JP3475875B2 - Electrolytic sterilizing water and its manufacturing apparatus - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electrolytic sterilizing water and a manufacturing apparatus therefor, and more specifically, it contains acidic water produced on the anode side by electrolyzing salt-added water through a diaphragm. The present invention relates to electrolytic sterilized water and an apparatus for producing this electrolytic sterilized water.

[0002]

2. Description of the Related Art By electrolyzing dilute chlorine compound-added water through a diaphragm, acidic electrolyzed water is obtained on the anode side and alkaline electrolyzed water is obtained on the cathode side. Since the acidic electrolyzed water obtained on the anode side contains chlorine, hypochlorous acid, and other oxidizing components, the acid electrolyzed water obtained on the anode side is used for purposes such as sterilization. To be

Further, this sterilizing water can be made to have a sterilizing power several to several tens of times higher than that of sodium hypochlorite which is generally used, by making the pH strong acidic. It has been known. Specifically, the pH is 2.
It is known that the sterilizing power when 0 and the effective chlorine concentration are set to 50 ppm is almost equal to the sterilizing power when pH is 8.0 and the effective chlorine concentration is set to 200 ppm.

[0004]

The acidic electrolyzed water obtained conventionally has a maximum effective chlorine concentration of 50 to 100 ppm.
And, theoretically, the effective chlorine concentration is 200 to 400 ppm.
It has the sterilizing power of sodium hypochlorite to the extent. However, when conventional electrolyzed water is put to practical use, effective chlorine is consumed due to the presence of organic substances, and the sterilizing power is reduced.
As a result, theoretical sterilizing power cannot be obtained depending on the sterilization target.

Specifically, the bacterial species Lactobacillus
us acidophilus JCM1132 n =
2 average, Pseudomonas aerugin
osa IID1117 n = 2 For each of the average and the case where the organic substance (serum) was not added, the results of measuring the bactericidal activity with acidic water and sodium hypochlorite are shown in Tables 1 and 2. there were. In addition,
In Tables 1 and 2, +, ++, ++++, ++++ are:
Number of viable bacteria is 1-9, 10-99, 100-9, respectively
It shows that the number is 99, 1000 or more.

[0006]

[Table 1]

[0007]

[Table 2]

As can be seen from Tables 1 and 2, acid water has a stronger bactericidal activity when no organic matter is added, but sodium hypochlorite has a bactericidal activity when organic matter is added. Is strong.

More specifically, Escherichi
Table 3 shows the results of measuring the bactericidal activity of electrolyzed water and sodium hypochlorite with and without addition of an organic substance (serum) to the a coli IFO15034 strain. In addition, in Table 3,
-, +, ++, ++++, ++++ have 0, 1-9, 10-99, 100-999, and 1 viable cells, respectively.
It indicates that the number is 000 or more.

As an experimental method, 10 μl of the bacterial solution washed with physiological saline was inoculated into 1 ml of a sample (acidic water / sodium hypochlorite with or without serum added), and 100 μl was taken after 30 seconds. The cells were spread on a neutralizing agent-containing agar medium (SCDLP medium) and cultured at 35 ° C. for 24 hours.

[0011]

[Table 3]

As can be seen from Table 3, the sterilizing power of the electrolyzed water is stronger when the organic substance is not added, whereas the sodium chlorite is stronger when the organic substance is added.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide electrolytic sterilized water and a manufacturing apparatus therefor capable of exhibiting sufficient sterilizing power even in the presence of organic substances. I am trying.

[0014]

[0015]

[0016]

An electrolytic sterilizing water producing apparatus according to claim 1 is characterized in that electrolyzing means for electrolyzing chlorine compound-added water through a diaphragm, and anode water and cathode water taken out from the electrolyzing means. And mixing means for obtaining electrolytic sterilized water, and adjusting the electrolytic current density of electrolysis to adjust the effective chlorine concentration in the range of 150 to 400 ppm, and the adjusting range of the electrolytic current density is 5 A / dm ^{2 to} 40 A. /
The adjusting means is set to dm ² .

