JPH10128336A - Method and apparatus for preparing disinfectant, disinfectant, and strilization method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make the total amount of raw water added with hydrochloric acid to be a raw material be produced as a disinfectant having a high sterilization effect by passing raw water added with hydrochloric acid through an electrolytic bath without a diaphragm between positive and negative electrodes and electrolyzing the raw water by passing current between the electrodes. SOLUTION: Raw water W in a raw water tank 1 is introduced from a raw water sending pipe 2 into an electrolytic bath 5. In this process, hydrochloric acid A of relatively high concentration is injected into the water W to make the water W in the bath 5 hydrochloric-acid-added raw water AW of a given concentration. In this state, the electrodes 7 in the bath 5 are energized for electrolysis. Since liquid reduced by the cathode and liquid oxidized by the anode are mixed always in the bath 5, the pH of the water remains almost unchanged by the electrolysis. The water AW is converted into electrolyzed liquid E with a strong oxidizing effect by the anodic oxidation, which is discharged from an electrolyzed liquid discharge pipe 8 as a low pH disinfectant having a strong sterilization effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a bactericide comprising an electrolytically treated liquid having a high bactericidal action, characterized by electrolyzing hydrochloric acid-containing raw water (hereinafter sometimes referred to as electrolytic treatment). The present invention relates to an apparatus for producing the same, a disinfectant produced by the method, and a method for disinfecting raw water. More specifically, the present invention is characterized in that, by subjecting the hydrochloric acid-added raw water to electrolytic treatment by an electrolytic cell having no diaphragm between the positive and negative electrodes, the electrolytic treatment solution is collected without being separated into anode water and cathode water. A method for producing a germicide comprising an electrolytically treated solution having a high bactericidal effect, wherein the entire electrolytically treated solution has a high sterilizing effect.
A disinfectant produced by the production apparatus and the method,
And a method for sterilizing raw water using the method. In the present specification, percentages are values by weight unless otherwise specified.

[0002]

2. Description of the Related Art Heretofore, there has been known a method of obtaining acidic water or alkaline ionized water by electrolyzing water. Generally, when performing electrolysis of water for the purpose of obtaining acidic water or alkaline ionized water, an electrolytic cell is used (supervised by Kunihiko Watanabe et al., “New Water Science and Utilization Technology”, 200-207).
P., Science Forum, 1992). A conventional electrolytic cell is provided with an electrode comprising an anode and a cathode inside, the anode and the cathode are separated by a diaphragm, and has a structure divided into an anode chamber and a cathode chamber. Water having increased electric conductivity by adding a small amount of electrolyte such as salt to the tank was supplied, and a direct current was applied to the electrodes to perform electrolysis of water.

[0003] To explain the operation of a conventional electrolytic cell, water to be electrolyzed (hereinafter referred to as raw water) is first used.
It is sent to the anode and cathode compartments of the electrolytic cell by a pump and electrolyzed, but in the anode compartment, the raw water is oxidized and some of the hydroxyl ions are removed as oxygen gas, so it is discharged from the anode compartment. The water to be produced has a high oxidation-reduction potential and exhibits acidity, so-called acidic water. On the other hand, the water discharged from the cathode chamber has a low oxidation-reduction potential and is alkaline because the raw water undergoes a reducing action and a part of the hydrogen ions are removed as hydrogen gas in the cathode chamber. Become. Acidic water has a bactericidal action,
It is used for sterilizing and cleaning instruments, fingers, etc. at medical sites and the like, and alkaline ionized water is used for drinking. As described above, in recent years, acidic water having a bactericidal effect has been produced by electrolytic treatment and used as a kind of bactericide. On the other hand, various raw waters used in our daily life, factory facilities, etc., generally require a sterilization treatment in many cases, and a more effective sterilization treatment method has always been long-awaited. In some cases was used. For example, heat exchange is performed by circulating cooling water between a condenser installed in a cooling facility such as a factory and a cooling tower attached thereto, and various bacteria grow in such cooling water. It was easy to do and became a hygiene problem. Therefore, attempts have been made to prevent the propagation of various bacteria by installing an electrolytic cell in the circulation line of the cooling water (see, for example, JP-A-5-87489). In addition, a flush toilet is provided with an electrolytic cell in a toilet and treated with flush water flowing into a toilet (see, for example, Japanese Patent Application Laid-Open No. 3-33333).
No. 2), water that has been electrolyzed by an electrolytic cell is frozen and used in an ice state (for example, see Japanese Patent Application Laid-Open No.
No. 218062). Further, a technique of equipping a water storage tank such as a bath or a pool with an electrolytic cell and sterilizing the stored water is also known (for example, Japanese Patent Application Laid-Open No. 7-2).
No. 56262).

With respect to the conventional electrolytic treatment method (hereinafter referred to as prior art 1), various improved techniques have been announced. For example, a technique has been reported in which, during the electrolytic treatment, water that is not used among acidic water and alkaline ionized water is effectively used. The following prior art is known as a technique for reducing the scale adhesion to the cathode. That is, a means for selectively adding an alkali neutralizing agent and an acidic neutralizing agent to the cathode chamber and the anode chamber of the electrolytic cell in a switchable manner is used. And a method of appropriately reversing the polarity of the electrodes of the electrolytic cell and reversing the functions of the cathode chamber and the anode chamber to prevent the scale from adhering to the cathode (Japanese Patent Laid-Open No. 4-9).
No. 9295. Conventional techniques 2) and the like are known.

In order to solve the same problem, the present inventors have developed the following technology, and have already applied for a patent. That is, a technique has been completed in which hydrochloric acid is added to raw water in a cathode chamber of an electrolytic cell to make it acidic in advance, and alkali ion water which is nearly neutral is generated in the cathode chamber and fed back to the raw water. Japanese Patent Application No. 7-63384 (prior art 3). Further, a technique is also known in which raw water is filtered, salt is added thereto, and electrolytic treatment is performed by a conventional method to obtain acidic water having a pH of 1.5 to 3.3, and the acidic water is used as a bactericide (Japanese Patent Application No. Hei 10-26139). No. 7-274921.Prior art 4).

However, the prior art 1 has the following problems. Calcium and the like dissolved in the raw water adhere to the surface of the cathode as a scale and reduce the efficiency of the electrolytic treatment.
Long-term driving becomes difficult. Since both surfaces of the diaphragm are exposed to acid and alkali and electricity flows, the diaphragm is greatly consumed and the running cost is high. When it is desired to take out only acidic water as a bactericide, the alkaline ionized water is discarded, so that water and electric power corresponding to the alkaline ionized water are wasted.

On the other hand, in the prior art 2, in order to reduce the above-mentioned problem, a method of appropriately reversing the functions of the anode and cathode of the electrolytic cell is adopted. The disadvantage is that extra equipment is required. Further, in order to reduce the above-mentioned problems, a method of neutralizing unused alkali ion water with an acid and reusing the same can be considered. However, since this method only adjusts pH, other methods such as oxidation-reduction potential and the like are considered. Has the disadvantage that the original effect cannot be obtained. Further, the prior art 3 has a disadvantage that the problem of the prior art, that is, the point that the running cost becomes expensive cannot be solved. Furthermore, in the prior art 4, since the alkaline water is generated simultaneously with the acidic water (bactericide), a large loss of power and water is generated, and a large amount of acidic water having a low pH is obtained from neutral raw water. There is a drawback that power is required and the running cost is generally high. Further, the apparatus tends to be complicated, for example, a facility for filtering raw water is separately required to prevent scale adhesion to the cathode. Also, in the conventional method for sterilizing raw water using an electrolytic cell, the conventional electrolytic cell has the above-mentioned problems (1) to (5), and as a result, there is no satisfactory sterilizing method.

[0008]

In view of the above prior art, the present inventors have conducted intensive research on a new method for producing a bactericide using electrolysis. As a result, the raw water containing hydrochloric acid was placed between the positive and negative electrodes. By passing the solution through an electrolytic cell having no diaphragm, and by electrolytically treating the hydrochloric acid-added raw water, the sterilizing effect of the electrolytically treated solution is dramatically improved, and the electrolytically treated solution after the electrolytic treatment has an excellent sterilizing effect. They have found that they can be suitably used as fungicides, and have completed the present invention.

An object of the present invention is to solve the above-mentioned problems of the prior art and eliminate the need to dispose of alkaline ionized water at all.
That is, to provide a new method for producing a bactericide obtained as a bactericide having a high bactericidal action, the entire amount of the hydrochloric acid-added raw water as a raw material, the diaphragm of the electrolytic cell is unnecessary, and the structure of the apparatus is simple, To provide a method for producing a new disinfectant capable of obtaining a large amount of disinfectant with a small-scale device,
It is an object of the present invention to provide a method for producing a bactericide which can be operated for a long time without fear of sticking scale and has a high bactericidal effect easily and at low cost. Another object of the present invention is to provide an apparatus for easily producing the bactericide having a high bactericidal effect. Still another object of the present invention is to provide a bactericide comprising an electrolytically treated liquid having a high bactericidal action produced by the above method. Still another object of the present invention is to provide a method for sterilizing raw water using the above method.

