JPH09113483A - Orp sensor for strong electrolyte and method for measuring orp of strong electrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To shorten the rising time of an ORP sensor for sensing a strong electrolyte being delivered from the electrolyte bath. SOLUTION: At the time of back wash where the electrolyte is not delivered or immediately after driving an apparatus, a reference electrode 3 comprising the Ag/AgCl electrode of an ORP sensor is applied with a negative potential from a power supply 6 for feeding a positive potential to an indication electrode 4 comprising a Pt electrode. After applying a voltage for a predetermined time, a switched 5 is turned on to begin the measurement. Consequently, a DC voltage is applied to activate the surface of both electrodes thus enhancing the affinity to strong electrolyte. This constitution shorten the rising time and the true ORP value of electrolyte can be measured quickly.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to reduction of measurement response time of an electrolyzed water producing apparatus using an oxidation-reduction potential (hereinafter referred to as ORP) sensor as an electrolysis detecting means.

[0002]

2. Description of the Related Art An electrolyzed water generator divides the inside of an electrolytic cell into a cathode chamber and an anode chamber by means of a diaphragm, inserts an electrode into its polar chamber, and electrolyzes the raw water supplied into the polar chamber by energizing the electrodes. As a result, cathode water is electrolytically generated in the cathode chamber and anode water is electrolytically generated in the anode chamber.

Further, a supply means for supplying a chlorine-based electrolyte to the raw water to be supplied to the electrolytic cell is provided, and the chlorine-based electrolyte is added and mixed with the raw water from the supply means and then electrolyzed while being supplied to the electrolytic cell to obtain a strong power. There is a device that performs strong electrolysis to obtain strong electrolyzed water. Strongly electrolyzed water obtained by such electrolysis, especially anodic water, has a high ORP and is used as cleaning water, disinfection and sterilization water.

It is desirable that the strong electrolyzed water used for the above purpose be continuously discharged in a stable state with a constant ORP. However, O of this strong electrolyzed water
RP is the amount of electrolyte to be input prior to electrolysis, the quality of raw water,
Strongly electrolyzed water with constant characteristics that constantly fluctuates due to changes in flow rate during electrolysis, fluctuations in voltage applied to the negative anode of the electrolytic cell, electrode consumption, and metal salt adhesion to the negative anode chamber and diaphragm. As stable as it is difficult to get. For this reason,
Strongly electrolyzed water discharged from the cathode / anode chamber side of the electrolytic cell is measured by an ORP sensor provided in a discharge pipe to determine whether the desired water quality is discharged, and the desired water quality is discharged from the measured value. Only when used for the above purpose.

Separately, the electric potential obtained by the ORP sensor is input to the control unit of the electrolyzed water producing apparatus to continuously discharge when the desired water quality is discharged, and to discharge when the desired water quality is not discharged. It can be stopped automatically, or the control unit can supply the electrolyte excessively to the water supply side to change its concentration, or automatically change the device driving conditions such as the electrolysis voltage to keep a constant desired ORP value. I try to get electrolyzed water.

FIGS. 6 and 7 are views showing the structure of an ORP sensor used with the above-described conventional ORP sensor display type strong electrolyzed water producing apparatus. Although the anode water is measured by the ORP sensor in the figure, the cathode water can be measured in the same manner.

In FIG. 6, the electrolytic cell 10 has a hermetically sealed structure, and the interior of the chamber is divided by a diaphragm 11, and the cathode electrode 2 is provided on one side.
2 is inserted into the cathode chamber 21, and the other anode electrode 12 is inserted into the anode chamber 13. An electrolytic current is applied to the cathode electrode and the anode electrode from an electrolytic power source 20 that applies a predetermined set voltage. A raw water supply port 23 leading to the cathode chamber and a raw water supply port 24 leading to the anode chamber are provided at the bottom of the electrolytic cell 10, and raw water is supplied from the husband's supply port. A discharge port 25 communicating with the cathode chamber and a discharge port 14 communicating with the anode chamber are formed in the upper part of the electrolytic cell 10.

The raw water supplied to the electrolytic cell 10 is tap water or the like. The electric conductivity of this raw water is adjusted by adding and mixing a chlorine-based electrolyte. A chlorine-based electrolyte is supplied to and mixed with the raw water supplied to the electrolyzer to increase the electric conductivity of the raw water and give a strong electrolytic action to the raw water. For example, salt is used as the electrolyte, and water is stored in the saline tank 26 as an aqueous solution, which is supplied to the saline injection device 28 by the metering pump 27. The supplied saline solution is metered into the raw water passing by the injector. If desired, the injected saline solution is further stirred and mixed by a mixing device (not shown), and is supplied to the electrolytic cell 10 from the pipe in a sufficiently mixed state.