[0017]

[0018]

The apparatus for producing electrolytic sterilized water according to claim 2 further includes a power source means capable of reversing the polarity of the DC voltage, and the mixing tank is a mixing tank for mixing the anode water and the cathode water taken out from the electrolyzing means. And a supply amount adjusting valve for controlling the amount of anode water and cathode water which are provided in each flow path and are supplied to the mixing tank, and a solenoid valve.

[0020]

[0021]

[0022]

[0023]

[0024]

According to the electrolytic sterilized water production apparatus of claim 1, the chlorine compound-added water is electrolyzed by the electrolyzing means with the diaphragm interposed, and the anode water and the cathode water taken out from the electrolyzing means by the mixing means. In mixing with and to obtain electrolytic sterilized water, the electrolytic current density of electrolysis is adjusted in the range of 5 A / dm ^{2 to} 40 A / dm ² by the adjusting means in order to adjust the effective chlorine concentration in the range of 150 to 400 ppm. . Therefore, by adjusting the electrolytic current density,
It is possible to produce electrolytic sterilized water having a high effective chlorine concentration with sufficient sterilizing power even in the presence of organic substances.

[0025]

[0026]

In the electrolytic sterilized water producing apparatus according to the second aspect of the present invention, the apparatus further comprises a power supply means capable of reversing the polarity of the DC voltage, and the mixing means mixes the anode water and the cathode water taken out from the electrolysis means. Since a mixing tank, a supply amount adjusting valve provided in each flow path and controlling the amount of anode water and cathode water supplied to the mixing tank, and a solenoid valve are adopted, they are arranged with a diaphragm interposed therebetween. The electrodes can be made to function alternately as an anode electrode and a cathode electrode, and the surface of each electrode can be put into a state suitable for electrolysis to improve the electrolysis efficiency, and also the polarity of the DC voltage can be reversed. Since each solenoid valve can be opened and closed selectively, the effective chlorine concentration is 150 to 400 ppm,
It is possible to obtain electrolytic sterilized water having a pH of 2 to 7.

[0028]

[0029]

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the electrolytic sterilized water and the manufacturing apparatus thereof according to the present invention will be described in detail below with reference to the accompanying drawings.

FIG. 1 is a schematic view showing one embodiment of the electrolytic sterilized water producing apparatus of the present invention.

This electrolytic sterilizing water producing apparatus comprises an electrolyzing apparatus 1 and a mixing apparatus 2 for mixing anode water and cathode water.
And a mixing ratio setting device 3 for setting the mixing ratio of the anode water and the cathode water.

The electrolyzer 1 comprises an electrolytic cell 12 to which chlorine compound-added water is supplied by a chlorine compound-added water supply pipe 11, and a diaphragm 13 provided at the center of the electrolytic cell 12.
And the electrode 1 arranged in each chamber partitioned by the diaphragm 13.
4 and a DC power supply 15 for applying a DC voltage between the pair of electrodes 14. In addition, chlorine compound added water supply pipe 1
Reference numeral 1 is for supplying chlorine compound-added water to each chamber partitioned by the diaphragm 13. Further, the DC power supply 15 is for inverting the polarity of the DC voltage applied between the electrodes periodically by, for example, a changeover switch (not shown). Further, as chlorine compounds, NaCl, KCl,
An inorganic chlorine compound such as HCl can be exemplified.

The mixing device 2 includes a produced water pipe 21 for leading out produced water in each chamber partitioned by the diaphragm 13.
It has a mixing tank 22 for receiving and mixing the generated water led out by both the generated water pipes 21, and an electrolytic sterilizing water outlet pipe 23 for deriving the mixed generated water as electrolytic sterilizing water.

The mixing ratio setting device 3 has a waste liquid pipe 31 for connecting an intermediate part of each produced water pipe 21 and a waste liquid tank (not shown), an adjusting valve 32 provided in the waste liquid pipe 31, and an opening / closing valve 33. is doing. Then, each on-off valve 33 is selectively opened corresponding to the polarity of the DC voltage.

The operation of the electrolytic sterilizing water producing apparatus having the above-mentioned configuration is as follows.