[0010]

Means for Solving the Problems The first invention of the present invention for solving the above-mentioned problems is to pass a hydrochloric acid-containing raw water through an electrolytic cell having no diaphragm between the positive and negative electrodes, A method for producing a bactericide comprising an electrolytically treated solution having a high bactericidal action, characterized in that a current is applied to both the immersed negative and positive electrodes and the above-mentioned hydrochloric acid-containing raw water is electrolytically treated, and an electrolytically treated liquid is collected. , Electrolytic treatment, and collection of the electrolytic treatment liquid are continuously performed, and the hydrochloric acid-added raw water is converted to a hydrochloric acid molar concentration of 0.001 mol / l or more and 6.4 mol / l.
The following hydrochloric acid is prepared by diluting, the collection of the electrolysis solution is performed after dilution with water, and the collection of the electrolysis solution is
It should be carried out in an effective chlorine concentration range of 0.1 ppm or more, energization should be performed with an alternating current exceeding a frequency of 0 Hz and 5 Hz or less, and energization should be 0.4 to 6.0 clon / ml of hydrochloric acid-added raw water. Desirable aspects are that the reaction is carried out with an amount of electricity of less than Coulomb and that the pH of the hydrochloric acid-added raw water is 0.5 or more and 3.0 or less.

[0011] A second invention of the present invention for solving the above-mentioned problems is a bactericide produced according to the first invention. A third invention of the present invention for solving the above-mentioned problems,
Raw water characterized by adding hydrochloric acid to raw water to prepare hydrochloric acid-added raw water, collecting an electrolytically treated liquid by performing the method of the first invention, and obtaining the collected electrolytically treated liquid as sterilized raw water. Sterilization treatment method. In the third invention, hydrochloric acid is added to a part of the raw water to prepare a hydrochloric acid-added raw water, and the electrolytic treatment liquid is collected by performing the method of the first invention. It is also possible to take a mode of returning to. A fourth invention of the present invention for solving the above problems is an electrolytic cell provided with an anode and a cathode which are not separated by a diaphragm, a water supply means for passing raw water through the electrolytic cell, and a water supply means through the water supply means. A disinfectant manufacturing apparatus comprising an electrolytically treated liquid having a high bactericidal action, comprising: hydrochloric acid adding means for adding hydrochloric acid to raw water to be liquefied; and a discharge line for discharging the electrolytically treated liquid from the electrolytic cell. is there. Further, the fourth invention of the present invention provides an electrolytic cell provided with a cathode and an anode which are not separated by a diaphragm, a hydrochloric acid-containing raw water storage means for storing hydrochloric acid-containing raw water, and a hydrochloric acid-containing raw water storing means for storing hydrochloric acid in the electrolytic cell. A device for producing a sterilizing agent comprising an electrolytically treated liquid having a high sterilizing effect, comprising: a hydrochloric acid-added raw water passing means for passing the added raw water; and a discharge pipe for discharging the electrolytically treated liquid from the electrolytic cell. It is also possible to adopt a mode in which the discharge pipe is provided with an electrolytic solution diluting means for mixing and diluting water with the electrolytic solution.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in detail,
First, the method for producing a bactericide according to the first invention of the present invention will be described. In the first invention of the present invention, the hydrochloric acid-added raw water is defined as water to which hydrochloric acid is added or water obtained by adding hydrochloric acid to an aqueous solution in which a chemical substance is dissolved,
In order to maximize the effect of the present invention, it is desirable to use hydrochloric acid-containing raw water obtained by adding a relatively high concentration of hydrochloric acid to water. In other words, it is desirable to use hydrochloric acid-containing raw water containing only hydrogen chloride. In this case, if the concentration of hydrochloric acid is too high, an irritating odor is felt due to the generation of hydrogen chloride gas, and the surrounding members may be corroded by the influence. Should not be too high. Actually, 500cc beaker of hydrochloric acid (36.46%, manufactured by Junsei Chemical Co., Ltd.) of food additive standard was used.
Was diluted with a predetermined amount of pure water, and the presence or absence of a pungent odor was confirmed. When the molarity of hydrochloric acid was 9.5 mol / l,
At 7.7 mol / l and 7.0 mol / l, a pungent odor was felt, but at 6.4 mol / l, no pungent odor was felt. When the concentration was lower than 6.0 mol / l, no pungent odor was observed. Was. Therefore, in the present invention, the molar concentration of hydrochloric acid for preparing hydrochloric acid-added raw water is 6.4 mol / mol.
1 or less is desirable. In addition, as described later, the hydrochloric acid molarity of the hydrochloric acid-added raw water prepared with hydrochloric acid is 0.001 mol.
/ L or more is desirable, so that the molar concentration of hydrochloric acid as a raw material is naturally desirably 0.001 mol / l or more. That is, 0.001 mol / l hydrochloric acid may be used as raw water with hydrochloric acid added without particular dilution. The raw water with hydrochloric acid is passed from a raw water tank through a raw water supply pipe by a raw water pump to an electrolytic cell having no diaphragm. A predetermined amount of hydrochloric acid is mixed into the raw water supply pipe from a hydrochloric acid tank by a hydrochloric acid pump, and the pH of the raw water is 0.5 to 3.0, preferably p.
H 0.8 to 3.0 was adjusted to prepare a hydrochloric acid-added raw water, and the solution was passed through an electrolytic cell having no diaphragm. In addition, the hydrochloric acid-added raw water prepared in advance may be passed as it is. Also,
The means for passing the liquid can be appropriately selected.

In the electrolytic cell, the positive and negative electrodes are disposed without being separated by a membrane. The positive and negative electrodes are immersed in raw water containing hydrochloric acid, energized, and the raw water containing hydrochloric acid is electrolyzed. The energization is performed by applying an alternating current or a direct current having a frequency of more than 0 Hz to 5 Hz or less, preferably more than 0 Hz and 2 Hz or less to 0.4 to 6.0 coulombs, preferably 0.8 to 3.0 coul / ml of the hydrochloric acid-added raw water. Done at the rate of Coulomb. The electrolytic treatment liquid is taken out of the electrolytic cell through an electrolytic treatment liquid discharge pipe, and can be used as it is or diluted with water as a disinfectant.

As described in the prior art,
An ordinary electrolytic cell for electrolyzing water has a structure in which an anode and a cathode are separated by a diaphragm. In general, electrolysis is not limited to electrolysis of water, and is often performed for the purpose of separating various products from a solution. For this purpose, an electrolytic cell having a diaphragm is usually used. However, in the present invention, since the electrolytic treatment is performed for the purpose of converting the properties of the raw water added with hydrochloric acid, there is no need to separate the liquid generated at the anode and the liquid generated at the cathode, and an electrolytic cell having no diaphragm is used. You get.

It is presumed that the reason why the sterilizing effect of the electrolytically treated solution is remarkably improved by electrolytically treating the hydrochloric acid-containing raw water in an electrolytic cell having no diaphragm is as follows. By performing the electrolytic treatment, chloride ions are oxidized on the surface of the anode and changed to hypochlorous acid. As a result, a liquid having a high sterilizing action is generated.

On the other hand, hydrogen gas is generated on the surface of the cathode to increase the pH. However, in the electrolytic cell used in the production method of the present invention, since there is no diaphragm between the anode chamber and the cathode chamber, both waters are mixed. Then, the pH slightly increases due to the change of a part of the hydrochloric acid to hypochlorous acid, but in the end, in the electrolytic treatment solution,
It is presumed that the bactericidal action generated at the anode remains as it is, and that the whole hydrochloric acid-added raw water becomes an electrolytically treated solution having a high bactericidal action.

Next, a preferred embodiment of the first invention of the present invention will be described. In the production method of the present invention, it is also possible to perform the electrolytic treatment continuously. That is, the raw water containing hydrochloric acid is continuously passed through the electrolytic cell, the electrolytic treatment is continuously performed, and the electrolytically treated liquid is continuously taken out. Thereby, a large amount of bactericide can be produced.

In the production method of the present invention, the electrolytically treated solution may be diluted with water and collected. That is, after the hydrochloric acid-containing raw water having a low pH is subjected to electrolytic treatment in advance, the electrolytic treatment solution is diluted with water to obtain a bactericide having a desired concentration. Generally, when the pH of the hydrochloric acid-added raw water is low, the electric resistance at the time of the electrolytic treatment decreases, the electrolytic treatment can be performed at a lower voltage, and the amount of electric power used can be reduced. Further, if only a small amount of the hydrochloric acid-added raw water having a low pH is electrolyzed and then diluted, only a small amount of liquid is required for the electrolysis treatment, so that a large amount of a bactericide can be obtained with a small device. In this case, as described in the test example described below, when the effective chlorine concentration of the diluted electrolytic treatment solution is reduced to less than 0.1 ppm, the sterilizing effect is reduced. Therefore, the dilution is
It is preferable from the viewpoint of the sterilization effect that the effective chlorine concentration of the electrolyzed solution after dilution falls within a range of 0.1 ppm or more.
In general, the effective chlorine concentration of the electrolytic treatment solution depends on the current value at the time of energization, but in any case, the disinfectant desirably has a range in which the effective chlorine concentration is 0.1 ppm or more. Further, focusing on the pH, the pH of the diluted electrolytic treatment solution is preferably 7.0 or less, and particularly preferably in the range of 3.5 or more and 6.5 or less. That is, if the pH of the electrolyzed solution after dilution is in such a range, free hypochlorous acid can be relatively stably present in the solution.

