JP2018038995A - Sterilized sea water, sterilized fresh water generation method and device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide water for breeding and aquaculture of marine organisms or freshwater organisms, water for sterilizing and washing fresh seafood, water for maintaining freshness when transporting fresh seafood, equipment and machinery installed in a place where fresh seafood is handled Providing a method for producing aseptic seawater and aseptic fresh water used for various purposes such as washing water, and an apparatus for producing the water. An electrolytic tank 1 containing an electrolytic stock solution 2 is placed in a tank 3 containing seawater or fresh water, and electrolyzed water and electrolytic gas (chlorine) are obtained by electrolysis from seawater or fresh water in the container. After sterilizing with hypochlorous acid to obtain seawater or fresh water having sterilizing ability, neutralizing hypochlorous acid by adding a neutralizing agent such as sodium thiosulfate 9 and then aseptic seawater and fresh water Get 12. An apparatus in which a fine electrolytic gas discharge pore is provided in the upper part 4 of the electrolytic cell 3 and a valve 8 is provided in the lower part of the container to facilitate the discharge of the electrolyte at the end of electrolysis. [Selection] Figure 1

Description

Detailed Description of the Invention

  The present invention relates to a production method and a production apparatus for producing sterilized seawater or sterilized fresh water.

  The sterilized seawater or sterilized fresh water in the present invention refers to electrolyzed water having a sterilizing ability generated by non-diaphragm electrolysis using a chlorine salt solution or hydrochloric acid or dilute hydrochloric acid as the electrolyzed water. The same shall apply hereinafter) to make sterile raw water, and then neutralize the effective chlorine component contained in the electrolyzed water (neutralizing sterilizing ability) to prepare water that is prepared in a sterile or nearly aseptic condition.

The electrolyzed water that constitutes the sterilized seawater or sterilized fresh water has the effect of sterilizing the effective chlorine component produced during electrolysis of the electrolyzed water. To be aseptic.
Further, the effective chlorine component is neutralized and prepared in a sterilized state or a state close to sterilization so that the effective chlorine component has a concentration that does not affect the organisms to be reared and cultured.
As a result, adverse effects on the organism and fresh fish and shellfish of the sterilized seawater or sterilized freshwater are eliminated. It is used for various purposes such as water for maintaining freshness when transporting seafood, and water for cleaning equipment and machinery installed in a place where fresh seafood is handled.

It has already been proposed to use diluted electrolyzed water prepared by diluting electrolyzed water having sterilizing ability with water or seawater for washing and sterilizing live fish and shellfish (see Patent Document 1). In addition, a method for producing water for sterilization adjusted to a predetermined pH by diluting electrolyzed water having sterilizing ability with clear water has already been proposed.
JP 2003-259755 A JP-A-8-318273

  By the way, as means for diluting the electrolyzed water having sterilizing ability with the diluting water, the electrolyzed water is once introduced and stored in the storage tank, and the diluting water is introduced into the storage tank in which the electrolyzed water is stored. In general, a means for mixing is adopted, and a means for introducing the dilution water into the lead-out line for the electrolyzed water and mixing the dilution water with the electrolyzed water in the lead-out pipe is adopted. Is common.

  However, in the case where the former method is adopted, when diluted electrolytic product water is prepared in the storage tank, diluted electrolytic product water cannot be collected from the storage tank, and dilution in the storage tank is not possible. There is a problem that after the electrolyzed water is consumed, the collection of the diluted electrolyzed water must be interrupted. Further, when the latter method is adopted, since the electrolytically generated water and the dilution water are mixed in the outlet pipe through which the electrolytically generated water flows, concentration spots are easily generated in the prepared diluted electrolytically generated water. In addition, the amount of electrolytically generated water and dilution water introduced into the outlet conduit is greatly regulated, and there is a problem when a large amount of diluted electrolytically generated water is consumed in a short time. There's a problem.

Furthermore, when the seawater is electrolyzed, iron dioxide is generated and the electrolyzed seawater turns brown, and the water for sterilization and washing of fresh seafood, which is the purpose of use of the sterilized seawater, water for maintaining freshness when transporting fresh seafood, and fresh seafood At present, it cannot be used as cleaning water for equipment and machinery installed in places where food is handled.
Moreover, the apparatus has to be large, and is unsuitable for carrying or transporting, and can only be used by being fixedly installed in one place. In addition, the raw water must be continuously supplied at a constant pressure, and can only be used in a place where such water supply facilities are provided. Moreover, the apparatus is expensive and not suitable for wide use. Therefore, the object of the present invention is to eliminate these problems.

  The present invention relates to a production apparatus for producing sterilized seawater or sterilized fresh water. The production method according to the present invention is a production apparatus for producing sterilized seawater or sterilized fresh water.