Raw water is branched at the entrance of the electrolytic cell 10, and is supplied from the supply port 23 to the cathode chamber, and the other is supplied from the supply port 24 to the anode chamber. Cathode water electrolytically generated in the electrolytic cell 10 is discharged from the cathode chamber discharge port 25, and anode water is discharged from the anode discharge port 14. The cathode water is drained through a conduit communicating with the discharge port 25. Further, the anode water is connected to the discharge port 14 through the conduit 1
5 through the three-way valve 16 to the ORP sensor 9,
Water is discharged from the pipe opening 18 via the RP sensor 9. The three-way valve 16 switches to the water discharge side pipe line when the degree of electrolysis of electrolyzed discharge water, that is, the ORP is within a predetermined range, and switches to the drain pipe 17 outside the predetermined range.
The RP anode water is drained from the drain pipe 17 of the three-way valve 16. The signal obtained from the ORP sensor is input to the CPU included in the control unit 19, and each unit is controlled by arithmetic processing.

FIG. 7 shows an ORP sensor. The body 30 constituting the ORP sensor 9 is formed of a highly insulating member such as polyacetal or nylon. An ORP sensor composed of a reference electrode 31 formed with an AgCl film and an indicator electrode 32 formed of Pt is projected on the surface of the interior 33 of the body so as not to block running water inside the body.

The ORP sensor 9 is used to OR the anode water.
P is measured, and the detection measurement signal is supplied to the CPU forming the control unit 19. A predetermined reference value is recorded in advance in the CPU, and the outflow direction of the three-way valve 16 is freely switched by the comparison calculation processing with the measurement signal of the ORP sensor 9, and only the desired ORP is discharged. This result is returned to the control unit,
Anode water with a constant degree of electrolysis is always discharged.

Therefore, even if the flow rate of raw water fluctuates greatly at the beginning of electrolysis or due to a change in water pressure on the raw water side, in such a case, the three-way valve 16 switches to the drain pipe 17, so that the anode water to be discharged is not predetermined. There is no fear that the above water will be mixed, and the anode water having a constant ORP value can be discharged and used from the beginning of electrolysis.

However, in the apparatus having the above structure,
In driving the device, it takes a rise time for the ORP sensor to show an accurate value. In particular, when the ORP sensor has been in contact with air for a long time after the use is stopped, the electrode surface is not so familiar with the strong electrolyzed water and the OR
The P sensor does not show the correct value. Therefore, even if the desired ORP water is actually discharged, if the ORP sensor does not show an apparently accurate value, the strongly electrolyzed water being discharged is discharged as water that does not match the purpose. The water is wasted until the correct value is displayed.

[0014]

SUMMARY OF THE INVENTION In order to reduce the rise time of the ORP sensor for strong electrolyzed water discharged from the electrolytic cell, the present invention aims to reduce the ORP during the electrolyzed water discharge suspension period such as backwash time or immediately after the device is driven. Sensor reference electrode, Ag /
By applying a negative potential to the AgCl electrode and a positive potential to the indicator electrode Pt electrode, the surfaces of both electrodes are activated to improve the familiarity of the electrode surfaces with the strong electrolyzed water, thereby shortening the rise time. It is what The activation of the electrode surface by applying the above voltage to both electrodes shortens the start-up time even if the ORP sensor is in contact with air for a long time after the use is stopped, and the maintenance is easy and economical. It is possible to provide a high ORP sensor for measuring strong electrolyzed water.

[0015]

SUMMARY OF THE INVENTION Therefore, claim 1 of the present invention is provided.
In the ORP sensor device for measuring strong electrolyzed water, the electrolytic cell is divided into a cathode chamber and an anode chamber by an ion permeable diaphragm, and an anode and a cathode electrode are provided in the electrode chamber of the husband and the electrolysis power source for applying a predetermined direct current between the electrodes. In order to generate the cathode water in the cathode chamber and the anode water in the cathode chamber by electrolyzing the raw water supplied to the electrolytic bath by energization between the electrodes, a chlorine-based electrolyte aqueous solution is supplied to the raw water supplied to the electrolytic bath. A supply means for supplying is provided, and the degree of electrolysis on the discharge side of the electrolytic cell of the strong electrolyzed water generating device is adapted to cause electrolysis while supplying raw water to which the chlorine-based electrolyte aqueous solution is added and mixed by the supplying means to the electrolytic cell. In the case where an ORP sensing member composed of Ag / AgCl as a reference electrode for detecting electricity and Pt as an indicator electrode is provided, prior to electrolysis, a negative potential is applied to the reference electrode of the ORP sensing member and a positive potential is applied to the indicator electrode. It applied, characterized in that.

ORP for measuring strongly electrolyzed water according to claim 2 of the present invention
The sensor device is the ORP sensor device for measuring strong electrolyzed water according to claim 1, characterized in that a negative potential is applied to the reference electrode and a positive potential is applied to the indicator electrode during power-on or during a period during which electrolyzed water discharge is suspended. .

ORP for measuring strongly electrolyzed water according to claim 3 of the present invention
The sensor device is the ORP sensor device for measuring strong electrolyzed water according to claim 1, wherein when the rise of the ORP sensor is judged to be slow, a negative potential is automatically applied to the reference electrode and a positive potential is applied to the indicator electrode. It is characterized by

ORP for measuring strongly electrolyzed water according to claim 4 of the present invention
The sensor device is the ORP sensor device for measuring strong electrolyzed water according to claim 1, claim 2 and claim 3, wherein the voltage applied to the reference electrode and the indicator electrode is 10V to 20V, and the application time is 30 seconds to 3 seconds. It is characterized by being minutes.