In the production method of the present invention, a direct current can be applied during the electrolytic treatment as in the conventional case. However, even in this case, the electrolytic cell of the present invention has an advantage that the scale is less attached to the cathode surface than the conventional electrolytic cell. This is because the electrolytic cell of the present invention does not have a diaphragm, so that the anode water and the cathode water are mixed, and the pH of the cathode surface is prevented from increasing due to the low pH of the hydrochloric acid-added raw water. That is because

However, in the manufacturing method of the present invention, it is desirable to supply an alternating current during the electrolytic treatment.
The reason is that since the electrolytic cell used in the production method of the present invention does not have a diaphragm, the negative and positive electrodes can be appropriately reversed, but if an alternating current is applied, the negative and positive electrodes are periodically reversed. As a result, the scale adhesion to the cathode surface can be more effectively suppressed than the direct current. Note that the alternating current is a current in which the positive and negative polarities are reversed periodically, and the waveform of the current is not particularly limited. However, if it is a rectangular wave as described in the examples described later,
It is preferable because the negative and positive poles are reversed instantaneously.

In the manufacturing method of the present invention, the frequency of the alternating current to be supplied is desirably higher than 0 Hz and not higher than 5 Hz. The reason for this is that if the frequency of the alternating current is too high, there is no reaction even if the electrolytic treatment is performed. As described in the test examples described below, it is desirable to use an alternating current of 5 Hz or less, particularly 2 Hz or less. In addition, "frequency is 0
The range of "exceeding Hz" does not include 0 Hz, but an alternating current having a frequency of 0 Hz means a direct current.

In the production method of the present invention, the electrolytic treatment is carried out with an amount of electricity of 0.4 to 6.0 klon / ml of the hydrochloric acid-added raw water (hereinafter referred to as hydrochloric acid-added raw water 1 ml).
The unit of the number of coulombs per ml may be described as c / ml. ). As described in the test examples described below, when electrolysis is performed at an electric quantity of 0.4-colon or more per 1 ml of the hydrochloric acid-added raw water, the bactericidal effect of the bactericide increases, and when the electric quantity is 0.8-cron or more. It is preferable to have a stronger bactericidal action. In addition, the quantity of electricity is 6.0 c.
When the concentration exceeds / ml, the effect of the electrolytic treatment becomes unnecessarily high, and waste of power increases. That is, the amount of generated gas such as chlorine gas, hydrogen gas, and oxygen gas increases, but the sterilization effect of the electrolytic treatment solution itself does not improve.
The tendency to waste power is increased. Therefore, the quantity of electricity is desirably 6.0 c / ml or less.

In the production method of the present invention, the pH is 0.5
Use hydrochloric acid-added raw water of not less than 3.0 and not more than 3.0. When the pH of the hydrochloric acid-added raw water is 3.0 or less, there is an advantage that the electric resistance at the time of the electrolytic treatment is reduced and the electrolytic treatment can be performed at a lower voltage. However, when the pH is extremely low, the sterilizing effect of the electrolytic treatment solution is not improved even though the amount of generated gas such as chlorine, hydrogen, and oxygen at the time of the electrolytic treatment increases, so that waste of electric power increases. Therefore, it is desirable that the pH of the hydrochloric acid added raw water is at least 0.5 or more, preferably 0.8 or more. The pH of the hydrochloric acid-added raw water is important because it particularly affects the efficiency and the like in the electrolytic treatment. Focusing on the concentration of the hydrochloric acid-containing raw water, the hydrochloric acid molar concentration of the hydrochloric acid-containing raw water is 0.1%.
Desirably, it is 001 mol / l or more and 1 mol / l or less. When the method of the present invention is performed in a home, factory, cafeteria, or the like, it is complicated to prepare hydrochloric acid-containing raw water from high-concentration hydrochloric acid. Therefore, it is preferable to use hydrochloric acid-containing raw water prepared in advance. In this case, the molar concentration of hydrochloric acid in the raw water containing hydrochloric acid is 0.05 mol / l or more,
If it is / l or less, waste of electric power is small as long as the sterilizing effect can be ensured, and even if a direct current is used, scale adhesion to the cathode surface is small, which is preferable.

The second invention of the present invention is a bactericide produced by the above-mentioned production method. The disinfectant of the present invention is characterized by having no particularly unpleasant off-taste or off-odor besides sour taste and no residue after drying since it uses raw water added with hydrochloric acid as a starting material. Therefore, it is particularly preferable to use it when sterilizing pipes, filling devices, containers, and the like in the fields of the food industry, the pharmaceutical industry, and the like. The bactericide of the present invention produced by the above production method is preferably diluted with water, and the pH after the dilution is adjusted to 7.0 or less, particularly preferably to a pH of 3.5 or more and 6.5 or less. A third invention of the present invention is a method for sterilizing raw water using the method of the first invention. The first invention of the present invention can be used as a method for sterilizing raw water.
In the present invention, the raw water specifically refers to water or an aqueous solution in which a chemical substance is dissolved, for example, an aqueous solution or suspension having a total solid content of 300 ppm or less. It can also be said that it is desirable to perform the treatment. If hydrochloric acid is added to such raw water to prepare hydrochloric acid-added raw water and the electrolytic treatment of the first invention of the present invention is performed, the generated electrolytically treated liquid can be regarded as sterilized raw water. Also, a hydrochloric acid-added raw water is prepared by adding hydrochloric acid to a part of the raw water, an electrolytic treatment of the first invention of the present invention is similarly performed, and an electrolytic treatment liquid is collected. It may be a mode of returning. According to the method of the third invention of the present invention, unlike the prior art, no alkaline water is generated, and there is no need to dispose of the alkaline water. Therefore, according to the third aspect, the sterilization treatment can be performed without discarding the raw water at all. That is, it can be said that a sterilization method which solves the above-mentioned problems of the conventional electrolytic cell. As described above, in the third invention of the present invention, since the sterilization treatment can be performed without discarding the alkaline water, the application range is extremely wide and can be used for the sterilization treatment of various liquids. The raw water in the third invention of the present invention includes drinking water, various wastewaters, cooling water for cooling towers, water used as raw material for ice, washing water for toilets,
And water storage in baths, pools, water tanks, fish farms, etc., but are not limited to these. The specific embodiment of the third invention of the present invention will be described later.

[0025] A fourth invention of the present invention is the apparatus for producing a bactericide, wherein at least an electrolytic tank provided with a cathode and an anode which are not separated by a diaphragm, a water supply means for passing raw water through the electrolytic tank, It is provided with a hydrochloric acid addition means for adding hydrochloric acid to raw water flowing through the water supply means, and a discharge pipe for discharging the electrolytic treatment liquid from the electrolytic cell. The electrolytic cell of the present invention comprises a container and negative and positive electrodes, and there is no membrane separating the negative and positive electrodes. The container constituting the electrolytic cell has a hydrochloric acid-added raw water inlet and an electrolytic treatment solution outlet. The shape of the container may be any shape such as a rectangular column or a cylinder, and the material of the container is desirably excellent in corrosion resistance to hydrochloric acid, and examples thereof include polyvinyl chloride, FRP, and polyethylene. The shape of the electrode may be a known one, but the material of the electrode needs to be chemically stable even when reacted with the hydrochloric acid-added raw water, and platinum is optimal as the material. A discharge pipe for discharging the electrolytic treatment liquid is connected to the electrolytic treatment liquid discharge port of the electrolytic cell.

The apparatus of the present invention employs a configuration in which a relatively high concentration of hydrochloric acid is diluted with raw water, and the diluted hydrochloric acid-containing raw water is passed through an electrolytic cell while being appropriately prepared. Raw water is passed through the electrolytic cell by water supply means. The water supply means may be of any type, but an example is shown in which a raw water supply pipe branched from a water pipe or a water tap is connected to the hydrochloric acid-added raw water inlet of the electrolytic cell via a water supply pump. In this case, the facility cost is low because of a simple structure in which the tap water is simply drawn directly from the water pipe. Further, as in a preferred embodiment described later, a raw water tank may be disposed upstream of the water supply tank, and the raw water may be temporarily stored in the raw water tank and then passed through the electrolytic cell.

