 to the aqua- And a mixing tank 610 to be mixed with seawater. The aseptic underground seawater and the mixing tank 610 may be installed to be located at a height of several meters or more from the ground, and sterilized water may be supplied to the aquarium 500 by water pressure. At this time, the mixing tank 610 may be designed to be positioned at the same height as the chambers constituting the sterilization treatment unit 300 and the neutralization treatment unit 400.

The sterilized aquaculture water supplied to the aquaculture tank 500 provides an environment in which the fishes growing in the aquaculture tank 500 can be cultured in a sterilized aquaculture state.

As described above, the sterilized water used in the fish culture in the aquarium 500 is discharged to the outside through the aquatic effluent discharge unit 700 so as to be continuously discharged. The aquaculture wastewater discharged at this time is neutralized and sterilized by the harmful component as described above, and the fish is used naturally, so that it does not adversely affect the environment.

According to the present invention, the sterilizing treatment unit 300 and the neutralization treatment unit 400 of the fish sterilization system of the present invention have a very efficient and preferable structure and have a characteristic meaning.

According to the present invention, the first chamber to the eighth chamber, in which the sterilizing treatment and the neutralization treatment are performed, may be configured such that the sterilizing treatment unit 300 is composed of two chambers and the neutralization treatment unit 400 is composed of six chambers. As an embodiment of the present invention.

According to a preferred embodiment of the present invention, the number of chambers of the sterilizing unit 300 may be 1 to 7, and the number of chambers of the neutralization unit 400 may be 1 to 7. The configuration of such a chamber is appropriately adjusted and designed in accordance with the number of chambers, the size, the height, the shape, the chamber of the sterilization treatment unit and the chamber of the neutralization treatment unit according to the size of the fish farm, It is possible to construct a sterile fish aquaculture system (SAS) which can apply the fish farming method.

As described above, according to a preferred embodiment of the present invention, the oxidant generator 200 can be applied to an ozone generator or an electrolyzer, and generates oxidant in the number of the form supplied from the aqua supply unit 100 And the aquaculture produced water is supplied to the chamber of the sterilizing treatment unit 300 and supplied.

Therefore, the sterilizing treatment unit 300 and the neutralization treatment unit 400 may have a plurality of chambers that are partitioned, and each chamber may have a structure capable of pulling in or pumping the water. According to the present invention, the chamber may be divided into one to one chamber-1 partition depending on the total number of the chambers. In the lower end of the first partition, a through-hole is formed in a space into which the culture water can flow, The water from the first chamber to the bottom can be transferred to the next chamber. A second overhang of the second chamber is formed at the upper end of the second chamber so that a lower overflow stage is formed at the upper end of the second chamber so that the number of the formulations of the second chamber overflows to be collected in the third chamber, , And the even-numbered bulkhead can be configured to be able to move the water through the upper end. As a result, the culture water flowed in one direction and the neutralization treatment was performed while the culture water flowed and flowed between the chambers. .

In addition, the input of the neutralizing agent is essentially introduced into the last chamber of the sterilizing treatment unit through the neutralizing agent input unit. The natural water is overflowed through the flowing water, so that the water is taken into the chamber of the neutralizing unit, And the neutralization process can be performed in multiple stages by passing through various chambers thereafter.

In this case, when the sterilizing time is long, the neutralizing agent is separated from the upper and lower ends of the chamber for neutralization treatment at a proper position, and the sterilization treatment is performed during the neutralization treatment And may be further sustained. This neutralizing agent input process can be appropriately designed by adjusting the size of the fish farm, the quality of the aquaculture water, the amount of the amniotic fluid supplied, and the like.

The sterilization system for fish according to the present invention can be applied to the sterilization system of fishes according to the present invention and the sterilization system for fishes according to the present invention can be used at low cost and high efficiency. The method of the present invention and the sterilization culture system of fish according to the present invention are aseptic aquaculture method which is low in the mortality rate of fish and does not require antibiotics and vaccine, and is very useful as a new aquaculture method from the conventional aquaculture method.

In addition, in the case of the new fish sterilization system of the present invention, high-concentration oxidants (0.1 to 7 ppm) are generated unlike the conventional ones, thereby completely eliminating harmful microbes such as pathogenic bacteria and providing excellent time, space and economic efficiency. It is possible to supply 30-60 tons of sterilized aquaculture water and it is possible to supply sterilized aquatic water of several thousand tons to tens of thousands of tons per minute by simple design control of the system and to maintain the residual amount of oxidant in sterilized aquaculture water at least 0.06ppm, ppm, and most preferably 0.003 ppm or less, so that a large amount of fish-sterilized form can be obtained in a very economical and environmentally friendly manner.

Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited by the following examples.

However, in the following examples, a water-based sterilized fish farming system consisting of 8 chambers (tanks) measuring 60 cm in length, 50 cm in length, and 80 cm in height corresponding to 1/1000 of the actual facility size available on a 5,000 m ² aquaculture area Was constructed as one embodiment and the following test was carried out.

Comparative Example  One

In order to remove oxidant by activated carbon after producing sterilized oxidant and ozone 0.8mg / L (ppm) by electrolysis device and ozone feeder in 60 ton yield per minute corresponding to cultivation area of 5,000㎡, As a result of calculation to prepare activated carbon, it was concluded that a space of 400m ³ of activated carbon is required and 28 activated carbon towers with a diameter of 5m and a height of 1.5m should be installed.

Therefore, this method requires a high cost, a huge space at the site, and it is confirmed that the method can not be used in fish farms using a large quantity due to difficulty in regeneration processing.

Manufacturing Example  One

Jeju Island Seokgu Seokwon Seawater and underground seawater were mixed at 50:50 and electrolyzed at a flow rate (20 -30 cm / sec), which is generally supplied at a fish farm, while varying the voltage and current density as shown in Table 3 below. Bromate) were analyzed.

Since the concentration of organic matter, sodium bromide (NaBr) concentration, and salinity are all different in the region by region, the selected area is selected as the most standard area and location.

Voltage (Volt) Current density (A / cm 2) TRO concentration
(mg / L) (ppm) Bromate content
(/ / L) (ppb) Remarks
(Detection limit 0.27 / / L) 2.5 0.00694 0.1 2.6 0.00865 0.8 2.8 0.0104 1.42 3.0 0.0137 2.0 trace 3.2 0.018 2.5 trace 3.4 0.0245 3.5 trace 3.6 0.032 4.7 4.46 3.8 0.0383 5.2 5.04 4.0 0.0465 6.0 6.54 4.2 0.0538 6.7 9.94 4.4 0.0612 7.0 9.99 4.5 or more 10.0 51.1 5.0 or higher 16.0 61.5 A solution prepared by dissolving NaBrO ₃ (reagent grade) in distilled water to make 10 ppb 8.93 Control test

Manufacturing Example  2

The concentration of bromate was measured after electrolysis under the conditions shown in Table 4 while flowing the groundwater below the surface with a flow rate of 20 -30 cm / sec. The sodium bromate (NaBr) content in seawater was 63.3 mg / L as Br.

Voltage (Volt) Bromate content (/ / L) Remarks 2.8 Non-detection Detection limit 0.27 / / L 3.0 Non-detection Detection limit 0.27 / / L 3.2 Non-detection Detection limit 0.27 / / L 3.6 4.4 3.8 5.0

Manufacturing Example  3

Bromate content was measured by electrolysis at the flow rate of 20 -30 cm / sec only in the sea surface water under the conditions shown in Table 5 below. The results are shown in Table 5 below. The sodium bromate (NaBr) content in seawater was 63.7 mg / L as Br.

Voltage (Volt) Bromate content (/ / L) Remarks
3.2 Non-detection Detection limit 0.27 / / L 3.6 Non-detection Detection limit 0.27 / / L 3.8 4.49 4.0 7.43 4.2 9.59

Manufacturing Example  4

The underground seawater was slowly electrolyzed at a rate of 10-20 cm / sec to produce a high concentration TRO under the following conditions. The TRO concentration in the water column was diluted with sea water to a concentration of 1 ppm TRO, and the bromate formation concentration was measured. The results are shown in Table 6 below.

Voltage (Volt) Raw TRO concentration
mg / L, ppm Dilution TRO concentration
mg / L, ppm Bromate content
([Mu] g / L) Remarks
3.2 3.4 0.95 Non-detection Detection limit 0.27 / / L 3.4 4.9 1.05 Non-detection Detection limit 0.27 / / L 3.6 5.9 1.07 Non-detection Detection limit 0.27 / / L 3.8 6.8 0.94 4.1

Example  One

First, the water collected in the off-shore of Jeju Island was regulated in the electrolytic unit so that the total residual oxidant (TRO) of 1.0 ppm was continuously generated in the electrolytic apparatus, and then the water was supplied to the sterilizing treatment unit at a flow rate of 60 l / Respectively. 3A and 3B according to the present invention, the third to eighth chambers (430, 440, 450 and 460 in FIG. 3A), which are the neutralization treatment units, , 470) were installed in two chambers with a mesh of 1.0 mesh at intervals of 40 cm. Next, the sodium thiosulfate (Na ₂ S ₂ O ₃ .5H ₂ O) solution, which is 1.0-1.7 times the total residual oxidant (TRO) Sodium sulfate pentahydrate (0.265%) was prepared and placed in a separate container. The mixture was injected into a third chamber (430 in FIG. 3A) at a rate of 60 ml / min and air was injected by a blower to allow mixing.