The chlorine compound-added water is supplied to each chamber of the electrolytic cell 12 by the chlorine compound-added water supply pipe 11 and a DC voltage is applied between the pair of electrodes 14 by the DC power supply 15 to thereby supply the chlorine compound. The added water can be electrolyzed to generate anode water and cathode water in each chamber. In this case, the polarity of the DC voltage applied between the pair of electrodes 14 is periodically reversed, so that the electrodes arranged with the diaphragm sandwiched between them are alternately anode electrodes,
It can function as a cathode electrode, and the surface of each electrode can be put into a state suitable for electrolysis to improve electrolysis efficiency.

By supplying the produced anode water and cathode water to the mixing tank 22 through the produced water pipes 21, respectively, the anode water and the cathode water are mixed to produce electrolytic sterilized water by the electrolytic sterilized water outlet pipe 23. It can be outsourced.

Further, by setting the opening of the adjusting valve 32 corresponding to the cathode water and opening the on-off valve 33 to adjust the amount of the cathode water supplied to the mixing tank 22, the anode water and the cathode water can be adjusted. The pH of the resulting electrolytically sterilized water can be adjusted by adjusting the mixing ratio with water. Furthermore, by adjusting the electrolytic current value and / or the chlorine compound-added water concentration, the effective chlorine concentration is adjusted to 150 to
It can be 400 ppm. Specifically, for example, the salt concentration is 0.3%, the liquid flow rate in the electrolytic cell 12 is 1000 ml / min, a flat plate electrode is used, and the electrolytic current density is set to 5 A / dm ² , thereby generating effective chlorine. The concentration can be 159 ppm, the salt concentration is 0.3%, and the liquid flow rate in the electrolytic cell 12 is 1000 ml /
min, a flat plate electrode is used, and the electrolytic current density is 10 A
/ Dm ² to set the effective chlorine concentration to 2
It can be 47 ppm, the salt concentration is 0.2%, the liquid flow rate in the electrolytic cell 12 is 1000 ml / min,
By adopting a flat plate electrode and setting the electrolysis current density to 5 A / dm ² , the effective chlorine concentration produced can be 140 ppm, the salt concentration is 0.2%, and the liquid flow rate in the electrolytic cell 12 is 1000 ml / min. By adopting a flat plate electrode and setting the electrolytic current density to 10 A / dm ² , the effective chlorine concentration produced can be set to 214 ppm.

As a result, the effective chlorine concentration is 150 to 400.
It is possible to obtain electrolytic sterilized water having a ppm of 2 to 7 and a pH of 2 to 7.

Of course, by maximizing the opening of the adjusting valve 32, it is possible to obtain electrolytic sterilized water only with the anode water.

Here, since the sterilizing factor of electrolytic sterilizing water is presumed to be hypochlorous acid, the pH is 2 to 7 as shown in FIG.
A high sterilizing power can be achieved by setting to.

Electrolytic sterilized water 10 obtained as described above
When 1 kg of cucumber, shredded cabbage, or parsley was put in 1 liter and stirred for 2-3 times, Table 4 to Table 6
The results shown in are obtained. In Table 4, the effective chlorine concentration is 1
When the electrolytic sterilizing water of 94 ppm is used, Table 5 shows the case of using the electrolytic sterilizing water of effective chlorine concentration of 177 ppm, and Table 6 shows the case of using the electrolytic sterilizing water of effective chlorine concentration of 159 ppm, respectively. There is. And the pH of these electrolytic sterilization water is set to 6.3-6.7.
Further, the upper row corresponding to the sterilization object shows the data before the sterilization treatment, and the lower row shows the data after the sterilization treatment. Further, in these tables, BGLB is Br
illiant Green Lactose Bil
It is an abbreviation for e.

[0044]

[Table 4]

[0045]

[Table 5]

[0046]

[Table 6]

After the shredded cabbage in the presence of organic matter was pre-washed with water, electrolytic sterilized water having a pH of 6.3 and an effective chlorine concentration of 232 ppm, a pH of 8.8 and an effective chlorine concentration of As a result of performing sterilization treatment using 218 ppm of sodium hypochlorite and measuring the number of viable cells immediately after sterilization and the number of viable cells after storage for 2 days, the results shown in FIG. 3 and Table 7 were obtained.

[0048]

[Table 7]

As is clear from the results of this measurement, it is found that a bactericidal activity about twice is obtained immediately after sterilization and a bacteriostatic effect about 100 times is obtained after storage for 2 days.