Further, the apparatus of the present invention is provided with a hydrochloric acid adding means for adding hydrochloric acid to raw water flowing through the water supply means, that is, raw water before reaching the electrolytic cell. The hydrochloric acid adding means may be in any mode.For example, when hydrochloric acid is commercially available in the form of a filled container, a hose is directly inserted into the filled container and the other end of the hose is connected with hydrochloric acid. A mode in which it is connected to one end of a supply pipe and the other end of the hydrochloric acid supply pipe is connected to a raw water supply pipe.

As a mode of connecting the hydrochloric acid supply pipe to the raw water supply pipe, the end of the hydrochloric acid supply pipe is cut into the raw water supply pipe,
A pipe that opens after being bent in the direction in which the raw water flows at the center of the raw water transmission pipe can be exemplified. In such a hydrochloric acid supply pipe, the hydrochloric acid is sucked by the dynamic pressure of the raw water flow inside the raw water supply pipe, and the hydrochloric acid is automatically added to the raw water flow by the function of the ejector. Become. In this case, it is desirable to provide a control valve in the hydrochloric acid supply pipe to control the amount of addition. It is also possible to forcibly send hydrochloric acid by a hydrochloric acid metering pump.

As an example of the means for adding hydrochloric acid, in addition to the above-mentioned embodiment in which a hose is inserted into the container filled with hydrochloric acid, a hydrochloric acid tank for storing hydrochloric acid is provided in advance, and a portion from the outlet of the hydrochloric acid tank to the raw water supply pipe is provided. An example in which communication is made by a hydrochloric acid supply pipe via a hydrochloric acid metering pump can be exemplified. The junction of the hydrochloric acid supply pipe and the raw water supply pipe may be provided at any place of the raw water supply pipe, and the metering pump for hydrochloric acid is preferably made of a material having excellent corrosion resistance to hydrochloric acid. When the junction of the hydrochloric acid supply pipe and the raw water water supply pipe is located on the upstream side of the water supply pump, it is desirable that the water supply pump itself also use a material having excellent corrosion resistance to hydrochloric acid. Examples of materials having excellent corrosion resistance to hydrochloric acid include Teflon (trade name), polyvinyl chloride, and polyethylene.

Next, the operation of the device of the present invention will be described. First, raw water is passed through the electrolytic cell by the water supply means. Before the raw water reaches the electrolytic cell, a relatively high concentration of hydrochloric acid is added to the raw water by hydrochloric acid adding means. Therefore, the hydrochloric acid-added raw water whose pH has been adjusted is passed through the electrolytic cell. In the electrolytic cell, the electrolytic treatment is carried out by energizing both the positive and negative electrodes immersed in the hydrochloric acid-added raw water. The electrolytically treated liquid is discharged from a discharge pipe provided in the electrolytic cell, and can be obtained as a disinfectant. In another aspect of the apparatus of the present invention, a hydrochloric acid-added raw water storage unit and a hydrochloric acid-added raw water passage unit are provided in place of the water supply unit and the hydrochloric acid addition unit, and have a simpler structure. The hydrochloric acid-added raw water storing means is a means for temporarily storing the hydrochloric acid-added raw water prepared in advance, and a simple container can be used. However, a material which is not corroded by hydrochloric acid is preferable. The hydrochloric acid-added raw water passing means is a means for passing the hydrochloric acid-added raw water from the hydrochloric acid-added raw water storage means to the electrolytic cell, and examples thereof include a pump and an ejector. A simple container may be used as the hydrochloric acid-added raw water storing means. For example, a hose is directly inserted into the container and the other end of the hose is connected to the electrolytic cell. A structure similar to the structure can be taken. In such an embodiment, the hydrochloric acid-added raw water prepared in advance can be passed through the electrolytic cell by the hydrochloric acid-added raw water storage means and the hydrochloric acid-added raw water flow-through means to obtain a disinfectant.

Further, the apparatus of the present invention is provided with an electrolytic solution diluting means for mixing and diluting the electrolytic solution with water in the discharge pipe. The electrolytic treatment liquid diluting means may be any means as long as water can be added to the electrolytic treatment liquid discharged from the electrolytic tank. For example, the electrolytic treatment liquid is temporarily stored in an open tank, and this tank is The flow rate and p
An embodiment in which water is added at a flow rate according to H and mixed is exemplified. In order to maximize the bactericidal effect of the collected bactericide, it is desirable to mix and dilute water with the electrolytically treated solution discharged from the electrolytic cell as soon as possible. In addition, since the electrolytic treatment solution contains various gases, it is desirable to dilute the solution in a sealed state. The device of the present invention can also be used as a raw water sterilization treatment device. When the device of the present invention is used as a raw water sterilization treatment device, the discharge line is
It may be connected to a pipe or the like through which raw water flows, and the electrolytic treatment solution may be mixed and diluted with the raw water. In the case where the discharge pipe is provided with an electrolytic treatment liquid diluting means, the electrolytic treatment liquid may be "water".
Are mixed and diluted, and the range of the term “water” includes raw water.

As an embodiment of the apparatus of the present invention, the apparatus shown in FIG. 1 can be exemplified. FIG. 1 is a diagram showing an embodiment of the apparatus of the present invention. In FIG. 1, a raw water supply pipe 1a is connected to a raw water tank 1. Since the raw water W is supplied through a float valve (not shown), the raw water tank 1
Is kept constant. A raw water supply pipe 2 is connected to the raw water tank 1, and is connected to an electrolytic cell 5 via a raw water pump 3. Furthermore, a hydrochloric acid supply pipe 10 that joins the raw water supply pipe 2 from the hydrochloric acid tank 9 via the hydrochloric acid metering pump 4 includes:
The raw water pump 3 is connected to the raw water supply pipe 2 at an upstream portion 10a. The electrolytic cell 5 is connected to an electrolytic treatment liquid discharge pipe 8 for discharging a germicide. In the electrolytic cell 5, there is no membrane for separating the positive and negative electrodes, and it is a single chamber. The electrodes 7 are installed and each is connected to a power source 6.

Next, the operation of the apparatus having the above configuration will be described. The raw water W is passed through the raw water supply pipe 2 by the raw water pump 3 to the electrolytic cell 5. A relatively high concentration of hydrochloric acid A is injected into the raw water W through the hydrochloric acid supply pipe 10 by the hydrochloric acid metering pump 4. In this way, the raw water W passed through the electrolytic cell becomes a hydrochloric acid-containing raw water AW having a certain concentration. Next, the electrode 7 in the electrolytic cell 5 is energized to perform the electrolytic treatment. In the electrolytic cell, the solution reduced at the cathode and the solution oxidized at the anode are always mixed, so that the pH before the electrolytic treatment is maintained. It is almost the same value as the hydrochloric acid added raw water AW. Chlorine, hypochlorous acid, ozone, and the like generated by the oxidation reaction at the anode tend to exist in a relatively stable free state due to the strong acidity of the electrolytic treatment solution. Accordingly, the hydrochloric acid-added raw water AW becomes an electrolytic treatment solution E having a strong oxidizing effect, and has a low pH from the electrolytic treatment solution discharge pipe 8 and has a strong oxidizing effect and can be suitably used as a disinfectant having a high sterilizing effect. The liquid E is discharged.

As another embodiment of the apparatus of the present invention, for example, the apparatus shown in FIG. 2 can be exemplified. FIG. 2 is a diagram showing another embodiment of the apparatus of the present invention. In the apparatus of FIG. 2, most of the components are the same as those of the apparatus shown in FIG. 1 as denoted by the same reference numerals as those in FIG. 1, and detailed description is omitted. The apparatus shown in FIG. 2 is provided with a means for diluting the electrolytic treatment liquid. As a means for diluting the electrolytic solution, a diluting water pipe 12 is provided in the raw water tank 1 separately from the raw water pipe 2. The dilution water feed pipe 12 joins the electrolytic treatment liquid discharge pipe 8 from the electrolytic tank 5 at a junction 12a, and a disinfectant feed pump 11 is disposed downstream of the junction 12a. In addition, the dilution water transmission pipe 12
Is provided with a flow control valve 13. Other components are the same as those of the apparatus of FIG.