Here, it is necessary to add sodium thiosulfate, which is a neutralizing agent, at a ratio of 1.7 times as much as the equivalent amount, because the oxidants generated from the electrolytic apparatus and the ozone feeder are not only removed by the following oxidation-reduction reaction, Because there are many other kinds of. In this embodiment, it has been confirmed that the sodium thiosulfate neutralizing agent is neutralized to 0.000 ppm after a certain period of time when the amount of the sodium thiosulfate neutralizer is 1.7 times as much as the equivalent amount.

At this time, air was injected into the neutralization treatment section from the fourth chamber (440 in FIG. 3A) to the eighth chamber (480 in FIG. 3A), but the sodium thiosulfate pentahydrate solution was not injected. It is presumed that the reaction for removing sodium hypochlorite (NaOCl), which is one of various components from the total residual oxidant generated in the electrolytic apparatus, with sodium thiosulfate proceeds by the following reaction formula (4).

[Reaction Scheme 4]

_{4NaClO + Na 2 S 2 O 3} + 2NaOH → 4NaCl + 2Na 2 SO 4 + H 2 O

The measurement results of the total residual auction (TRO) removal rate (%) remaining in the aquaculture after the neutralization treatment are shown in Table 7 below.

division First chamber sterilization
Processing unit Second chamber sterilization
Processing unit Third chamber neutralization
Processing unit Fourth chamber neutralization
Processing unit Fifth chamber neutralization
Processing unit The sixth chamber
Neutralization
Processing unit Seventh chamber neutralization
Processing unit 8th chamber neutralization
Processing unit Running time
(accumulate) 4 minutes 4 minutes
(8 minutes) 4 minutes 4 minutes
(8 minutes) 4 minutes
(12 minutes) 4 minutes
(16 minutes) 4 minutes
(20 minutes) 4 minutes
(24 minutes) TRO 1.01 ppm - 0.05 ppm 0.03 0.02 0.01 0.005 0.000 Removal rate 0% - 95% 97% 98% 99% 99.5% 100%

Example  2

The sterilization system of the fish was applied in the same pouring method as in Example 1 except that an oxidant was generated by an ozone feeder without generating oxidant by an electrolytic apparatus and a process of aquaculture water treatment was performed.

The results of measurement of the total residual oxidant (TRO) removal rate (%) remaining in the aquaculture after the treatment are shown in Table 8 below.

division The first chamber
Sterilization
Processing unit The second chamber
Sterilization
Processing unit Third chamber neutralization
Processing unit Fourth chamber neutralization
Processing unit Fifth chamber neutralization
Processing unit Fifth chamber neutralization
Processing unit Seventh chamber neutralization
Processing unit 8th chamber neutralization
Processing unit Running time
(accumulate) 4 minutes 4 minutes
(8 minutes) 4 minutes 4 minutes
(8 minutes) 4 minutes
(12 minutes) 4 minutes
(16 minutes) 4 minutes
(20 minutes) 4 minutes
(24 minutes) TRO 1.02 1.02 0.06 0.05 0.04 0.01 0.005 0.000 Removal rate - - 94% 95.1% 96% 99% 99.5% 100%

The major components of the oxidant generated by the electrolytic device are sodium hypochlorite or hypochlorous acid and the oxidant main component produced by the ozone supply is hydrobromic acid (HOBr) ) Or sodium hypobromite (NaOBr) (Sodium HypoBromite). However, it was confirmed that the oxydant was completely removed by this embodiment regardless of the oxidant.

Example  3

In Examples 1 and 2 The bolts and currents were adjusted to produce a total residual oxidant (TRO) of 1.0 ppm successively in the electrolytic apparatus using the same pour-type fish sterilization system, and water was added to the first chamber, which was a sterilization treatment at a flow rate of 30 L / min . A sodium hypothalosulfate pentahydrate solution at a concentration of 0.265% was prepared in a third chamber (430 in FIG. 3A) as a neutralization treatment unit and placed in a separate container. Then sodium thiosulfate (sodium thiosulfate) was added so that the total residual oxidant (TRO) 5 hydrate solution was injected at a rate of 30 ml / min.