FIG. 4 and Table 8 are data showing an example of changes in the produced effective chlorine concentration before and after reversing the polarity of the DC voltage. The salt concentration is 0.1% and the electrolytic cell 1
The liquid flow rate in No. 2 was set to 800 ml / min, a flat plate electrode was adopted, and the electrolytic current density was set to 10 A / dm ² .

[0051]

[Table 8]

As is clear from FIG. 4 and Table 8, the concentration of produced effective chlorine (ppm) decreases when electrolysis is continued, but the produced effective chlorine concentration is changed by reversing the polarity (performing pole change). Can be increased. The reason for this is that chlorine continues to be deposited on the electrode due to continued electrolysis, which reduces the chlorine generation performance.However, by reversing the polarity of the DC voltage, the substance deposited on the electrode due to the electrode reaction is peeled off and the surface of the electrode is removed. This is because the chlorine generation performance can be restored by cleaning the. As a result, the effective chlorine concentration of electrolytic sterilization water can be increased.

FIG. 5 is a schematic view showing another embodiment of the electrolytic sterilized water producing apparatus of the present invention.

This electrolytic sterilized water production apparatus comprises an electrolysis apparatus 1 and a mixing apparatus 2 for mixing anode water and cathode water.
And a mixing ratio setting device 3 for setting the mixing ratio of the anode water and the cathode water.

Since the electrolyzer 1 has the same structure as the electrolyzer 1 shown in FIG. 1, detailed description thereof will be omitted.
In addition, chlorine compound added water supply pipe 11 and DC power supply 1
5 is also omitted in the figure.

The above-mentioned mixing device 2 has the same structure as that of the mixing device 2 shown in FIG. 2
Reference numeral 4 denotes an exhaust unit that exhausts only gas components from the mixed gas-liquid mixture flow.

The mixing ratio setting device 3 has a waste liquid pipe 31 for connecting an intermediate portion of each produced water pipe 21 to a waste liquid tank (not shown), an on-off valve 33 and a capillary 34 provided in the waste liquid pipe 31, and a waste liquid pipe 31. And an orifice 35 provided on the upstream side of the connection position. Then, each on-off valve 33 is selectively opened corresponding to the polarity of the DC voltage.

The operation of the electrolytic sterilized water producing apparatus having the above-described structure is as follows.

Similar to the electrolytic sterilizing water production apparatus shown in FIG.
Electrolytic sterilized water can be obtained by generating anode water and cathode water from the electrolyzer 1 and supplying them to the mixing device 2 through the generated water pipe 21.

In this embodiment, the orifice 35 provided upstream of the connection position of the waste liquid pipe 31.
The pressure head difference can be made large and the flow rate can be made constant. That is, the waste liquid pipe 3 is hardly affected by the state of the generated water pipe 21 (such as the drawn state).
The flow rate at the connection position 1 can be made constant.
Therefore, the amount of the generated water discharged through the waste liquid pipe 31 can be accurately controlled, and thus the amount of the generated water supplied to the mixing device 2 can be accurately controlled, so that the anode water and the cathode water can be controlled. The mixing ratio of can be controlled with high accuracy.

Further description will be made.

If the diameter of the orifice 35 is d (m), the head difference {(p1-p2) / γ} is H (m), and the flow coefficient is C, the flow rate Q (m ³ / sec) is given by the following equation. Desired. ^{Q = C * (πd 2/} 4) * (2gH) 1/2 However, gamma is the specific weight (1000kg / m ^3), g is the gravitational acceleration.

Here, the diameter d of the orifice 35 is set to 6 mm.
And 1.5 mm, flow rate Q is 1000 ml / min, 450
Table 9 shows the head difference (m) and the water pressure difference (kg / cm ² ) when set to ml / min.

[0064]

[Table 9]

Since the water pressure flowing into the electrolytic cell 12 is about 1 to 3 kg / cm ² when tap water source water is used, the pressure difference created by the orifice having a diameter of 1.5 mm is considered to be within a practical range. Become. Then, if the orifice is set near the water outlet, the piping resistance after the orifice can be reduced, it is easy to make the resistance constant, and a stable flow rate can be obtained. In addition, it is possible to send at high pressure from the electrolytic cell 12 to the orifice,
If a thin tube with a smaller resistance is used, the fluctuation component is less likely to be affected (loss), and for example, fluctuation in the flow rate due to the bending difference of the pipe is less likely to occur. In other words, a constant flow rate can be realized.