The operation of the apparatus shown in FIG.
Is discharged through the electrolytic solution discharge pipe 8, but at the junction 12a, it joins with the dilution water sent through the dilution water feed pipe 12, is mixed and diluted. The diluted electrolytic treatment liquid flows through the treatment liquid discharge pipe 8, and at the junction 12 a, merges with the dilution water sent through the dilution water supply pipe 12, is mixed and diluted.
The diluted electrolytic treatment liquid is sent by the germicide sending pump 11 and can be collected as the germicide Ed. The flow rate of the dilution water can be adjusted by the flow control valve 13. In the embodiment shown in FIG. 2, the electrolytic treatment liquid E discharged from the electrolytic cell 5 can be immediately diluted, and the electrolytic treatment liquid E can be diluted in a closed state.
There is a specific effect that the gas contained in the electrolytic treatment liquid E does not escape. Further, as another embodiment of the device of the present invention, for example, the device shown in FIG. 3 can be exemplified. FIG. 3 is a diagram showing another embodiment of the device of the present invention.
In the apparatus shown in FIG. 3, most of the components are common to the apparatus shown in FIG. 1, as denoted by the same reference numerals as those in FIG. 1, and a detailed description thereof will be omitted. The device of FIG.
A hydrochloric acid-added raw water storage means 14 is provided.
It is connected to the. An electrolytic treatment liquid discharge pipe 8 for discharging a sterilizing agent is connected to the electrolytic bath 5, and the electrolytic treatment liquid discharge pipe 8 is connected to an ejector 19 through an orifice 16. Is connected to a dilution water supply pipe 12. The dilution water feed pipe 12 is a constant flow valve 16
And is connected to the dilution water source 17. Other components are the same as those of the apparatus of FIG. The operation of the apparatus shown in FIG. 3 will be described. In the hydrochloric acid-added raw water storage means 14, a hydrochloric acid-added raw water AW prepared in advance is stored. The dilution water is supplied from the dilution water source 17 through the dilution water supply pipe 12 to the ejector-1.
9 (in the direction of arrow Y), the flow rate of which is constant.
Is controlled to be constant. Since the ejector 19 sucks the electrolytic treatment liquid discharge pipe 8, the hydrochloric acid added raw water storage means 14 is used.
The hydrochloric acid-added raw water AW stored in the tank flows through the hydrochloric acid-added raw water pipe 15 (in the direction of arrow X1), and flows through the electrolytic cell 5. The electrolytic solution E discharged from the electrolytic bath 5 flows through the electrolytic solution discharge pipe 8 and reaches the ejector 19 (in the direction of the arrow X2), and is mixed and diluted with the dilution water from the dilution water source 17. The diluted electrolytic treatment liquid can be collected as a bactericide Ed. The ratio of the flow rate of the electrolytic treatment solution to the flow rate of the dilution water is
It is adjusted by an orifice 16 previously installed in the electrolytic solution discharge pipe 8. In the apparatus shown in FIG.
The function of No. 19 also serves as the function of the means for passing the hydrochloric acid-added raw water, and the structure is simple. Next, an embodiment using the apparatus of FIG. 3 will be described. The disinfectant produced by the apparatus shown in FIG. 3 can be added to, for example, flush water of a flush toilet. Generally, flush toilets are easily contaminated by various bacteria, and may be contaminated with bacteria. It is known to use an electrolytic cell in such a case, but since the conventional electrolytic cell has the above-mentioned problems, a more desirable flush toilet can be obtained by applying the apparatus of FIG. . FIG. 4 is a view showing a flush toilet using the apparatus of FIG. In FIG. 4, FIG.
The same reference numerals as those in FIG. 3 denote the same components as in FIG. 3, and a detailed description thereof will be omitted. In FIG. 4, a flush water pipe 24 is connected to the toilet 25, and the flush water pipe 24 is connected to the system 23. The washing water is stored in the system 23. The system 23 is provided with a float valve 21. The float valve 21 is connected to a flush water supply pipe 12a, and the end of the flush water supply pipe 12a is connected to a flush water supply source 17a. . The washing water supply pipe 12a is provided with a disinfectant manufacturing apparatus 20 shown in FIG. The operation of the apparatus shown in FIG. 4 will be described.
The water level of the heater 23 drops. The position of the float 22 of the float valve 21 is lowered, and the float valve 21 is opened.
The cleaning water W0 is supplied from the cleaning water supply source 17a to the cleaning water supply pipe 12
The water is sent to the system 23 through a. The washing water W0 is sent until the water level of the system recovers. On this occasion,
The disinfectant manufacturing apparatus 20 operates to produce the disinfectant, and the disinfectant is mixed into the cleaning water W0 via the ejector 19. Thereby, the system 23, the washing water pipe 2
The sterilized washing water flows through 4 and the toilet 25.
The operation of the disinfectant manufacturing apparatus 20 is based on the float valve 2
Various automatic operations, such as interlocking with 1, are also possible. Further, a pump may be used instead of the ejector-19. In the apparatus of FIG. 4, unlike the conventional electrolytic cell, the above-mentioned problems (1) to (4) do not exist, and thus the manufactured disinfectant can be suitably used. In particular, the apparatus shown in FIG. 4 has an advantage that it can cope with flush toilets in which there is no system. Incidentally, in a flush toilet that is recently popular and has a shower attached to the toilet, and the shower can clean the anus after defecation, the disinfectant produced by the apparatus of the present invention is used for the shower. It is extremely sanitary if used as water. In this case, the operation of the shower and the apparatus of the present invention may be automated so as to be linked. Next, an embodiment of a sterilization treatment method according to the third invention of the present invention will be described. For convenience of explanation, an apparatus for performing a sterilization process will be exemplified, and the description of the apparatus will be replaced with the description of the sterilization method. The sterilization method of the present invention can be carried out, for example, by using the apparatus shown in FIG. FIG. 5 is a diagram showing an example of a sterilization apparatus for performing the sterilization method of the present invention.
The device of FIG. 5 is obtained by changing some of the components of the device of FIGS. 1 to 3, and most of the components are denoted by the same reference numerals as in FIGS. 1 to 3. 2 is common to the apparatuses shown in FIGS. 1 to 3 and detailed description is omitted. In FIG. 5, one end of a raw water supply pipe 2 is connected to a raw water supply source 1.
7b. The raw water transmission pipe 2 is a raw water transmission pipe 2
a and a raw water transmission pipe 2b, and the raw water transmission pipe 2b is provided with a sterilization treatment device 30. This sterilization apparatus 30 is an application of the apparatus shown in FIG. The raw water transmission pipe 2a is provided with a flow control valve 32, and the raw water transmission pipe 2a.
b is provided with a flow control valve 31. The electrolytic treatment solution discharge pipe 8 joins with the raw water supply pipe 2a to form the raw water supply pipe 2c. The operation of the apparatus shown in FIG. 5 will be described. In the raw water supply pipe 2, raw water W1 flows from a raw water supply source 17b (in the direction of arrow Y) by a pump (not shown), and branches into the raw water supply pipe 2a and the raw water supply pipe 2b. Flow (respectively in the directions of arrows Y1 and Y2). These flow ratios are determined by the flow control valve 31.
And 32. Hydrochloric acid A having a relatively high concentration is injected into the raw water flowing through the raw water supply pipe 2b through the hydrochloric acid supply pipe 10. Next, the liquid is passed through the electrolytic cell, subjected to electrolytic treatment, and discharged from the electrolytic treatment liquid discharge pipe 8 (in the direction of arrow X2). The electrolytic treatment liquid merges with the raw water flowing through the raw water transmission pipe 2a and flows through the raw water transmission pipe 2c (in the direction of arrow Y3). Thus, the raw water W1 is sterilized. According to the apparatus shown in FIG. 5, unlike the conventional electrolytic cell, no alkaline water is generated, and there is no need to dispose of the alkaline water. In addition, since a part of the raw water W1 is collected by the raw water supply pipe 2b and prepared as the hydrochloric acid-containing raw water AW, the flow rate of the raw water W1 does not greatly increase after the sterilization treatment. Next, FIG.
When the mode using the device is explained, first, an operation of sterilizing drinking water and converting it into drinking water can be exemplified. In this case, the “raw water supply source 17b” in FIG. 5 is set as the supply source of drinking water. That is, the drinking water flowing from the drinking water supply source 17b is sterilized by the apparatus shown in FIG. 5, becomes water suitable for drinking, and is supplied to waterworks or the like. Another example of the use of the apparatus in FIG. 5 is sterilization of wastewater discharged from factories, homes, and the like. In this case, the “raw water supply source 17b” in FIG. 5 is used as the wastewater discharge source. That is, if the wastewater discharged from the wastewater discharge source 17b is sterilized by the apparatus shown in FIG.
Environmental pollution due to pathogenic bacteria and the like can be prevented. Further, as another utilization form of the apparatus of FIG. 5, an operation of freezing water sterilized by the apparatus of FIG. 5 to obtain sanitary ice can be exemplified. Generally, when transporting fresh seafood, ice is often packed to maintain freshness, but the ice used for this purpose is desirably sanitary. If ice is produced from water sterilized by the apparatus shown in FIG. 5, it is sanitary and preferable because it maintains the sterilizing action. Further, another use form of the apparatus of FIG. 5 will be described. As an example, a sterilization treatment of cooling tower cooling water as shown in FIG. 6 can be exemplified. FIG. 6 is a diagram showing an example in which the sterilizing apparatus of FIG. 5 is provided in a circulation channel of cooling tower cooling water. In FIG.
The cooling tower 33 and the condenser 34 of the cooling facility are connected by a circulation line 37. Circulation line 37
Is provided with a pump 35. The circulation line 37 is provided with the sterilization apparatus 30 shown in FIG. Further, a chlorine concentration meter 36 is provided in the circulation line 37, and an output line 36 a of the chlorine concentration meter 36 is connected to a controller 38. The output line 4 a of the controller 38 is connected to the metering pump 4 for hydrochloric acid of the sterilizing apparatus 30, and the output line 6 a is connected to the power supply 6. 6, the cooling water is circulated through the circulation line 37 by the pump 35 (in the direction of arrow Y).
6 is measured. The measured value of the chlorine concentration is transmitted to the controller 38 via the output line 36a, and based on this, the controller 38 calculates the optimum sterilization condition and outputs the same via the output lines 4a and 6a. By controlling the hydrochloric acid metering pump 4 and the power supply 6 to sterilize the cooling water, it is possible to prevent germs from growing. In the embodiment of FIG. 6, the point that the pH of the cooling water or the effective chlorine concentration can be controlled, and thus the corrosion of each device can be suppressed, is an advantageous effect as compared with the conventional electrolytic cell. Further, FIG.
Explaining another utilization form of the device, a sterilization treatment of a water storage tank as shown in FIG. 7 can be exemplified. FIG. 7 is a diagram illustrating an example in which the water treatment tank is provided with the sterilization apparatus of FIG. 5. In FIG. 7, most of the components are common to the device shown in FIG. 6, as denoted by the same reference numerals as those in FIG. 6, and detailed description is omitted. In FIG. 7, a water storage tank 39 is provided with a circulation pipe 37, and the circulation pipe 37 is provided with a pump 35, the sterilization apparatus 30 shown in FIG.
Is provided. The operation of FIG.
The raw water W2 in 9 is circulated in the circulation pipe line 37 by the pump 35 in the arrow Y direction. The chlorine concentration of the raw water W2 is measured by the chlorine concentration meter 36, and the sterilizing apparatus 3 is used as in FIG.
0 is sterilized. That is, the raw water W in the water tank 39
2 can be sterilized, and the breeding state of various bacteria can be freely controlled. In this case, control may be performed by the controller 38 so that the effective chlorine concentration in the water tank 39 becomes an optimum value. In addition, as the water storage tank 39 of FIG.
Examples include a bath, a pool, an aquarium, a fish pond, and the like. When used in a bath, it is preferable to install a filtration device and a heating device in the circulation line 37. When used in a pool, chlorine is directly blown into water, and sodium hypochlorite is added to water. Has an advantageous effect in that the sterilizing power is strong, the facility is simple, and the handling of chlorine gas is not required as compared with the method of injecting chlorine gas. It is clear that all of the above-mentioned problems of the conventional electrolytic cell have been solved in all the examples exemplified above, and it can be understood that the present invention is extremely effective. Incidentally, in the conventional electrolytic cell, in many cases, a salt such as sodium chloride was mixed into the raw water to perform the electrolytic treatment to increase the electrolytic efficiency, but in the present invention, even the hydrochloric acid-containing raw water containing no salts is used. Electrolytic treatment can be performed efficiently. When the hydrochloric acid-containing raw water containing no salts is used as described above, there is an advantage that the salts do not precipitate as solids when the electrolytic treatment solution is used. That is, no salt adheres to the inside of the cooling tower 33 in FIG. 6, and no salt adheres to the wall surface of the water storage tank 39 in FIG. As described above, when the salt-containing raw water containing no salt is used, the present invention has a far more advantageous effect than the conventional one.

