JPH11285524A - Device for manufacturing ozone-containing sterilizing water, and ozone-containing sterilizing water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make easily manufacturable an ozone-containing sterilizing water having a high sterilizing effect by providing a solution manufacturing means for dissolving a sterilizing agent and a pH adjusting means for adjusting the pH of the solution to be acidic and dissolving ozone in the solution which is adjusted to be acidic in pH and also where the sterilizing agent is dissolved. SOLUTION: The device for manufacturing acidic water by electrolytically oxidizing a salt solution, for example, without using a diaphragm, or the like, is used as a solution manufacturing part 1 for dissolving the sterilizing agent such as sodium hypochlorite. Acid is added to the solution manufactured by the part 1 or the solution before dissolving the agent and the pH adjusting part 2 is constituted by the device, etc., for making pH acidic. The device, etc., for generating ozone by an ozone generator such as a very low temp. operation glow electric discharge-type ozone generator and dissolving ozone by bubbling, etc., is used as an ozone dissolving part 3 and an initial-stage ozone gas density is controlled by the operation time of an ozone gas generating device so that the dissolving degree of ozone gas is controlled.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for producing sterilized ozone-containing water and an sterilized ozone-containing water, and more particularly, to an apparatus for producing sterilized ozone-containing water in which a disinfectant and ozone are dissolved, and an ozone-containing sterilized water. About water.

[0002]

2. Description of the Related Art Conventionally, it is known that ozone has a bactericidal activity. In order to produce a solution capable of sufficiently exerting the bactericidal effect of ozone, ozone is dissolved at a high concentration. It is also known that it must be done.
However, ozone is relatively insoluble in water, and the amount of ozone dissipated is greater than the amount of dissolved ozone,
It is almost impossible to dissolve ozone so that the sterilizing effect can be sufficiently exerted without using a special device such as an ejector and a mixing device. As a result, the sterilizing effect of ozone is sufficiently exhibited. I can't let it.

On the other hand, it is known that by combining germicides having different germicidal mechanisms, a significantly higher germicidal effect can be obtained than when using a germicide alone. This seems to be no exception for ozone water. Therefore, for example, Japanese Patent Application Laid-Open No.
As shown in JP-A-65, it is considered that an extremely high sterilizing effect can be obtained by employing an aqueous solution of sodium hypochlorite containing ozone.

[0004]

However, the stability of ozone in water is low, and this tendency increases as the pH increases, and at pH 7.6, about 60% of the initial concentration after 30 minutes, p
In the case of H8.5, it becomes about 10% of the initial concentration after 30 minutes, and is extremely unstable and easily decomposed. Therefore, when the disinfectant acts in the neutral to alkaline (or basic) region, it is not practical to enhance the disinfecting effect by using ozone in combination.

When an aqueous solution of sodium hypochlorite is used as a bactericide, it has a high bactericidal effect in an acidic region. Is reduced,
It is thought that the sterilization effect can be enhanced by using ozone in combination. However, even in this case, when a bactericide is added after producing a solution containing ozone (ozone water), the ozone reacts with the bactericide or a part of the bactericide components, and the concentration of ozone decreases. Therefore, the sterilization effect cannot be enhanced by using ozone in combination.

Therefore, there is a demand for an apparatus capable of producing sterilized ozone-containing water without such inconvenience, but such an apparatus has not been proposed.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an apparatus for producing sterilized water containing ozone, which can greatly suppress the decrease in the concentration of ozone and can enhance the sterilizing effect by using ozone together. And an ozone-containing sterilizing water having a high sterilizing effect.

[0008]

According to the first aspect of the present invention, there is provided an apparatus for producing sterilized water containing ozone, wherein a dissolving solution producing means for dissolving the disinfectant and the pH of the solution before or after dissolving the disinfectant are adjusted to be acidic. pH adjusting means, pH is adjusted to acidic,
And an ozone dissolving means for dissolving ozone in the dissolving solution in which the disinfectant is dissolved.

[0009] The apparatus for producing sterilized ozone-containing water according to claim 2 employs sodium hypochlorite as a germicide. The apparatus for producing sterilized ozone-containing water according to claim 3 employs, as a solution production means, one that produces a solution in which sodium hypochlorite is dissolved by electrolytic treatment.