Specifically, the diameter of the orifice is 1.5 m.
m, the flow rate is 450 ml / min, the pressure before the orifice (outlet of the electrolytic cell) is 0.32 kg / cm ² , and the pressure after the orifice (outlet of the liquid) is 0.16 kg / cm ² .

However, when the diameter of the orifice is 6 mm, the pressure difference is hardly obtained, and the primary pressure is also low. Therefore, a constant flow rate cannot be realized.

Specifically, the diameter of the orifice is 6 mm,
When the flow rate is 500 ml / min, the pressure before the orifice (electrolytic cell outlet) is 0.1606 kg / cm ² , and the pressure after the orifice (liquid outlet) is 0.16 kg / cm ² .

The capillary 34 corresponds to the adjusting valve 32 of the electrolytic sterilizing water manufacturing apparatus of FIG. 1, and is different from the adjusting valve 32 in that the flow rate is fixed. Further, although it is difficult to manufacture the adjusting valve 32 that can cope with the case where the flow rate is low, the capillary can be manufactured easily, and therefore, when the flow rate is constant and low, it is preferable to employ the capillary.

Further description will be given.

Reynolds number Re when the inner diameter d (m) of the capillary is 1 mm and the flow rate is 60 ml / min.
Becomes Re = v × d / ν. Here, v is a flow velocity (m / sec), and v is a kinematic viscosity coefficient of water (= 1.00 × 10 ⁻⁶ m ² / sec).

Here, v = {1000 × (60/6
0)} / (0.05 × 0.05 × 3.14) = 1.27
m / sec.

Therefore, Reynolds number Re = 1.27
× 0.001 / 1.00 × 10 ⁻⁶ = 1270. Then, since Re <2320, a laminar flow occurs.

Then, the capillary length is calculated by setting the head loss to the capillary outlet to 1.5 m.

The head loss h is expressed by the following equation.

H = λ (l / d) × (v ² / 2g) where λ is the friction coefficient of the pipe, l is the pipe length (m), d is the pipe diameter (m), v is the flow velocity (m / sec), g is the gravitational acceleration.

The pipe friction coefficient λ is 6 in the case of laminar flow.
Since it is represented by 4 / Re, λ = 0.05.

Therefore, l = 0.36.

That is, the inner diameter is 1 mm and the length is 36 cm.
You can use the capillary of.

Further specific examples will be described.

The inner diameter is 6 m at each of the left and right outlets of the electrolytic cell.
m pipe is attached, and the inner diameter is 1.5 mm about 50 cm ahead.
Each orifice is provided. Further, a T-shaped branch is provided immediately after the orifice, one of which is guided to the capillary structure via an electromagnetic valve, and the other is connected to the mixing tank. However, it is also possible to connect to the supply line to the mixing tank. The inner diameter of the capillary structure is 1 m.
m, the tip of a tube of 30 cm in length has an inner diameter of 0.5 mm,
It has a structure in which a tube having a length of 1 cm is attached.

This structure is adopted and 0.2% NaCl is used.
The effective chlorine concentration and pH value of the electrolyzed sterilized water when 40 A constant current electrolysis was performed using the solution, and the electrodes arranged with the diaphragm sandwiched were alternately functioning as the anode electrode and the cathode electrode are shown in FIG. , B.
Further, the production amount and the waste liquid amount were as shown by A and B in FIG. 7.

As can be seen from FIGS. 6 and 7, even when the polarities are interchanged, a substantially constant amount of production, effective chlorine concentration, p
H has been achieved. It is considered that this is because the orifice was provided to make the flow rate constant and the supply amount to the mixing tank could be controlled accurately.

Further, when the electrolytic current value was changed from 10 A to 40 A, the effective chlorine concentration was changed as shown in FIG. 8, and a substantially constant pH value was obtained as shown in FIG.
The generation flow rate changed as shown in FIG. Also, FIG.
In FIG. 10, the solid line shows the case where the right electrode is set as the anode, and the broken line shows the case where the left electrode is set as the anode. The solid line and the broken line show almost the same change characteristics.