Next, the present invention will be described in detail with reference to test examples. Test Example 1 This test was performed to examine the relationship between the frequency and the sterilizing effect when electrolytic treatment was performed using a rectangular wave alternating power supply. 1) Preparation of sample The flow rate of the raw water was adjusted to 900 ml per minute, the number of rotations of the raw water pump 3 and the quantitative pump 4 for hydrochloric acid was adjusted to adjust the pH of the hydrochloric acid-added raw water to 2.4, The alternating current to be supplied is 14 A, and the frequency is 0.5 Hz.
A sample of a disinfectant was produced in the same manner as in Example 4 described below using the apparatus of Example 3 described below except that the frequency was changed stepwise from 10 Hz to 10 Hz.

2) Test method The bactericidal effect of the bactericide produced under each condition was tested by the following method. E. coli [University of Tokyo Institute of Medical Science (IID) O111 strain. The same shall apply hereinafter) to a 50 ml sterilized ordinary broth medium (manufactured by Eiken Chemical Co., Ltd.), inoculate one loop of platinum, and incubate at 37 ° C. for 20 hours (culture number 1).
1 × 10 ⁸ / ml. 1) Add 1 ml, mix evenly,
The mixture was allowed to stand at room temperature for 2 minutes, and the number of bacteria (N) in the mixture was measured by a conventional method (Yukichi Tsugo et al., “Daily Handbook”, No. 513-51).
4, Asakura Shoten Co., Ltd., 1973). In addition, the number of bacteria (N ₀ ) of the control similarly tested using sterile physiological saline instead of the bactericide sample was also measured.
The ratio of the number of bacteria of the fungicide sample to the number of bacteria of the control (N ₀ /
N) was calculated and the ratio was expressed as a logarithmic value to test the bactericidal effect.

3) Test results The results are as shown in Table 1. As is clear from Table 1, a sample having a frequency of 5 Hz or less exhibited a bactericidal effect, and a sample having a frequency of 2 Hz or less exhibited an extremely high bactericidal effect. As a result, in the present invention, it was found that the frequency of the alternating current was 5 Hz or less, more preferably 2 Hz or less. Incidentally, the bactericide according to the present invention,
Similar tests were conducted for other devices and other manufacturing methods, and almost the same results were obtained.

[0039]

[Table 1]

Test Example 2 This test was conducted to examine the relationship between the amount of electrolytic electricity and the bactericidal effect when electrolytic treatment was performed using a DC power supply. 1) Preparation of sample The flow rate of the raw water was adjusted to 900 ml per minute, the number of revolutions of the raw water pump 3 and the quantitative pump 4 for hydrochloric acid was adjusted to adjust the pH of the hydrochloric acid-added raw water to 2.6, Table 2 shows the amount of electrolytic electricity assuming that the current flowing is a direct current.
As shown in Example 2, a fungicide sample was produced in the same manner as in Example 4 described below, except that the concentration was changed stepwise from 0.27 c / ml to 1.3 c / ml.

2) Test Method The bactericidal effect of each bactericide sample was tested in the same manner as in Test Example 1.

3) Test results The results are as shown in Table 2. As is clear from Table 2, a sample having an electrolysis amount of 0.4 c / ml or more exhibited a bactericidal effect, and a sample having 0.8 c / ml or more exhibited an extremely high bactericidal effect. From these results, it was found that in the electrolysis treatment of the present invention, the value of the amount of electrolysis was 0.4 c / ml or more, more preferably 0.8 c / ml or more. In addition, about the disinfectant which concerns on this invention, it tested similarly about another apparatus and another manufacturing method, but almost the same result was obtained.

[0043]

[Table 2]

Test Example 3 This test was conducted to examine the relationship between the effective chlorine concentration of the bactericide and the bactericidal effect. 1) Preparation of sample Except that the flow rate of raw water was adjusted to a rate of 470 ml per minute, and the amount of electrolysis electricity was changed stepwise by using a flowing current as a direct current, thereby changing the effective chlorine concentration.
A fungicide sample was produced in the same manner as in Example 4 described below. The obtained sample was diluted by an appropriate amount, and the available chlorine concentration was determined by the iodine method (edited by the Pharmaceutical Society of Japan, “Hygiene Test Method / Comment”, 10th
66, Kanehara Shuppan Co., Ltd., 1990) to obtain a group of samples in which the effective chlorine concentration gradually changed from 0.05 ppm to 6.4 ppm. The pH of each sample was adjusted to about 5.

2) Test Method The bactericidal effect of each bactericide sample was tested in the same manner as in Test Example 1.

3) Test results The results are as shown in Table 3. As is evident from Table 3, the bactericidal effect is reduced in samples having an effective chlorine concentration of less than 0.1 ppm. As a result, it was found that in the production method of the present invention, it is desirable to use the disinfectant in a state where the effective chlorine concentration is 0.1 ppm or more.
In addition, about the disinfectant which concerns on this invention, it tested similarly about another apparatus and another manufacturing method, but almost the same result was obtained.

[0047]

[Table 3]

[0048]

Next, the present invention will be described in detail with reference to examples.
The present invention is not limited at all by the following Examples. Embodiment 1 One embodiment of the manufacturing apparatus of the present invention is shown in FIG. The device shown in FIG. 1 includes the following devices. In FIG. 1, each component and its operation are as described in the embodiment as described above. Raw water tank 1 ・ ・ ・ 100 l tank made of vinyl chloride manufactured by Hokuetsu Giken Kogyo Co., Ltd. Raw water pump 3 ・ ・ ・ ・ ・ ・ Elepon SL-35 SFD hydrochloric acid tank 9 ・ ・ ・ ・ ・ ・ Hokuetsu Giken Kogyo Manufactured by Hokuetsu Giken Kogyo Co., Ltd., electrode distance 2 mm, electrode area 5000 cm ² , no diaphragm Electrode 7 -Hokuetsu Giken Kogyo Co., Ltd., Platinum coating-Titanium net Power supply 6: Chuo Seisakusho, SM93-1280 Electrolytic treatment solution discharge pipe 8: Hokuetsu Giken Kogyo Co., Ltd.