According to a fourth aspect of the present invention, there is provided an apparatus for producing ozone-containing sterilized water, comprising: ozone water producing means for producing ozone water containing ozone; acid water producing means for producing acidic water; and ozone water produced. And mixing means for mixing the acidic water. The ozone-containing sterilizing water according to claim 5 is obtained by dissolving ozone in a dissolving solution in which a sterilizing agent is dissolved, and has an ozone concentration of 0.5 mg / l or more.

[0011]

In the apparatus for producing sterilized ozone-containing water according to claim 1, the disinfectant is dissolved by the dissolving solution producing means, and the pH of the solution before or after dissolving the disinfectant is adjusted to acidic by the pH adjusting means. Then, the pH is adjusted to acidic by the ozone dissolving means, and ozone is dissolved in the dissolving solution in which the germicide is dissolved.

Therefore, not only is the consumption of ozone at the time of mixing ozone and another germicide reduced, but also because the solution is acidic, the initial concentration of dissolved ozone is high and the decomposition rate of ozone is slow. As a result, ozone-containing sterilized water that can enhance the sterilizing effect by using ozone together can be easily and reliably produced. According to the apparatus for producing sterilized ozone-containing water according to claim 2, even when sodium hypochlorite is used as a bactericide, the bactericidal effect of sodium hypochlorite can be enhanced by the pH adjusting means. In addition, a disinfectant having a high bactericidal activity can be obtained by further dissolving ozone, and the same action as in claim 1 can be achieved.

In the apparatus for producing sterilized ozone-containing water according to the third aspect, a means for producing a solution in which sodium hypochlorite is dissolved by electrolytic treatment is used as a solution producing means. In addition to the method for producing electrolytic acid water described above, the same operation as that of claim 1 can be achieved. The sodium hypochlorite or chlorine-based disinfectant according to claims 2 and 3 has been regarded as a problem because it produces an organic halogen compound such as trihalomethane which is harmful to the human body and has carcinogenic properties. However, when ozone is used in combination with sodium hypochlorite or a chlorine-based germicide, the amount of chlorine can be reduced, so that the amount of organic chlorine compounds generated can be reduced. Also,
Ozone does not directly oxidize and decompose organic chlorine compounds that do not have unsaturated bonds, such as chloroform.However, when ozone decomposes in water, it produces oxidatively active species such as hydroxyl radicals and superoxide, which causes ozone oxidation. It is thought that difficult substances are also oxidatively decomposed, and the production amount of organic chlorine compounds can be further reduced.

According to a fourth aspect of the present invention, there is provided an apparatus for producing sterilized water containing ozone, wherein ozone water containing ozone is produced by an ozone water producing means, acid water is produced by an acidic water producing means, and produced by a mixing means. The produced ozone water and the produced acidic water are mixed. Therefore, not only the consumption of ozone at the time of mixing ozone with other disinfectants is reduced, but also the ozone water is mixed, so that the initial concentration of dissolved ozone is increased. As a result, ozone-containing sterilized water that can enhance the sterilizing effect by using ozone together can be easily and reliably produced.

In the case of the ozone-containing sterilizing water according to the fifth aspect, ozone is dissolved in the dissolving solution in which the sterilizing agent is dissolved, and the ozone concentration is 0.5 mg / l or more. , A sufficient bactericidal effect can be achieved.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of an apparatus for producing sterilized ozone-containing water according to the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a block diagram showing one embodiment of the apparatus for producing sterilized ozone-containing water of the present invention.