Therefore, by changing the electrolytic current value, it is possible to change the effective chlorine concentration while keeping the pH value substantially constant.

FIG. 11 is a schematic view showing a main part of still another embodiment of the electrolytic sterilizing water producing apparatus of the present invention.

The electrolytic sterilized water manufacturing apparatus differs from the electrolytic sterilized water manufacturing apparatus shown in FIG. 5 only in that the orifice 35 and the capillary 34 are linearly arranged.

When this embodiment is adopted, since the anode water or the cathode water whose flow rate is made constant by the orifice 35 tends to flow toward the capillary 34, the waste liquid flow rate by the capillary 34 can be controlled more accurately. It can be carried out.

Next, the cabbage sterilization test results and the cutting board sterilization test results using broth will be described.

The cabbage sterilization test is conducted as follows.

(1) Sterilization step The outer leaf, browning part and worm-eaten part of the cabbage are removed and cut into quarters to remove the core. Shred the cabbage with a slicer (100 g).

Pre-clean cabbage with running tap water in a 10 liter container.

The cabbage is thoroughly washed with running tap water in a 10 liter container.

Immerse in sterilizing liquid for 5 minutes in a 10 liter container.

Rinse the cabbage with running tap water in a 10 liter container.

The cabbage is cooled by putting it in a cold water tank.

Drain the water.

20 g each is put in a stomacher bag and kept at 15 ° C.
Store in a constant temperature bath.

(2) Viable cell count measuring step 5 g of cabbage is placed in a homogenizer container, and 20 ml of sterilized water is placed therein.

13000 rpm for 2 minutes with a homogenizer
Grind with.

Filter with sterile filter paper, and use the filtrate as a sample stock solution (n = 2).

0.5 ml of the sample stock solution is placed in a clean test tube containing 4.5 ml of sterilized water and mixed well.

This is repeated to make a dilution series.

1 ml each of the sample stock solution and the diluted solution is placed in a Petri dish, and 15 ml of 55 ° C. standard agar medium is placed.

Incubate at 35 ° C. for 48 hours.

The growth settlement per plate is calculated. The numbers of two colonies are averaged, and the dilution ratio is multiplied to calculate the viable cell count per 1 g of cabbage.

The above is also performed for the number of days elapsed (sample stored at 15 ° C.).

In carrying out the above-mentioned sterilization step and viable cell count measurement step, pH 8.7, effective chlorine concentration 188 ppm
Sodium hypochlorite, pH 6.9, available chlorine concentration 1
When 87 ppm of electrolytic sterilized water was used as a sterilizing solution, the viable cell counts on day 0 were both below the detection limit.
The viable cell count on the day was 2.7 × 10 ^{4 in} the former case and 3.1 × 10 ³ in the latter case.

A chopping board sterilization test using broth is performed as follows.

10 g of commercially available ground pork is crushed together with 100 ml of pure water (sterile water obtained by sterilizing Millipore water) with a stomacher to prepare a stock solution of gravy.

This was diluted 10 times and 100 times to prepare a stock solution / 1
Use 0-fold dilution / 100-fold dilution. As a control, pure water is used instead of meat juice.

To a polyethylene cutting board piece (4 cm in length and width, 1.5 cm in heat), 40 drops of 25 μl were added so that the stock solution / 10 times dilution solution / 100 times dilution solution was spread over the entire surface, and the solution was placed in a desiccator or the like. A sample dried for 18 hours is used.

Put 50 ml of electrolytic sterilized water in a Petri dish,
The sample is added to this so that the gravy coating surface is on the bottom, the coating surface is in contact with electrolytic sterilized water, and the sample is pulled out after contact for a certain period of time.

This sample is immersed in a petri dish containing 5 ml of 0.01N sodium thiosulfate to neutralize available chlorine, and the gravy remaining on the cutting board is washed out.

100 μl of this solution was inoculated into a regular agar medium (making a dilution step), cultured at 35 ° C. for 24 hours, and the number of bacteria was counted. (Number of general bacteria) As an electrolytic sterilization liquid,
With an effective chlorine concentration of 58.7 ppm and a pH of 6.95,
And effective chlorine concentration is 211.1 ppm, pH 6.18
I used the one.