Example 2 This example is an example of a method for producing a disinfectant using the production apparatus of Example 1 and the contents will be described with reference to FIG. First, the apparatus was preliminarily operated as follows. Raw water is supplied from the raw water tank 1 storing the raw water (well water) to the electrolytic cell 5 by the raw water pump 3 at a rate of 1000 liters per hour, and the food additive standard hydrochloric acid (manufactured by Junsei Chemical Co., Ltd.).
36.46%) was continuously added to the raw water by the hydrochloric acid metering pump 4 from the hydrochloric acid tank 9 storing the hydrochloric acid, the hydrochloric acid-containing raw water was experimentally prepared, and the prepared hydrochloric acid-containing raw water was collected.
Was measured, the number of revolutions of the hydrochloric acid metering pump 4 was adjusted, and the pH of the hydrochloric acid-added raw water was adjusted to 2.5.

Next, raw water was supplied from the raw water tank 1 storing raw water to the electrolytic tank 5 by the raw water pump 3 at a rate of 1000 liters per hour based on the conditions set by the preliminary test. Hydrochloric acid (manufactured by Junsei Chemical Co., Ltd. 3
6.46%) was continuously added to the raw water by the hydrochloric acid metering pump 4 from the stored hydrochloric acid tank 9 to prepare hydrochloric acid-containing raw water having a pH of 2.5 and passed continuously through the electrolytic cell 5 to add hydrochloric acid. An alternating current having a frequency of 2 Hz is applied to the electrode 7 immersed in raw water,
Electric current is supplied at a rate of 0.8 coulomb per 1 ml of the hydrochloric acid-added raw water, the hydrochloric acid-added raw water is subjected to electrolytic treatment, an electrolytic treatment liquid is collected from the electrolytic treatment liquid discharge pipe 8, and the pH 2.5 and the oxidation-reduction potential 1
130 mV of fungicide was obtained continuously at a rate of about 1000 l per hour. The obtained fungicide was tested by the same method as in Test Example 1, and as a result, log (N ₀ / N) was 7.0 or more, and a remarkable bactericidal effect was recognized.

Embodiment 3 Another embodiment of the manufacturing apparatus of the present invention will be described. The configuration of each component is the same as that of the first embodiment (each component is denoted by the same reference numeral as in FIG. 1 and is not shown), and the apparatus of this embodiment includes the following devices. I have. Raw water pump 3 ········································································································································· Yuasa Ionics Co. MARK-IL (electrode spacing 2 mm, no diaphragm) Power supply 6 DC power supply (Kikusui Electric, PAK35-20A) and rectangular wave alternating power supply (Omron Corporation, DC power supply S82D-3024 2) The combination of the units generates ± 24V and the frequency can be arbitrarily converted.) Other than the above-mentioned devices, the same devices as in the first embodiment were used.

Embodiment 4 This embodiment is an example of a method for producing a bactericide using the apparatus of Embodiment 3 and the contents will be described with reference to FIG. First, the apparatus was preliminarily operated as follows. Raw water is supplied from the raw water tank 1 storing raw water (well water) to the electrolytic cell 5 by the raw water pump 3 at a rate of 130 liters per hour, and from the hydrochloric acid tank 9 storing reagent grade 1 hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.). Hydrochloric acid metering pump 4 continuously adds to raw water, prepares hydrochloric acid-added raw water on a trial basis, collects prepared hydrochloric acid-added raw water, measures pH, and measures the pH.
Was adjusted to adjust the pH of the raw water containing hydrochloric acid to 1.45.

Next, raw water was supplied from the raw water tank 1 storing raw water to the electrolytic cell 5 by the raw water pump 3 at a rate of 130 liters per hour based on the conditions set by the preliminary test. (Manufactured by Kanto Kagaku Co., Ltd.) was continuously added to the raw water by the hydrochloric acid metering pump 4 from the stored hydrochloric acid tank 9 to prepare a hydrochloric acid-added raw water having a pH of 1.45. A direct current is applied to the electrode 7 immersed in the added raw water at a current value of 21 A and a voltage of 6.3 V to electrolyze the hydrochloric acid added raw water, and an electrolytically treated liquid is collected from the electrolytically treated liquid discharge pipe 8 to have a pH of 1.45 and A bactericide having an oxidation-reduction potential of 1170 mV was obtained. Further, the obtained bactericide was diluted 10 times with well water, pH 2.55, oxidation-reduction potential 1
135 mV of sterile water was obtained. The obtained bactericide and germicidal water were tested by the same method as in Test Example 1. As a result, both had log (N ₀ / N) of 7.0 or more, and both showed a significant bactericidal effect. Further, the germicide obtained in Example 4 was diluted 20 times with well water to obtain bactericidal water having a pH of 5.1. The effective chlorine concentration of this sterilized water was 3.0 ppm. The sterilized water diluted 20-fold was tested by the same method as in Test Example 1. As a result, log (N ₀ / N) was 7.0 or more, and a remarkable sterilizing effect was recognized. Further, the above 1
The sterilized water diluted 0-fold and the sterilized water diluted 20-fold were respectively put into containers, and stored at room temperature for 3 days in a light-shielded state. After that, each sterilizing effect was tested by the same method as in Test Example 1. , Log (N ₀ / N) was 5.3 for a 10-fold dilution and 7.0 or more for a 20-fold dilution. Therefore, the pH after dilution is 5.1,
It has been found that the bactericidal effect can be maintained for a longer time. Furthermore,
The same experiment was carried out on sterilized water of various pHs by changing the degree of dilution. When the pH after dilution was 7.0 or less, there was little deterioration with time of the bactericidal effect.
It turned out that the range of 5 or more and 6.5 or less was preferable.

Embodiment 5 Another embodiment of the apparatus of the present invention will be described. Another embodiment of the device of the present invention is shown in FIG. The aspect of each component of the device in FIG. 2 is denoted by the same reference numeral as in FIG.
This is the same as FIG. 1, and a detailed description thereof will be omitted. Each device of the apparatus shown in FIG.
The same equipment is used, and the following equipment is added. Disinfectant solution sending pump 11: centrifugal pump manufactured by Iwaki Co., MD-30R Flow control valve 13: manufactured by Towa Techno Co., manual type In FIG. As described above, the embodiment is as described above. still,
Since a centrifugal pump is used as the disinfectant liquid sending pump 11, it is possible to stir after mixing the electrolytically treated water and the dilution water.

Embodiment 6 This embodiment is an example of a method for producing a bactericide using the apparatus of Embodiment 5 and the contents will be described with reference to FIG. First, the apparatus was preliminarily operated as follows. Raw water is supplied from the raw water tank 1 storing the raw water (well water) to the electrolytic cell 5 by the raw water pump 3 at a rate of 130 liters per hour, and the pH of the hydrochloric acid-added raw water is set to 1. Adjusted to 45.

Next, by the same procedure as in the fourth embodiment,
Hydrochloric acid-containing raw water having a pH of 1.45 was prepared and continuously passed through the electrolytic cell 5 to electrolyze the hydrochloric acid-containing raw water. Further, the centrifugal pump 11 is operated to adjust the flow rate control valve 13, and 1170 liters of dilution water per hour is fed from the raw water tank 1 to the junction 12 a, and the electrolytically treated liquid discharged from the electrolytically treated liquid discharge pipe 8 is discharged. And diluted. The flow ratio between the dilution water and the electrolytic treatment liquid is 9: 1. Then, a bactericide having a pH of 2.55 and an oxidation-reduction potential of 1135 mV was obtained. The obtained fungicide was tested by the same method as in Test Example 1, and as a result, log
(N ₀ / N) was 7.0 or more, and a remarkable bactericidal effect was observed.

Embodiment 7 Another embodiment of the apparatus of the present invention will be described. Another embodiment of the device of the present invention is shown in FIG. The components of the apparatus shown in FIG. 3 and the operation thereof are as described above as the embodiments thereof. Vessel (hydrochloric acid-containing raw water storage means) 14: Polyethylene terephthalate electrolytic cell 5: Home-made electrode 7: Titanium platinum plating 20 × 85, electrode spacing 2 mm Power supply 6 OMRON S8E1-01505E Constant flow valve 18 Kakudai 0651A Orifice 16 ····· Teflon tube 1mm diameter Ejector-19 ··· Polyethylene water flow pump Dilution water source 17・ ・ ・ Public water supply The apparatus shown in FIG. 3 has a simple structure since the dilution water source 17 is simply connected to a household water tap, and is suitable mainly for use in ordinary households, factories, canteens, and the like. It is. In addition, there is no moving part such as a rotary pump at all, and there is an advantage that it is inexpensive and has good maintenance and inspection properties, and since it is small and lightweight, it is easy to carry.