In order to solve the problem, the inventor has invented a compact electrolytic cell composed of an electrode and a container for housing the electrode. In addition, a chlorine salt solution or a stock solution for electrolysis of hydrochloric acid or dilute hydrochloric acid was poured into a container of an electrolytic tank from an injection portion with a lid provided on the top. Moreover, the upper part of the container was provided with pores that let the electrolytic gas come out of the electrolytic cell as fine bubbles. In addition, it was confirmed that the pores could be provided in the injection part with a lid or in the joint part between the injection part with the lid and the electrolytic cell container, and any structure was adopted. By providing the pores, the electrolytic gas became fine bubbles, which can be easily dissolved in the raw water in which the electrolytic cell is immersed. Furthermore, by providing a valve in the lower part of the electrolytic cell container, the shape of the electrolytic cell container was determined by knowing that the electrolyte could be easily discharged at the end of electrolysis. The electrolytic cell into which the electrolytic stock solution was injected was immersed in a container in which raw water was previously stored for electrolysis, so that it was possible to prepare electrolytic water without the need for pressurized water supply equipment such as tap water. Furthermore, in order to prevent the electrolytic gas from leaking outside from the container storing the raw water during electrolysis, the problem has been solved by adopting a structure in which the container storing the raw water can be sealed.

An embodiment of the present invention will be described based on FIG. 1 and FIG. FIG. 1 is an overall view illustrating a use state. (1) The electrolytic cell main body is electrically coupled with (5) the control unit by (6) power supply wire. (6) In the middle of the electrical cord, (3) (4) inner lid for raw water container is attached, (1) The electrolytic cell is put in (3) raw water container, and (4) inner lid is applied. , (3) The raw water container can be sealed. FIG. 2 is an external view and a sectional view for explaining the structure of the electrolytic cell. The main body is composed of (20) upper part and 21 lower part, (20) upper part is hollow, and (19) electrode plate holds and incorporates one cathode and one anode. (19) Each electrode plate is connected to a cathode and an anode of a DC power source incorporated in a control unit by (6) an electric cord, respectively. Further, at the upper end of the upper part (20), (14) an electrolytic stock solution injection part is installed, and (17) by opening the lid, (1) the electrolytic stock solution can be injected into the electrolytic cell. Further, 23 pores (not shown) are provided at the junction of the electrolytic solution inlet and the upper portion 20 to serve to make the electrolytic gas into fine bubbles.
The lower part 21 includes (1) the bottom of the electrolytic cell and at the same time discharges the electrolyte. (18) The discharge port and the valve (16) that can open and close the discharge port are built in. {Circle around (16)} The valve is opened and closed by using the 22 handle provided on a part of the valve at the lower part of the valve and by rotating the valve body.
The procedure for preparing electrolyzed water using this apparatus is as follows. First, (2) raw water is poured into (3) raw water container.
Next, (1) the electrolytic cell's (16) valve is closed, (14) the electrolytic solution is injected from the electrolytic solution injection part, and (17) the lid is closed. (1) The electrolytic cell is put into the (3) raw water container. (6) (4) The inner lid attached to the electric cord is fitted into the mouth of (3) raw water container, and (3) the raw water container is sealed. Next, (5) start the electrolysis by turning on the start switch installed in the control unit.
When the electrolysis is completed, (1) the electrolytic cell is lifted from (2) raw water, (16) the valve is opened, (14) the electrolytic solution injection part is opened, (17) the lid is opened, and the internal electrolyte is added to the raw water. Then, (1) electrolytic cell is immersed again in (2) stock solution, and (1) electrolytic cell is washed. (1) The electrolytic cell is pulled up, and (3) the contents of the raw water container are stirred to prepare electrolytic water. (8) Open the raw water transfer valve, (11) Transfer to a sterile water tank, (13) Add sodium thiosulfate from the sodium thiosulfate tank, (10) Open the sodium thiosulfate addition valve, and add effective chlorine concentration Aseptic seawater or aseptic fresh water is prepared.

上記表を説明すると原水である海水は富山県で採取された海洋深層水１０Ｌとし、原液は２１％食品添加物塩酸を飲用可能な水で希釈し３％、６％、９％の希塩酸とした。
投入型電解槽は株式会社ホクエツ製の「アピアミニ」を使用し、電解毎に１０ｍＬを電解槽に注入し原水１０Ｌに浸漬後、ＤＣ５Ｖ、を印加し電気分解したその時の電流値は１．０Ａ〜１．６Ａであった。
結果どの電解でも有効塩素濃度が１０ｍｇ／Ｌ以上の除菌海水の生成が確認できた。
また、除菌海水を無菌海水とする為、０．０１ｍｏｌ／Ｌのチオ硫酸ナトリウムを添加し次亜塩素酸を中和した結果は以下の通りである。