The results of measurement of the total residual oxidant (TRO) removal rate (%) remaining in the aquaculture water after the treatment are shown in Table 9 below.

division First chamber sterilization
Processing unit The second chamber
Sterilization
Processing unit Third chamber
Neutralization processing section The fourth chamber
Neutralization processing section The fifth chamber
Neutralization processing section The sixth chamber
Neutralization processing section Seventh chamber
Neutralization processing section The eighth chamber
Neutralization processing section Running time
(accumulate) 8 minutes 8 minutes
(16 minutes) 8 minutes 8 minutes
(16 minutes) 8 minutes
(24 minutes) 8 minutes
(32 minutes) 8 minutes
(40 minutes) 8 minutes
(48 minutes) TRO 1.02 1.0 0.05 0.03 0.01 0.005 0.000 0.000 Removal rate - Natural decline 95% 97% 99% 99.5% 100% 100%

As shown in Table 3, when the oxidant was removed by communicating aquaculture water containing a total residual oxidant (TRO) of 1.0 ppm at a flow rate of 30 liters per minute to a neutralization water tank having a width of 60 cm, a length of 50 cm and a height of 80 cm, (470 in FIG. 3A), the removal rate of the oxidant has already reached 100%, so it can be confirmed that the remaining eighth chamber (480 in FIG.

In other words, considering the concentration of the oxidant, the infusion rate, and the size of the water tank, it is possible to design and manufacture the sterilization system of the fish according to the size of each farm and apply it to commercial scale.

Example  4

A solution of 0.572% sodium dithionite anhydride (a) and 0.336% (0.572 ÷ 1.7) hydrate (b) was prepared in the same manner as in Example 1 and charged into a neutralization tank and 60 ml / Respectively. It is presumed that the neutralization reaction will be carried out according to the following reaction formula (5). The results are shown in Table 10 below.

[Reaction Scheme 5]

2Na ₂ S ₂ O ₄ + H ₂ O -> Na ₂ S ₂ O ₃ + 2NaHSO ₃

Na ₂ S ₂ O ₃ + ₄ NaOCl + ₂ NaOH -> ₄ NaCl + ₂ Na ₂ SO ₄ + H ₂ O

2NaHSO ₃ + 2NaOCl - > 2NaCl + 2NaHSO ₄

division The first chamber
Sterilization
Processing unit The second chamber
Sterilization
Processing unit Third chamber
Neutralization
Processing unit The fourth chamber
Neutralization
Processing unit The fifth chamber
Neutralization
Processing unit The sixth chamber
Neutralization
Processing unit Seventh chamber
Neutralization
Processing unit The eighth chamber
Neutralization
Processing unit Running time
(accumulate) 4 minutes 4 minutes
(8 minutes) 4 minutes
4 minutes
(8 minutes) 4 minutes
(12 minutes) 4 minutes
(16 minutes) 4 minutes
(20 minutes) 4 minutes
(24 minutes) (a) TRO 1.01  1.0 0.04 0.03 0.02 0.01 0.005 0.000 (a)
Removal rate Natural decline 96% 97% 98% 99% 99.5% 100% (b) TRO 0.06 0.04 0.02 0.01 0.005 0.000 (b)
Removal rate 94% 96% 98% 99% 99.5% 0.000

As a result of the experiment, it is possible to remove the residual oxidant, which can fish the aquaculture in a short time, to 0.06 ppm, and it is confirmed that the cumulative neutralization time is completely neutralized from 20 to 24 minutes to 0.003 ppm.

Example  5

A 0.85% solution of ascorbic acid was prepared in the same manner as in Example 1, and the solution was neutralized while injecting 60 ml per minute into a neutralization tank. It is presumed that the neutralization reaction will be carried out according to the following reaction formula (6). The results are shown in Table 11 below.

[Reaction Scheme 6]

C ₆ H ₈ O ₆ + NaOCl -> C ₆ H ₆ O ₆ + NaCl + H ₂ O

division The first chamber
Sterilization
Processing unit The second chamber
Sterilization
Processing unit Third chamber
Neutralization
Processing unit The fourth chamber
Neutralization
Processing unit The fifth chamber
Neutralization
Processing unit The sixth chamber
Neutralization
Processing unit Seventh chamber
Neutralization
Processing unit The eighth chamber
Neutralization
Processing unit Running time
(accumulate) 4 minutes 4 minutes
(8 minutes) 4 minutes 4 minutes
(8 minutes) 4 minutes
(16 minutes) 4 minutes
(24 minutes) 4 minutes
(32 minutes) 4 minutes
(40 minutes) TRO 1.01 1.0 0.04 0.03 0.01 0.01 0.000 0.000 Removal rate Natural decline 96% 97% 99% 99% 100% 100%

As a result of the above experiment, ascorbic acid can be confirmed to be neutralized in a slightly longer time than the inorganic neutralizing agent.