Embodiment 8 This embodiment is an example of a method for producing a disinfectant using the production apparatus of Embodiment 7 and the contents will be described with reference to FIG. Food additive standard hydrochloric acid (manufactured by Junsei Chemical Co., Ltd. 3
(4.66%) was diluted with distilled water to prepare 0.1 mol / l hydrochloric acid-added raw water, and stored in the container 14. Dilution water source 1
The tap faucet No. 7 was opened, diluting water was allowed to flow into the ejector 19, the flow rate was adjusted by the constant flow rate valve 18, and the outlet flow rate of the ejector 19 was adjusted to 2.5 l / min. At this time, the flow rates of the hydrochloric acid-added raw water and the electrolytic treatment liquid flowing through the hydrochloric acid-added raw water pipe 15, the electrolytic tank 5, and the electrolytic treatment liquid discharge pipe 8 were 50 ml / min. When a direct current of 1.5 A was applied to the electrode 7 of the electrolytic cell 5 to subject the hydrochloric acid-added raw water to electrolytic treatment, a disinfectant of pH 3.4 was added at 2.5 l / min.
We were able to obtain continuously with the ability. The obtained bactericide was tested by the same method as in Test Example 1, and as a result, a remarkable bactericidal effect was recognized. 0.1 m prepared in Example 8
ol / l hydrochloric acid added raw water has high handling safety,
Safe to use at home.

[0059]

As described above in detail, according to the present invention, the hydrochloric acid-added raw water is passed through an electrolytic cell having no diaphragm between the positive and negative electrodes, and electricity is supplied to the negative and positive electrodes immersed in the hydrochloric acid-added raw water. The present invention relates to a method for producing a disinfectant comprising an electrolytically treated solution having a high bactericidal action, which comprises subjecting raw water to electrolytic treatment and collecting an electrolytically treated solution, an apparatus for producing the disinfectant, and a disinfectant produced by the method. The effects of the present invention are as follows. 1) According to the production method or apparatus of the present invention, the entire amount of the supplied hydrochloric acid-added raw water can be used as a bactericide, so that there is no need to dispose of the alkaline ionized water generated from the cathode, and use of electric power and water The amount is reduced. 2) According to the manufacturing method or apparatus of the present invention, since the diaphragm is not used in the electrolytic cell, the electrolytic cell and the auxiliary equipment have a simple structure, and the maintenance and management cost of the diaphragm is reduced. 3) According to the production method or the apparatus of the present invention, since the raw water having a low pH added with hydrochloric acid may be diluted after being subjected to the electrolytic treatment, the amount of the electrolytic treatment may be small. It is possible to reduce the cost and power consumption. 4) According to the production method or apparatus of the present invention, scale adhesion to the electrodes can be prevented, so that long-time operation is possible,
Manufacturing costs are reduced. 5) The bactericide of the present invention is composed of an electrolytically treated liquid having a high bactericidal action, has a high bactericidal effect, and is used for food production equipment and facilities.
It can be used effectively for manufacturing equipment / equipment for pharmaceuticals, medical equipment, and disinfection of fingers of medical personnel. 6) The sterilization treatment method of the present invention can be applied to an extremely wide range of raw water, and can be applied in various fields such as production activities, service activities, and daily life.

[Brief description of the drawings]

FIG. 1 is a diagram showing an embodiment of the apparatus of the present invention.

FIG. 2 is a diagram showing another embodiment of the apparatus of the present invention.

FIG. 3 is a diagram showing another embodiment of the apparatus of the present invention.

FIG. 4 is a view showing a flush toilet using the apparatus of FIG. 3;

FIG. 5 is a diagram showing an example of a sterilization treatment apparatus for performing the sterilization treatment method of the present invention.

FIG. 6 is a diagram showing an example in which the sterilization apparatus of FIG. 5 is provided in a circulation channel of cooling tower cooling water.

FIG. 7 is a view showing an example in which the sterilization apparatus of FIG. 5 is provided in a water tank.

[Explanation of symbols]

 Reference Signs List 1 raw water tank 1a raw water supply pipe 2 raw water supply pipe 3 raw water pump 4 metering pump for hydrochloric acid 5 electrolytic tank 6 power supply 7 electrode 8 electrolytic treatment liquid discharge pipe 9 hydrochloric acid tank 10 hydrochloric acid supply pipe 11 disinfectant liquid supply pump 12 dilution water supply pipe 12a confluence point 13 flow control valve 14 container 15 raw water pipe with hydrochloric acid added 16 orifice 17 dilution water source 18 constant flow valve 19 ejector 20 disinfectant manufacturing apparatus 21 float valve 22 float 23 system 24 washing water supply pipe 25 Toilet bowl 30 Sterilizer 31 Flow rate control valve 32 Flow rate control valve 33 Cooling tower 34 Condenser 35 Pump 36 Chlorine concentration meter 37 Circulation line 38 Controller 39 Water tank A Hydrochloric acid W Raw water AW Hydrochloric acid added raw water E Electrolytic treatment Liquid Ed Disinfectant W0 Wash water W1 Raw water W2 Raw water

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C02F 1/50 550 C02F 1/50 550D 560 560F

Claims (14)

[Claims] 1. An aqueous solution containing hydrochloric acid is passed through an electrolytic cell having no diaphragm between the cathode and the anode, and electricity is applied to the cathode and the anode immersed in the aqueous solution containing hydrochloric acid. A method for producing a bactericide comprising an electrolytically treated solution having a high bactericidal action, characterized in that the bactericide is collected. 2. The method for producing a bactericide according to claim 1, wherein the passage of the hydrochloric acid-added raw water, the electrolytic treatment, and the collection of the electrolytic treatment liquid are performed continuously. 3. Hydrochloric acid-containing raw water is prepared by adding hydrochloric acid molar concentration of 0.003.
The method for producing a bactericide comprising an electrolytically treated solution having a high bactericidal action according to claim 1 or 2, which is prepared by diluting hydrochloric acid of 1 mol / l to 6.4 mol / l. 4. The method for producing a bactericide comprising an electrolytically treated liquid having a high bactericidal action according to claim 1, wherein the collection of the electrolytically treated liquid is performed after dilution with water. 5. The method according to claim 1, wherein the electrolytic solution is collected in an effective chlorine concentration range of 0.1 ppm or more.
The method for producing a bactericide comprising the electrolytically treated liquid having a high bactericidal action according to claim 1. 6. The method for producing a bactericide comprising an electrolytically treated liquid having a high bactericidal action according to any one of claims 1 to 5, wherein the energization is performed with an alternating current exceeding a frequency of 0 Hz and 5 Hz or less. 7. The method according to claim 1, wherein the energization is carried out at a rate of 0.
The method for producing a bactericide comprising an electrolytically treated liquid having a high bactericidal action according to any one of claims 1 to 6, wherein the method is carried out with an amount of electricity of 4 to 6.0 colonies. 8. The hydrochloric acid-added raw water has a pH of 0.5 or more and 3.0 or more.
A method for producing a bactericide comprising an electrolytically treated liquid having a high bactericidal action according to any one of claims 1 to 7, which is as follows. 9. A bactericide comprising an electrolytically treated liquid having a high bactericidal action, produced by the method according to claim 1. Description: 10. A hydrochloric acid-added raw water is added to the raw water to prepare a hydrochloric acid-added raw water, and the electrolytic treatment solution is collected by performing the method according to any one of claims 1 to 8. A method for sterilizing raw water, wherein the method is obtained as raw water for sterilizing processing. 11. Hydrochloric acid is added to a part of raw water to prepare hydrochloric acid-added raw water, and the electrolytic treatment solution is collected by performing the method according to any one of claims 1 to 8. A method for sterilizing raw water, comprising returning the processing liquid to the raw water. 12. An electrolytic cell provided with an anode and a cathode which are not separated by a diaphragm, a water supply means for passing raw water through the electrolytic cell, and a hydrochloric acid adding means for adding hydrochloric acid to raw water passing through the water supply means. And a discharge line for discharging the electrolytically treated liquid from the electrolytic cell. 13. An electrolytic cell provided with an anode and a cathode which are not isolated by a diaphragm, a hydrochloric acid-containing raw water storage means for storing hydrochloric acid-containing raw water, and a hydrochloric acid which passes hydrochloric acid-containing raw water from the hydrochloric acid-containing raw water storing means to the electrolytic cell. An apparatus for producing a bactericide comprising an electrolytically treated liquid having a high bactericidal action, comprising: an additional raw water flowing means; and a discharge pipe for discharging the electrolytically treated liquid from the electrolytic cell. 14. The sterilization comprising the electrolytically treated liquid having a high sterilizing action according to claim 12 or 13, wherein the discharge line comprises an electrolytically treated liquid dilution means for mixing and diluting the electrolytically treated liquid with water. Agent manufacturing equipment.