結果、海水でも次亜塩素の中和は有効塩素濃度から１．７７を商した０．０１ｍｏｌ／Ｌのチオ硫酸ナトリウムを添加すれば中和することが確認できた。
これはチオ硫酸ナトリウムを０．１ｍｏｌ／Ｌとすれば各１／１０で中和可能となる。
（化学式）
Ｎａ_２Ｓ_２Ｏ_３＋４Ｃｌ_２＋５Ｈ_２Ｏ→２Ｎ_ａＣｌ＋２Ｈ_２ＳＯ_４＋６ＨＣｌとか Ｌ−アスコルビン酸＋ＨＣｌＯ→酸化型アスコルビン酸＋ＨＣｌ＋Ｈ_２Ｏ等In the seawater sterilization method according to the present invention, salt water is electrolyzed in an electrolyzed electrolysis tank, and the obtained hypochlorous acid is added to a seawater storage tank to obtain sterilized seawater, and then sodium thiosulfate is added. After neutralizing hypochlorous acid, the generated seawater is transferred from the raw water storage tank to the sterilized seawater tank and completed.
The pH, ORP, and effective chlorine concentration after actually charging seawater as raw water and immersing it in an electrolytic cell containing dilute hydrochloric acid of each concentration, electrolyzing, and mixing with seawater as raw water after a predetermined time are as follows It is.

Explaining the above table, the raw sea water is 10 L of deep sea water collected in Toyama Prefecture, and the stock solution is diluted with 21% food additive hydrochloric acid with drinkable water to make 3%, 6% and 9% dilute hydrochloric acid. .
The input type electrolytic cell uses “Apiamini” manufactured by Hokuetsu Co., Ltd. 10 mL is poured into the electrolytic cell for each electrolysis and immersed in 10 L of raw water, and then DC5 V is applied and electrolysis is performed. 1.6 A.
Results The generation of sterilized seawater having an effective chlorine concentration of 10 mg / L or more was confirmed in any electrolysis.
Moreover, in order to use the sterilized seawater as sterile seawater, the result of neutralizing hypochlorous acid by adding 0.01 mol / L sodium thiosulfate is as follows.

As a result, it was confirmed that even in seawater, hypochlorous acid was neutralized by adding 0.01 mol / L sodium thiosulfate obtained by dividing 1.77 from the effective chlorine concentration.
If sodium thiosulfate is 0.1 mol / L, neutralization is possible at 1/10 each.
(Chemical formula)
Na ₂ S ₂ O ₃ + 4Cl ₂ + 5H ₂ O → 2N _a Cl + 2H ₂ SO ₄ + 6HCl or L-ascorbic acid + HClO → oxidized ascorbic acid + HCl + H ₂ O, etc.

Although the Example using the apparatus shown in FIG. 1 and FIG. 2 is shown, this is for the purpose of assisting the understanding of the present invention, and is not intended to limit the scope of the present invention to this example.

(1) The electrolytic cell was scaled up to 10 times the electrolytic area of Hokuetsu's “Apiamini”, and the amount of electrolyte that could be accumulated inside was increased from 10 mL to 100 mL.
{Circle around (3)} The raw water container is a resin container made by Dailite Co., Ltd. with a capacity of 100 L, and a portable mixer A720 type agitator made by Satake Corp. is placed in the tank.
(13) The neutralization solution container uses a resin 20 L container to store 0.01 mol / L sodium thiosulfate. (11) The sterile seawater tank uses a 500 L resin container. A portable mixer A720 type agitator manufactured by Satake Corp. and an AT-0923 residual chlorine concentration meter manufactured by 24 Sunny Trading Corp. are arranged.
(13) Addition of neutralization solution from 0.01 mol / L sodium thiosulfate container to (11) sterile water tank is added via (10) resin solenoid valve Type 131 type 15A manufactured by Sekisui Chemical Co., Ltd. (13) A 0.01 mol / L sodium thiosulfate container is placed above the (11) sterile water tank, and the neutralizing solution can be added only by opening the solenoid valve. The seawater that has been processed is taken out to the place of use by 26 manual valves.