Example  6

A 1.69% solution of cysteine hydrochloride monohydrate was prepared in the same manner as in Example 1, and the solution was placed in a neutralization tank and neutralized while injecting 60 ml per minute. It is presumed that the neutralization reaction will be carried out by the following reaction formula (7). The results are shown in Table 12 below.

[Reaction Scheme 7]

2C ₃ H ₇ NO ₂ S + NaOCl -> 2C ₃ H ₆ NO ₂ S + NaCl + 3H ₂ O + 2HCl

division The first chamber
Sterilization
Processing unit The second chamber
Sterilization
Processing unit Third chamber
Neutralization
Processing unit The fourth chamber
Neutralization
Processing unit
The fifth chamber
Neutralization
Processing unit The sixth chamber
Neutralization
Processing unit Seventh chamber
Neutralization
Processing unit The eighth chamber
Neutralization
Processing unit Running time
(accumulate) 4 minutes 4 minutes
(8 minutes) 4 minutes 4 minutes
(8 minutes) 4 minutes
(16 minutes) 4 minutes
(24 minutes) 4 minutes
(32 minutes) 4 minutes
(40 minutes) TRO 1.01 1.0 0.04 0.03 0.01 0.01 0.000 0.000 Removal rate Natural decline 96% 97% 99% 99% 100% 100%

As a result of the above experiment, it is considered that the neutralizing agent is excellent in the neutralizing power against oxidant as a biosynthetic amino acid.

Example  7

The same fish sterilization system as in Example 3 was used except that the zinc mesh was removed and no aeration was performed.

The results are shown in Table 13 below.

division First chamber sterilization
Processing unit The second chamber
Sterilization
Processing unit Third chamber
Neutralization
Processing unit The fourth chamber
Neutralization
Processing unit The fifth chamber
Neutralization
Processing unit The sixth chamber
Neutralization
Processing unit Seventh chamber
Neutralization
Processing unit The eighth chamber
Neutralization
Processing unit Running time
(accumulate) 8 minutes 8 minutes
(16 minutes) 8 minutes 8 minutes
(16 minutes) 8 minutes
(24 minutes) 8 minutes
(32 minutes) 8 minutes
(40 minutes) 8 minutes
(48 minutes) TRO 1.02 1.0 0.05 0.05 0.04 0.03 0.02 0.01 Removal rate   - Natural decline 95% 95% 96% 97% 98% 99%

When the aeration and zinc mesh are not used, it takes some time to remove the oxidant because it can remove the oxidant to less than 0.01 ppm after about 48 minutes. Therefore, the number or size of the reaction chambers may be required more.

Examples 8 to 9

In order to compare the oxidative removal efficiency using sodium sulfite and acidic sodium sulfite, it was assumed that all the conditions were the same as those of Example 3, neutralized by the following Reaction Scheme 8, and 0.604% solution of sodium sulfate equivalent weight of 1.760 /35.5 占 .7) was used and 0.586% solution (104.061 / 35.5 占 .7) of 1.7 times as acid sodium sulfite equivalent was injected at a rate of 30 ml / min each.

Oxidant removal rates were measured for each of the neutralizing agents used and the results are shown in Table 14 below.

[Reaction Scheme 8]

NaOCl + Na ₂ SO ₃ -> NaCl + Na ₂ SO ₄

_{NaOCl + NaHSO 3 -> NaCl +} NaHSO 4

corrector
Kinds division The first chamber
Sterilization
Processing unit The second chamber
Sterilization
Processing unit Third chamber
Neutralization
Processing unit The fourth chamber
Neutralization
Processing unit The fifth chamber
Neutralization
Processing unit The sixth chamber
Neutralization
Processing unit Seventh chamber
Neutralization
Processing unit The eighth chamber
Neutralization
Processing unit Running time
(accumulate) 8 minutes 8 minutes
(16 minutes) 8 minutes
8 minutes
(16 minutes) 8 minutes
(24 minutes) 8 minutes
(32 minutes) 8 minutes
(40 minutes) 8 minutes
(48 minutes) Sulfite
salt
(Example 8) TRO 1.02 1.0 0.13 0.09 0.08 0.06 0.04 0.03 Removal rate   - Natural decline 87% 91% 92% 94% 96% 97% Acid Sodium Sulfate
(Example 9) TRO 1.02 1.0 0.14 0.08 0.08 0.07 0.04 0.04 Removal rate Natural decline 86% 92% 92% 93% 96% 96%