This ozone-containing sterilizing water producing apparatus comprises a dissolving solution producing section 1 for dissolving a disinfectant, and a pH adjusting section 2 for adjusting the pH of the solution before or after dissolving the disinfectant to acidic.
And an ozone dissolving unit 3 whose pH is adjusted to be acidic and which dissolves ozone in a dissolving solution in which a germicide is dissolved. For example, the dissolving solution producing unit 1 uses a device for producing acidic water by electrolytically oxidizing a salt solution without using a diaphragm, a diaphragm, and performs electrolysis using sodium chloride (NaCl) as an electrolytic auxiliary. For producing acidic water by using sodium hypochlorite (NaC
A device for diluting (IO) with pure water can be exemplified. Also,
The disinfectant is preferably sodium hypochlorite, but it is a matter of course that disinfectants other than sodium hypochlorite may be used. Furthermore, when employing an apparatus for producing acidic water by electrolysis using sodium chloride (NaCl) as an electrolysis auxiliary, the effective chlorine concentration should be controlled by the sodium chloride concentration of the aqueous sodium chloride solution or the electrolysis time. Is possible. Specifically, under the same electrolysis conditions, the effective chlorine concentration can be increased by increasing the concentration of sodium chloride in the aqueous sodium chloride solution. By increasing the time, the effective chlorine concentration can be increased.

The pH adjusting unit 2 adjusts the pH to acidic (for example, by adding an acid such as hydrochloric acid (HCl) to the solution prepared by the solution manufacturing unit 1 or the solution before dissolving the bactericide. If a device for making the solution strongly acidic) or a device for performing electrolysis using a diaphragm as the solution production section 1 is adopted, the pH is made acidic (preferably strongly acidic).
For example, an apparatus for controlling the solution production unit 1 can be exemplified. The acid to be added may be an inorganic acid or an organic acid, but when sodium hypochlorite is used as a disinfectant, the disinfectant does not affect the composition of ozone. Considering this, it is preferable to use hydrochloric acid.

The ozone dissolving unit 3 generates ozone using an ozone generator such as a glow discharge (or creeping discharge) type ozone generator or an ultraviolet irradiation type ozone generator, and dissolves ozone by bubbling or the like. For example, a device for generating ozone water by a direct electrolysis type ozone water producing device and a device for mixing the ozone water can be exemplified. When an apparatus for dissolving ozone is employed, the solubility of ozone gas is represented by the product of the ozone gas concentration and the distribution coefficient (variable depending on temperature), so the initial ozone gas concentration is controlled by the operating time of the ozone gas generator. By doing so, the solubility of ozone gas can be controlled, and when the concentration of ozone gas is constant, the solubility of ozone gas can be controlled by controlling the gas-liquid contact time.

The operation of the apparatus for producing sterilized ozone-containing water having the above configuration is as follows. The disinfectant is dissolved in pure water or the like by the dissolving solution producing unit 1, and the pH of the solution before or after dissolving the disinfectant is adjusted to acidic by the pH adjusting unit 2. Here, the pH of the solution is preferably low, and the concentration of ozone dissolved by the subsequent treatment can be increased. Then, the ozone dissolving unit 3
Thereby, the pH is adjusted to be acidic, and the ozone-containing sterilized water can be obtained by dissolving ozone in the dissolving solution in which the disinfectant is dissolved.

This will be described in more detail. Table 1 shows the pH of the solution
And the change in ozone concentration caused by the ozone lamp irradiation time, bubbling time, and temperature.
The lower the H, the higher the dissolved ozone concentration.

[0022]

[Table 1]

The ozone lamp has a lamp length of 8
8mm, tube diameter 24.5mm, lamp current 0.26
A, lamp power is 10W, germicidal line illuminance is 6000μW /
cm ² , wavelengths of 253.7 nm and 184.
It irradiates 9nm light and uses 184.9nm light energy to generate ozone from oxygen in the air.
Bubbling is adopted as a gas-liquid contact method, and an oxygen atmosphere is adopted as an ozone generation condition. In Table 1, the ozone lamp irradiation time and the bubbling time are both shown in minutes, the temperature is shown in ° C., and the ozone concentration is shown in mg / l.

It is known that ozone reacts with halogen ions such as iodine and bromine in an aqueous solution to become oxygen. Since sodium hypochlorite or acidic water contains a large amount of chloride ions, it is possible that ozone reacts with chloride ions. Also, ozone OCl ^- and when reacted are to become oxygen and chlorine ions, comprising the interfering substance in each measurement ozone and chlorine. In consideration of such points, ozone-containing sterilized water obtained by adding sodium hypochlorite before bubbling of ozone gas, and ozone-containing sterilized water obtained by adding sodium hypochlorite after bubbling of ozone gas The ozone concentration, available chlorine concentration, and absorption spectrum of the sterilized water were measured and compared.