FIG. 12 is a graph showing the change in the viable cell count with the passage of contact time when the stock solution was used. Note that a
Is pure water, b is effective chlorine concentration 58.7pp
When using electrolytic sterilized water of m, c is effective chlorine concentration of 21
The case of using 1.1 ppm of electrolytic sterilized water is shown.

As can be seen from FIG. 12, in the contact time of 300 seconds, the electrolytic sterilized water having an effective chlorine concentration of 58.7 ppm was hardly sterilized in the same manner as pure water, while the effective chlorine concentration was 211.1 ppm. Electrolytic sterilization water of 10 ³
Is sterilized and the bactericidal power is at least 100 times as high as the number of bacteria. Theoretically, since the effective chlorine concentration is 4 times, it is possible that the bactericidal power of 4 times can be exhibited.
In fact, it can be seen that the bactericidal power of 25 times or more of this theoretical value could be achieved.

FIG. 13 is a graph showing changes in the viable cell count with the passage of contact time when a 10-fold diluted solution was used.
When a is pure water, b is an effective chlorine concentration of 5
When 8.7 ppm of electrolytic sterilized water was used, when c was used of electrolytic sterilized water having an effective chlorine concentration of 211.1 ppm,
Shown respectively.

As can be seen from FIG. 13, the effective chlorine concentration is 5
With 8.7 ppm of electrolytic sterilized water, it was not possible to sterilize below the measurement limit even after contacting it for 300 seconds, whereas with electrolytic sterilized water with an effective chlorine concentration of 211.1 ppm, it could be sterilized below the measurement limit with a contact time of 30 seconds. It was Therefore, it can be seen that the bactericidal power of 10 times or more, which is 2.5 times or more of the theoretical value, was achieved.

Furthermore, B. subtilis IFO3
Cultivated 134 strains to prepare spore fluid, which was broth / 10
0.5m for 9.5ml double dilution / 100 times dilution
Inoculation, the same treatment as above was performed, and B. The viable cell count of only subtilis was confirmed. In addition,
Preparation of spore fluid is described in B. subtilis IFO313
After culturing 4 strains in normal agar medium at 35 ℃ for 1 hour,
Achieved by two 10 minute heat treatments. Here, the spore bacterium is known to be difficult to sterilize.

FIG. 14 is a graph showing the transition of the viable cell count with the lapse of contact time in the case of using a spore solution containing no organic matter. In addition, when a is pure water,
Shows the case where electrolytic sterilized water with an effective chlorine concentration of 58.7 ppm was used, and c shows the case where electrolytic sterilized water with an effective chlorine concentration of 211.1 ppm was used.

As shown in FIG. 14, the effective chlorine concentration is 5
Whereas 8.7 ppm of electrolytic sterilized water could not be sterilized to below the measurement limit even if contacted for 600 seconds, electrolytic electrolytic sterilized water of effective chlorine concentration of 211.1 ppm could be sterilized to below the measurement limit. It was

FIG. 15 is a graph showing the change in the viable cell count with the elapse of contact time in the case of using a spore fluid containing an organic substance mixed with a 100-fold diluted broth. Note that a is pure water, b is electrolytic sterilized water with an effective chlorine concentration of 58.7 ppm, and c is an effective chlorine concentration of 211.1.
The case where the electrolysis sterilization water of ppm is used is shown, respectively.

As can be seen from FIG. 15, the effective chlorine concentration is 5
21 effective chlorine concentration compared to 8.7ppm electrolytic sterilization water
A sterilizing power of about 10 times could be achieved with 1.1 ppm of electrolytic sterilizing water. This is about 2.5 times the theoretical value.

[0125]

[0126]

[0127]

The invention according to claim 1 has a unique effect that electrolytic sterilization water having a high effective chlorine concentration having sufficient sterilizing power even in the presence of organic substances can be produced by adjusting the electrolytic current density.