Example 10

All conditions were the same as those of Example 3, and oxidative removal was performed using hydrogen peroxide (50%) as a neutralizing agent to measure the oxidative removal efficiency. A solution of 0.355 (35.5 / 34.01 x 2 x 1.7)% of hydrogen peroxide (50%) was prepared in order to use 1.7 times the amount of neutralizing agent than the equivalent amount expected to be neutralized as shown in the following reaction formula 9, put in a separate neutralization tank, . The results are shown in Table 15 below.

[Reaction Scheme 9]

NaOCl + H ₂ O ₂ -> NaCl + H ₂ O + O ₂

division The first chamber
Sterilization
Processing unit The second chamber
Sterilization
Processing unit Third chamber
Neutralization
Processing unit The fourth chamber
Neutralization
Processing unit The fifth chamber
Neutralization
Processing unit The sixth chamber
Neutralization
Processing unit Seventh chamber
Neutralization
Processing unit The eighth chamber
Neutralization
Processing unit Running time
(accumulate) 8 minutes 8 minutes
(16 minutes) 8 minutes 8 minutes
(16 minutes) 8 minutes
(24 minutes) 8 minutes
(32 minutes) 8 minutes
(40 minutes) 8 minutes
(48 minutes) TRO 1.02 1.0 0.08 0.07 0.07 0.06 0.06 0.06 Removal rate   - Natural decline 92% 93% 93% 94% 94% 94%

Experimental Example  1: Neutralization promoting effect test of zinc sheet

In a 2000 ml beaker, a thin zinc sheet (1 mm thick) was cut into a width of 10 mm and a length of 200 mm. Four of them were hanged from the basin to a distance of about 4 cm. 1500 ml of 2 ppm oxidant was placed in the beaker and then 8, 16, , 40 min, and 48 min, respectively, and the removal rate of the oxidant was tested.

The experimental results are shown in Table 16 below.

division 8 minutes 16 minutes 24 minutes 32 minutes 40 minutes 48 minutes TRO 0.94 0.39 0.12 0.12 0.1 0.08 Removal rate 53% 80.5% 94% 94% 95% 96%

As a result of the above experiment, it was confirmed that zinc facilitates the removal of oxidant.

Experimental Example 2: Streptococcus Para Ube lease (Streptococcus parauberis ) Microbial survival experiment measurement

Streptococcus ( Streptococcus spp.) , Which is introduced with the number of aquaculture and causes the most mortality in flounder Parauberis ) microorganisms were separately cultured to produce a culture water having a concentration of 10 ⁵ cfu / ml. Using this electrolytic apparatus, a total residual oxidant of 0.5 ppm corresponding to 1/2 of the above-mentioned Example 1 was produced, and the thus-prepared water was supplied to the first chamber (310 in FIG. 3A) Respectively. In addition, in order to make the residence time of the oxidant longer than that of the first embodiment by 2 times (16 minutes), the second chamber (320 in FIG. 3A) and the third chamber (430 in FIG. 3A) A solution of sodium thiosulfate (Na ₂ S ₂ O ₃ .5H ₂ O) at a concentration of 0.265% was supplied to the chamber in a fourth chamber (440 in FIG. 3A) at a ratio 1.7 times the oxydant equivalent ratio.

Subsequently, after the neutralization process from the fifth chamber (450 in FIG. 3A) to the eighth chamber (480 in FIG. 3A), the aquaculture water was collected and the total residual oxidant (TRO) and the number of bacteria of Streptococcus parabeuris As a result, it was confirmed that the total residual oxidant was removed by 100%, and Streptococcus parauberis was reduced by 1 to 5 cfu / ml to 99.9%. The results are shown in Table 17 below.