Bubbling ozone gas into pure water (ozone lamp irradiation time 10 minutes, bubbling 5 minutes, 4 ° C., pH 7.0.
0), the ozone concentration and the effective chlorine concentration in the case of
0.65 mg / l, 0 mg / l,
The absorption spectrum was 259 nm as shown in FIG.
It has an absorption maximum around. Further, sodium hypochlorite (4500 mg / l, pH 7.5) was added to pure water for 450 minutes.
Table 2 shows the ozone concentration and available chlorine concentration when diluted twice.
0 mg / l, 10 mg / l as shown in b of
The absorption spectrum was 234 nm as shown in FIG.
It has an absorption maximum around.

When ozone gas is bubbled after adding sodium hypochlorite, the ozone concentration and effective chlorine concentration are 0.63 mg / l, 10 m
g / l, and the absorption spectrum has a peak at around 259 nm as shown in FIG. 2 (c), and is the sum of the absorption spectrum of ozone water and the absorption spectrum of sodium hypochlorite (FIG. 2 (c)). (See the broken line).

Conversely, when sodium hypochlorite is added after bubbling ozone gas, the ozone concentration and effective chlorine concentration are 0.65 mg / kg as shown in Table 2d.
1 and 10 mg / l, and no peak is observed around 259 nm in the absorption spectrum as shown in (d) of FIG.

[0028]

[Table 2]

Since the absorption spectrum of sodium hypochlorite changes depending on the pH, all the solutions have a pH of 7.
0 was used so that the pH did not change even when mixed. In addition, the measurement of the ozone concentration is performed by the indigo method (for example,
Wavelength 6 decreases linearly with increasing dissolved ozone concentration
The effective chlorine concentration was measured by an iodine titration method (for example, a method of adding KI and titrating liberated I ₂ with Na ₂ S ₂ O ₃ ).

As can be seen from the above, regardless of the order in which the ozone-containing germicidal water was produced, the absorption spectrum showed no difference between the ozone concentration and the available chlorine concentration in the chemical analysis method. It is clearly distinguished by the presence or absence of a peak around 259 nm. That is, by bubbling ozone gas after adding sodium hypochlorite, it is possible to exhibit sufficient sterilizing power of ozone and sodium hypochlorite.

Next, a specific example will be described. In order to demonstrate the sterilizing power of ozone-containing aqueous sodium hypochlorite solution (sterilizing water), sterilizing water with different ozone concentration and effective chlorine concentration is manufactured, and a sterilization test is performed on the spores of Bacillus subtilis, which is considered to be the most resistant. Was done. Here, the saturated ozone concentration C ^* in the aqueous solution can be calculated by multiplying the _gas ozone concentration C _gas by the distribution coefficient m (depending on the temperature, about 0.2 at room temperature). By controlling C _gas , it is possible to control the ozone concentration in the aqueous solution.

First, Bacillus Subtili
Adjustment of the spore suspension was performed according to the following 1-9. 1. Inoculation Nutrient Agar (Eiken) S
1. Inoculate lanting 2. Incubation at 37 ° C for 7 days 3. Microscope 1 field of view Confirmation of 95-100% spore formation Bacterial collection 2 ml of sterile water is added to each slant and stirred. 4. Collect the cell suspension Heat treatment 65 ° C, 15 minutes, occasional stirring 6. Centrifuge 3000 rpm, 15 minutes After the operation of Washing 6, immediately discard the supernatant and wash with sterile water for 2 hours.
7. Washing once (3000 rpm, 15 minutes) 8. Heat treatment 80 ° C, stirring for 10 minutes, occasionally Adjustment Adjusted with sterile water so as to give a final concentration of 1 × 10 ⁸ cfu / ml. Then, a sterilization test was performed according to the following 1 to 6.