(3) Store 100 L of seawater in the raw water tank, (1) Add 100 mL of 6.0% dilute hydrochloric acid to the electrolytic tank, and (2) soak in seawater, then apply an electrolysis voltage of 5 V and the same current of 1.0 A. Apply to the electrolytic cell and electrolyze. Chlorine gas by electrolysis is discharged from the 232.0 mm pores at the top of the electrolytic cell and dissolved in seawater. After 10 minutes, 16 mg / L of effective chlorine was detected by the residual chlorine concentration meter, the application of voltage and current was stopped, and (1) the charging-type hypochlorous acid producing electrolytic cell was removed from (2) seawater. The electrolyte remaining inside the electrolytic cell is opened (16) by opening the lower valve of the electrolytic cell, and (3) discharged into the raw water tank. (7) Stir with a stirrer for 1 minute to eliminate concentration spots. At this point, the effective chlorine concentration of seawater is 19 mg / L, and it becomes seawater with sterilizing ability containing hypochlorous acid, and naturally becomes sterile. Next, (8) Open the manual valve, (11) Transfer the seawater containing effective chlorine to (11) Aseptic seawater tank, monitor with 24 residual chlorine concentration meter, (13) Stored in the neutralization tank (9) (2) Add neutralizing solution to 0 mg / L while stirring 0.01 mol / L of sodium thiosulfate through (7) solenoid valve and (4) stirring with a stirrer. (5) Residual chlorine concentration meter signal (10) The solenoid valve is automatically closed and the addition is completed. Further, stirring is automatically stopped after stirring for 1 minute to completely eliminate the density unevenness. At this point, the seawater becomes sanitized seawater that does not contain hypochlorous acid. Finally, it is taken out via a manual valve.
This technique is repeated several times, and {11} the liquid is stored while monitoring the liquid level in the sterilized seawater tank. {11} The bacteria are confirmed by culturing the sample water of the seawater in the sterile seawater tank. Aseptic conditions were confirmed.
As a result, the effective chlorine concentration was neutralized, and aseptic seawater that can be used for marine life and aquaculture was prepared.

Effect of the invention

The method for producing sterilized seawater or sterilized fresh water according to the present invention is installed in a place for handling fresh fish and shellfish sterilization and washing water, freshness-maintaining water during transport of fresh fish and shellfish, and fresh fish and shellfish It contributes to the improvement of hygiene in the production and distribution of seafood-related foods and the environment for the cleaning of existing facilities and machinery. In addition, since the apparatus and running cost are extremely low, it can be used widely.

Overall view of device and usage status External view and sectional view of electrolytic cell

1. Electrolyzer body 1. Raw water 3. Raw water storage tank 4. Inner lid 5. Control unit 6. Electric power supply wire 7. Raw water tank agitator 8. 8. Raw water transfer valve Sodium thiosulfate10. 10. Sodium thiosulfate addition valve Sanitized seawater tank or sanitized freshwater tank 12. Sanitized seawater or sanitized fresh water13. Sodium thiosulfate container 14. Electrolyte solution injection part 15. Electrolyte storage part of electrolytic cell 16. Electrolyte discharge opening / closing valve 17. Electrolyte solution injection part lid 18. Electrolyte outlet 19. Electrode plate 20. Electrolyzer main body upper part 21. Electrolyzer main body lower part 22. Electrolyte discharge opening / closing valve Valve rotation handle 23. Pore 24. Effective chlorine concentration meter 25. Aseptic water tank stirrer 26. Extraction manual valve

Claims (7)

In the technology to generate seawater or fresh water with a sterilization function, an electrolytic cell with the function of generating hypochlorous acid is immersed in raw water (hereinafter the same) that is seawater or fresh water, and the electrolysis contained in the electrolytic cell A method for producing sterilized seawater or sterilized fresh water, in which electrolytic solution is electrolyzed, and electrolytic products are mixed and diluted with raw water in which the electrolytic cell is immersed to produce electrolytic water having a sterilizing function. The method for producing sterilized seawater or sterilized freshwater according to claim 1, wherein the hypochlorous acid component contained after electrolysis is neutralized with sodium thiosulfate to produce sterilized seawater or sterilized freshwater. The electrolytic cell is a non-diaphragm electrolytic cell that does not have a diaphragm between the anode and the cathode, and is composed of an electrode and a container that accommodates the electrode. An electrolytic stock solution for accommodating the electrolytic stock solution is contained inside the electrolytic cell. An apparatus for producing sterilized seawater or sterilized fresh water, characterized by comprising an injection part with a lid for injection, wherein the electrolytic stock solution is a chlorine salt solution, hydrochloric acid or dilute hydrochloric acid. 4. The sterilized seawater or sterilized fresh water generating device according to claim 3, wherein the electrolytic cell according to claim 3 has pores for releasing electrolysis-generated gas at an upper part of a container accommodating the electrode. The pore according to claim 4 has an area of a circle having a diameter of 0.5 mm to 2.0 mm or less, and one or a plurality of pores are provided. apparatus. The sterilized seawater or sterilized fresh water generating apparatus according to claim 3, further comprising a valve for discharging the electrolytic product at a lower portion of the electrolytic cell according to claim 3. The electrolyzed water generating apparatus according to claim 3, wherein the electrolyzer insertion port of the raw water container can be tightly plugged in a state in which the electrolyzer is accommodated in the container in which the raw water is stored. 6. The sterilized seawater or sterilized fresh water generator according to 6.

Images