division First chamber sterilization
Processing unit The second chamber
Sterilization
Processing unit Third chamber sterilization
Processing unit The fourth chamber
Sterilization
Processing unit The fifth chamber
Neutralization
Processing unit The sixth chamber
Neutralization
Processing unit Seventh chamber
Neutralization
Processing unit The eighth chamber
Neutralization
Processing unit Residence time
(accumulate) 4 minutes 4 minutes
(8 minutes) 4 minutes
(12 minutes) 4 minutes
(16 minutes) 4 minutes 4 minutes
(8 minutes) 4 minutes
(12 minutes) 4 minutes
(16 minutes) TRO 0.5 0.4 0.3 - 0.03 0.02 0.001 0.000 TRO removal rate - Natural decline Natural decline Neutralization liquid
Injection 94% 96% 99.8% 100% Number of viable microorganisms - - - 5 3 4 One One microbe
Mortality rate - - - 99.9% 99.9% 99.9% 99.9% 99.9%

The microorganism test was conducted only for viable count, and no identification test was performed. When it was judged to be in the form of a growing colony of the microorganism to be detected, it was judged that it was not intentionally injected Streptococcus parauberis, so that the microbial mortality rate was 99.9%, whereas Streptococcus parauberis was 100% .

Experimental Example  3: Bromate in aquaculture ( Bromate )inspection

Sterilized seawater and underground seawater at 400 Liter / minute, 20 ~ 30cm / sec, 2.7Volt 1.2 ppm TRO concentration for 16 minutes (1.2.3.4 chamber is used as sterilization chamber) and 1.5% 55 ml per minute was added and the mixture was neutralized by aerating with aeration for 16 minutes (using 5.6.7.8 chamber as neutralization tank), and TRO was confirmed to be below 0.01 ppm.

On June 1, 2014, 5 - 10g of fish were introduced into a water tank of 8m in diameter, and water type sterile water fish farms were started. Two 300-400g of fish were randomly selected on December 1, Next, distilled water was added to make the total volume to 2,000 ml, centrifugal separation was performed, and the supernatant was collected and tested for bromate, which was not detected.

In addition, during the 6 month cultivation period, none of the diseases caused by the following diseases occurred at all.

(1) Rhabdo virus, VHSV (Viral hemorrhagic sepsis), Lymphocystis virus

② Vibrio disease (Vibrio anguillarum, etc.)

③ Edwardiella (Edwardsiella tarda et al.)

(4) Streptococcus parauberis, etc.

⑤ Scuticocilate

Therefore, as shown in the above embodiment, by applying the water-based fish culture method and the sterilization system of the fish according to the present invention, the harmful microorganisms such as various pathogenic microorganisms are killed and the harmful oxidant substances are completely removed It has been confirmed that the use of sterilized aseptic aquaculture water in the aquaculture tank can drastically reduce the death of fish by pathogenic microorganisms. In addition, considering the concentration of remaining oxidant in the culture system, the rate of water supply, and the size of aquaculture tank, it is possible to design a sterilization system for fish according to the size of each aquaculture, .

100 - Feed water supplier
200 - Oxidant Generating Unit
300 - sterilization treatment section
310 - a first chamber, 320 - a second chamber
400 - neutralization processor
401 - neutralizing agent inlet, 402 - neutralizing agent,
403 - Aeration devices
430 to 480 - Third to 8th chambers
500 - Aquaculture tank
600 - sterilized water supply section
610 - Mixed Tank
700 - Wastewater discharge section

Claims (16)