1. 1. 0.99 ml of each sample is dispensed into test tubes. 2. Inoculate 10 μl of adjusted spore fluid 3. Reaction with sterile water (5 minutes) 4. 0.1N in 0.9 ml of 0.01 N sodium thiosulfate
4. Add ml. 5. Create dilution series using pure water 0.1 ml smear on agar medium (medium: Nutrien)
t Agar) Then, the results of the above test are shown in FIG.
Shown in

Under the above test conditions, in order to kill 99.99% of the spores of Bacillus subtilis, when sodium hypochlorite is used alone, the effective chlorine concentration is 30 mg.
/ L is required. On the other hand, when 0.65 mg / l of ozone was coexisted, the spores of Bacillus subtilis were 99.9.
The effective chlorine concentration required to kill 9% is 10 mg /
l. From FIG. 3A, it can be seen that higher sterilizing power can be obtained when ozone coexists than chlorine alone (see the solid line). Further, from FIG. 3B, it can be seen that higher sterilizing power is obtained when chlorine is present together than when ozone is used alone (see the solid line).

In both FIGS. 3 (a) and 3 (b), the vertical axis indicates the ratio of the number of viable bacteria (N / N0), and the horizontal axis in FIG. 3 (a) indicates the chlorine concentration. The horizontal axis of b) indicates the ozone concentration. The black circle in FIG. 3A indicates that the ozone concentration is 0 m.
g / l, the white triangle has an ozone concentration of 0.22-0.
In the case of 28 mg / l, the black diamond shows an ozone concentration of 0.32.
-0.39 mg / l, open squares indicate the case where the ozone concentration is 0.44-0.45 mg / l, and solid triangles indicate the case where the ozone concentration is 0.65 mg / l. Equation (1) approximates the regression curve of

[0036]

(Equation 1)

In (a) of FIG.
It can be seen that the bactericidal activity is almost the same in the range of 22-0.45 mg / l, and that the bactericidal activity is significantly increased when the ozone concentration becomes 0.65 mg / l. In FIG. 3, (b) a black circle indicates a case where the available chlorine concentration is 0 mg / l, a white triangle indicates a case where the available chlorine concentration is 1-2 mg / l, and a solid diamond indicates a case where the available chlorine concentration is 4-7 mg / l. And the open squares indicate that the effective chlorine concentration is 9-
In the case of 14 mg / l, the black triangle indicates that the effective chlorine concentration is 18-
In the case of 22 mg / l, x indicates that the available chlorine concentration is 27-50.
The case of mg / l is shown, and the approximate expression for approximating each regression curve is as shown in Expression 2. However, an approximate expression for approximating × is not shown.

[0038]

(Equation 2)

In FIG. 3B, the ozone concentration of 0.65 mg / l is located below the approximation line at any available chlorine concentration. Therefore, an ozone concentration of 0.45-
It is believed that there is an inflection point between 0.65 mg / l. FIG. 4 is a block diagram showing another embodiment of the apparatus for producing sterilized ozone-containing water of the present invention.

This ozone-containing sterilizing water producing apparatus includes an ozone water generating apparatus 11 such as an ozone electrolytic reaction apparatus for generating ozone water by electrolyzing pure water, and an acidic water producing apparatus (using a diaphragm, which generates acidic water). And an apparatus for producing acidic water by performing electrolysis using sodium chloride as an electrolysis auxiliary), and a mixing apparatus 13 for mixing the generated ozone water and the acidic water.

FIG. 5 is a schematic view showing an example of an ozone water generating apparatus. The ozone water generation device 11 generates ozone water by bubbling ozone generated in the ozone generation unit 11b and the ozone generation unit 11b into pure water while replacing the inside with oxygen. Ozone water generator 11c and ozone water generator 11
c, an ozone water take-out unit 11d to take out the ozone water generated in step c, and an ozone gas absorption unit that absorbs surplus ozone not dissolved in pure water in the ozone water creation unit 11c (the first ozone solution is used to dissolve excess ozone in the potassium iodide aqueous solution). Absorber 11e1 and second absorber 1 containing activated carbon for absorbing ozone not absorbed by first absorber 11e1
1e2) 11e, a gas flow path 11f for flowing ozone gas therebetween, and a gas suction pump 1e.
1 g. In addition, 11h is a three-way valve.