[0128]

[0129]

According to the second aspect of the present invention, the electrodes arranged with the diaphragm sandwiched therebetween can be made to alternately function as the anode electrode and the cathode electrode, and the surface of each electrode is made suitable for electrolysis to improve the electrolysis efficiency. Since the electromagnetic valves can be increased and the solenoid valves can be selectively opened and closed according to the reversal of the polarity of the DC voltage, the unique effect that electrolytic sterilized water having an effective chlorine concentration of 150 to 400 ppm can be obtained. Play.

[0131]

[0132]

[Brief description of drawings]

FIG. 1 is a schematic view showing an embodiment of an electrolytic sterilizing water production apparatus of the present invention.

FIG. 2 shows the effect of pH on the form of free available chlorine in water.

FIG. 3 is a diagram showing measurement results of changes in viable cell count depending on the number of days elapsed after sterilization.

FIG. 4 is a diagram showing recovery of chlorine generation performance by polarity reversal of a DC voltage.

FIG. 5 is a schematic view showing another embodiment of the electrolytic sterilizing water production apparatus of the present invention.

FIG. 6 is a diagram showing an effective chlorine concentration and a pH value of electrolytic sterilizing water in the case where electrodes arranged with a diaphragm interposed therebetween are alternately made to function as an anode electrode and a cathode electrode.

FIG. 7 is a diagram showing the amount of electrolytic sterilized water produced and the amount of waste liquid in the case where electrodes arranged with a diaphragm interposed therebetween are alternately made to function as an anode electrode and a cathode electrode.

FIG. 8 is a diagram showing changes in effective chlorine concentration when the electrolytic current value is changed from 10 A to 40 A.

FIG. 9 is a diagram showing a pH value when the electrolytic current value is changed from 10 A to 40 A.

FIG. 10 is a diagram showing changes in the generated flow rate when the electrolytic current value is changed from 10 A to 40 A.

FIG. 11 is a schematic view showing a main part of still another embodiment of the electrolytic sterilized water production apparatus of the present invention.

FIG. 12 is a diagram showing changes in the viable cell count with the lapse of contact time when a stock solution is used.

FIG. 13 is a diagram showing a change in the viable cell count with the passage of contact time when a 10-fold diluted solution is used.

FIG. 14 is a diagram showing a change in the viable cell count with the passage of contact time when a spore solution containing no organic matter is used.

FIG. 15 is a diagram showing a change in the viable cell count with the lapse of contact time in the case of using a spore fluid in which an organic substance is mixed with a 100-fold diluted broth.

[Explanation of symbols]

1 Electrolyzer 2 Mixer 3 Mixing ratio setting device 13 Diaphragm 15 DC power supply 22 Mixing tank 32 Regulator valve 33 Open / close valve 34 Capillary 35 Orifice

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryoko Miyahara 3 Miyukigaoka, Tsukuba, Ibaraki Daikin Industry Co., Ltd. (56) References JP-A-2-111708 (JP, A) JP-A-4-111 94785 (JP, A) JP 10-151461 (JP, A) JP 6-335684 (JP, A) JP 8-257561 (JP, A) JP 8-183279 (JP, A) JP-A-7-132288 (JP, A) JP-A-8-309355 (JP, A) JP-A-9-150152 (JP, A) JP-A-9-299955 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C02F 1/46 A61L 2/18

Claims (2)

(57) [Claims] 1. An electrolysis means (1) for electrolyzing a chlorine compound-added water through a diaphragm (13) and an anode water and a cathode water taken out from the electrolysis means (1) are mixed to electrolyze. The mixing means (2) and (3) for obtaining sterilizing water and the electrolytic current density for electrolysis are adjusted to adjust the effective chlorine concentration in the range of 150 to 400 ppm, and the adjustment range of the electrolytic current density is 5 A / dm ² to. An electrolytic sterilized water production apparatus comprising: an adjusting means set to 40 A / dm ² . 2. The power supply means (15) capable of reversing the polarity of the DC voltage further comprises the mixing means (2) (3),
Mixing tanks (22) for mixing the anode water and the cathode water taken out from the electrolysis means (1), and the amounts of the anode water and the cathode water provided in the respective flow paths and supplied to the mixing tank (22). The electrolytic sterilized water manufacturing apparatus according to claim 1, further comprising a supply amount adjusting valve (32) for controlling the temperature and a solenoid valve (33).