delete (a) Supplying aquaculture water for freshwater or sea water to be supplied as aquaculture;
(b) Using electrolysis in the supplied water, but using Titanium or Niobium as the substrate metal and adding Ruthenium, Iridium, Tantalum and Platinum ) And 0.1 to 30 탆 of a metal selected from the oxide thereof is used as an anode to electrolyze seawater and fresh water, and the voltage is adjusted to 2.51 - 4.4 volts to produce 10 ppb or less of bromate An oxidant generating step of generating an oxidant by using an electrolytic method which causes the oxidant to be oxidized;
(c) a sterilization treatment step in which oxidant remains in the aquaculture water in a continuous flow of aquaculture, thereby sterilizing the fish pests in the aquaculture water;
(d) a neutralization treatment step of removing the oxidant so that the residual oxidant in the aquaculture water is 0.06 ppm or less by injecting a neutralizer into the sanitized wastewater water in the state where the water is continuously flowing;
(e) supplying a sterilized aqua regenerated water to the culture water tank of the fish; And
(f) a wastewater discharge step for discharging the wastewater used in the fish culture from the aquarium;
(C) and (d) are performed in a chamber partitioned by 2 to 8, and the aquaculture water is introduced into or pumped into a compartmented chamber, and flows in one direction, The sterilization process of the step (c) and the neutralization process of the step (d) are sequentially performed in each chamber,
At this time, the chambers of the respective chambers are alternately arranged with barrier ribs having a partition wall having a predetermined width and barrier ribs having upper ends having a predetermined width, and the water flows from the upper end to the lower end, And the water is flowed from the upper part to the lower part so that the water is flowed upward and downward continuously so that the water is flowed in. Having
Lt; RTI ID = 0.0 > sterile < / RTI >
The method of claim 2, wherein the total residual oxidant (TRO) value of the oxidant in step (c) is 0.1 to 7.0 ppm.
The method of claim 2, wherein the sterilization of step (c) is performed for 1 to 28 minutes.
[6] The method of claim 2, wherein the step (d) further comprises the step of accelerating the removal of oxidant by introducing at least one of a transition metal and a metal belonging to group IVA or ions thereof into a neutralization accelerator Method for the production of water - soluble sterile water fish.
[3] The method of claim 2, wherein step (d) further comprises an aeration step of removing the oxidant by injecting air.
The method according to claim 2, wherein the step (d) comprises the step of injecting at least one metal selected from the group consisting of zinc, iron, copper, chromium and tin or an ion thereof with a neutralization accelerator to accelerate the removal of oxidant, Further comprising an aerating step of removing the oxidant by injecting the sterilized water.
The method of claim 5 or 7, wherein the neutralization promoter is selected from the group consisting of a mesh drawing, a powder, a granule, a porous pellet, a cylindrical block, Wherein the water is fed in the form of the above-mentioned form.
3. The method of claim 2, wherein the neutralizing step (d) is performed for 1 to 48 minutes.
The method according to claim 2, wherein the step (c) comprises continuously supplying the neutralizer for performing the step (d) immediately after sterilization by contacting the oxidant with the aqua regia, Method of sterilization of fish.
Aquaculture water supply unit for supplying freshwater or sea water to the aquaculture water;
And an oxidant generating means by electrolysis, wherein electrolytic method is used in the supplied wastewater but titanium or niobium is used as a substrate metal and ruthenium, iridium, tantalum Tantalum) and platinum, or a metal selected from the group consisting of oxides thereof is coated on the surface of the substrate in an amount of 0.1 to 30 μm, and the seawater and fresh water are electrolyzed using the electrode as an anode. The voltage is adjusted to 2.51 to 4.4 volts to form a bromate ) Of 10 ppb or less is produced by an electrolysis method which produces an oxidant;
A sterilizing treatment section including an aquaculture treatment chamber for allowing the oxidant to remain in the aquarium while the aquaculture-producing aquaculture water is supplied and the aquatic bacteria in the aquaculture water are sterilized;
The sanitizer has a neutralizer input portion for introducing at least one neutralizer selected from sodium thiosulfate, sodium dithionite, ascorbic acid, cysteine, sulfur dioxide, sodium sulfite, acidic sodium sulfite and hydrogen peroxide during the movement of sterilized aquaculture water, A neutralization treatment section including a culture water moving chamber for allowing the number of cultivated cultures to be continuously moved so that residual oxidant in the culture water is neutralized to 0.06 ppm or less;
A sterilization water supply unit for supplying the sanitizing treatment and the neutralized sterilized aqua regia to the aquaculture water tank; And
A wastewater discharge unit for discharging wastewater from the aquarium;
Wherein the water-based sterilized water culture system comprises:
[12] The method of claim 11, wherein the neutralization of the neutralization treatment unit is performed such that the neutralization agent is introduced into the chamber of the neutralization unit by overflowing the neutralization agent injected from the neutralization agent input unit into the last chamber of the sterilization treatment unit, Characterized in that the water-based sterile water fish culture system.
12. The method of claim 11, wherein the neutralization treatment unit is further charged with at least one metal selected from the group consisting of zinc, iron, copper, chromium and tin, or an ion thereof as a neutralization accelerator, Form system.
14. The method of claim 13, wherein the neutralization promoter is introduced in a form selected from a mesh drawing, a powder, a granule, a plate, a porous pellet, or a cylindrical block. Lt; RTI ID = 0.0 > sterile < / RTI >
12. The apparatus of claim 11, wherein the neutralization processor further comprises at least one reaction enhancer selected from the group consisting of a blower, a compressor, a mixer, and a circulating pump Water - based sterile water fish culture system.
The water-based sterilizing fish according to claim 2, wherein the neutralizing agent is at least one neutralizing agent selected from sodium thiosulfate, sodium dithionate, ascorbic acid, cysteine, sulfur dioxide, sodium sulfite, acidic sodium sulfite and hydrogen peroxide. How to form.

Images