The operation of the ozone water generator 11 is as follows. First, by replacing the inside of the ozone generation unit 11b with oxygen and turning on the ozone lamp 11a,
Ozone gas is generated in the ozone generation unit 11b. The three-way valve 11h is controlled so that the ozone lamp 11a is turned on, and the ozone gas bypasses the ozone gas absorbing part 11e, and the gas suction pump 11g
Is operated, the ozone gas is dissolved in pure water in the ozone water creating section 11c and accumulated (creates ozone water). The above operation is performed for a predetermined time, and when the ozone concentration of the ozone water becomes high (or reaches a predetermined concentration), the ozone water extraction unit 11d extracts the ozone water from the ozone water generation unit 11c. After the ozone water is taken out, the ozone gas is supplied to the ozone water creation unit 11c.
By controlling the three-way valve 11h so that the ozone gas passes through the ozone gas absorption section 11e, excess ozone gas is absorbed and ozone gas in the ozone water generator 11 is removed.

When this apparatus for producing sterilized ozone-containing water is employed, sterilized ozone-containing water can be produced by mixing the generated ozone water with the generated acidic water. In this case, since there is no context between the addition of the ozone water and the addition of the acidic water, there is no inconvenience as in the case of adding sodium hypochlorite after bubbling ozone gas. ,
The produced ozone-containing sterilized water has sufficient sterilizing power.

[0044]

According to the first aspect of the present invention, not only is the consumption of ozone at the time of mixing ozone and another germicide reduced, but also because the solution is acidic, the initial concentration of dissolved ozone is increased, and Due to the slow decomposition rate of ozone, a unique effect is obtained in that ozone-containing sterilized water capable of enhancing the sterilizing effect can be easily and reliably produced.

According to the second aspect of the present invention, even when sodium hypochlorite is used as a bactericide, the bactericidal effect of sodium hypochlorite can be enhanced by pH adjusting means, and ozone can be further reduced. By dissolving, it is possible to obtain a germicide having a high bactericidal activity.
It has the same effect as. The invention of claim 3 can adopt a known method for producing electrolytic acidic water, and can also adopt claim 1.
It has the same effect as.

The invention according to claim 4 is not only because the consumption of ozone when mixing ozone with other germicides is reduced, but also because ozone water is mixed, the initial concentration of dissolved ozone is increased. As a result, it is possible to easily and surely produce ozone-containing sterilized water capable of enhancing the sterilizing effect. The invention of claim 5 has a unique effect that a sufficient sterilizing effect can be achieved by using ozone in combination.

[Brief description of the drawings]

FIG. 1 is a block diagram showing one embodiment of an apparatus for producing sterilized ozone-containing water of the present invention.

FIG. 2 is a diagram showing an absorption spectrum for explaining a difference in sterilized ozone-containing water caused by a difference in order of addition of ozone and sodium hypochlorite.

FIG. 3 is a graph showing changes in sterilizing power with respect to ozone concentration and effective chlorine concentration.

FIG. 4 is a block diagram showing another embodiment of the apparatus for producing sterilized ozone-containing water of the present invention.

FIG. 5 is a schematic diagram illustrating an example of an ozone water generation device.

[Explanation of Signs] 1 Dissolution liquid production unit 2 pH adjustment unit 3 Ozone dissolution unit 11 Ozone water generation device 12 Acid water production device 13 Mixing device

Claims (5)

[Claims] 1. A dissolving solution producing means (1) for dissolving a bactericide, and a p-solution for the solution before or after dissolving the bactericide.
A pH adjusting means (2) for adjusting H to acidic, and an ozone dissolving means (3) for dissolving ozone in a dissolving solution in which pH is adjusted to be acidic and a bactericide is dissolved. Ozone-containing sterilizing water production equipment. 2. The apparatus for producing sterilized ozone-containing water according to claim 1, wherein the sterilizing agent is sodium hypochlorite. 3. The apparatus for producing sterilized ozone-containing water according to claim 1, wherein the solution producing means (1) produces a solution in which sodium hypochlorite is dissolved by electrolytic treatment. 4. An ozone water producing means (11) for producing ozone water containing ozone, an acidic water producing means (12) for producing acidic water, and a mixture of the produced ozone water and the produced acidic water. And a mixing means (13) for mixing the ozone-containing sterilized water. 5. An ozone-containing sterilizing water obtained by dissolving ozone in a dissolving solution in which a sterilizing agent is dissolved, wherein the ozone-containing sterilizing water has an ozone concentration of 0.5 mg / l or more. .