ORP for measuring strong electrolyzed water according to claim 5 of the present invention
In the sensor method, the electrolytic cell is divided into a cathode chamber and an anode chamber by an ion-permeable diaphragm, and a positive and negative electrode is provided in each of the electrode chambers, and an electrolytic power source for applying a predetermined DC current is provided between the electrodes to provide an electrolytic cell in the electrolytic cell. In generating cathode water in the cathode chamber by electrolyzing the raw water supplied to the electrode by energization between the electrodes, and providing anode water in the anode chamber, a supply means for supplying a chlorine-based electrolyte aqueous solution to the raw water supplied to the electrolytic cell is provided, Ag as a reference electrode for detecting the degree of electrolysis on the discharge side of the electrolyzer of a strong electrolyzed water generator in which the raw water to which the chlorine-based electrolyte aqueous solution has been added and mixed by the supply means is electrolyzed / AgCl and an ORP sensing member made of Pt as an indicator electrode are arranged. After applying a negative potential to the reference electrode of the ORP sensing member and a positive potential to the indicator electrode, the ORP sensing member is operated. It is characterized in.

[0020]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is an explanatory diagram relating to an experiment for shortening the rise time of the ORP sensor of the present invention.
FIG. 2 is a diagram showing the relationship between the applied voltage and the rise time based on the above experimental results.

In FIG. 1, reference numeral 1 is a container corresponding to the tube in which the ORP sensor shown in FIG. 4 is arranged, and 2 is a container 1.
Known electrolytic solution filled with ORP, and 3 and 4 are reference electrodes, Ag / AgCl, which constitute the ORP sensor.
An electrode and an indicator electrode Pt electrode. Reference numeral 5 is a changeover switch, 6 is a power supply for supplying a DC voltage to both electrodes, 7 is an ORP measuring voltmeter, and 8 is a valve for discharging electrolyzed water or the like in the container.

Now, the changeover switch 5 is replaced with the measuring voltmeter 7.
The circuit is connected to the side, and the electrolytic water in the container is replaced with an electrolytic aqueous solution known to ORP. Then, for the ORP, the time until the value approaches the known ORP is measured. then,
It is possible to plot the time on the horizontal axis shown in FIG. 2 and the curve A ₁ showing the time / instruction ORP consisting of the instruction ORP on the vertical axis. Then, the water in the container is replaced again, and the changeover switch 5 is connected to the power source 6 side by a circuit, and then Ag / AgC is added.
A negative potential is connected to the l electrode and a positive potential is connected to the Pt electrode, and a voltage is applied for a predetermined time. After the application is completed, the changeover switch 5 is connected to the measuring voltmeter 7 side in the same manner as above,
The water in the container is replaced, an electrolytic aqueous solution of known ORP is added, and the time until the value of the ORP approaches the known ORP is measured. Then, a curve A ₂ showing the relationship of time / instruction ORP
Get. Thereafter, similarly, the application time and the applied voltage are changed to obtain the curve A ₃ ---- An.

From the above experimental results, it is possible to shorten the ORP rise time by applying a pretreatment voltage for a certain period of time, and obtain a suitable rise time by setting the above index to a certain value. You can

A preferred example of shortening the rise time by the above method is as follows. Applied voltage: 10 to 20 V Applied time: 30 seconds to 3 minutes If the polarities of the applied voltage are switched, it is impossible to obtain the preferable results as described above.

In the preferred embodiment described above, the rise time of the ORP can be set within 20 seconds. As a result, there is practically no waiting time, and it is possible to configure an electrolyzed water generator that eliminates the waste of discharging spouted water despite the originally having a predetermined ORP.

[0026]

EXAMPLE FIG. 3 is a diagram showing an example in which the above experimental results are applied to an ORP sensor used for measuring anode water of an electrolyzed water generator, and is contrasted with FIG. Members that operate in the same manner as in FIG. 6 are assigned the same reference numerals and duplicate explanations are omitted.
Although the ORP sensor is arranged in the anode water channel in the figure, it may be arranged in the cathode water channel or, of course, in the negative and anode water channels.

In the figure, 9 is an ORP sensor, and 1
9-1 is a control unit, 18 is a switching member, 29
Is an ORP sensor application power source, and 35 is a storage means.

In order to use the electrolyzed water producing apparatus for a long time, in order to remove the deposits accumulated in the cathode chamber and the cathode water flow path, reverse electrolysis in which the potential applied to the cathode and anode is reversed is carried out. FIG. 4 is a diagram showing the relationship between electrolysis / reverse electrolysis and ORP measurement / voltage application to the ORP measurement electrode.
It shows that a voltage is applied to the measurement electrode.

During the reverse electrolysis, the electrolyzed water that has flowed from the anode chamber to the three-way valve 16 via the pipe 15 is instructed by the control unit to supply water to the distribution pipe 17.
Drained from Therefore, electrolytic water does not flow to the ORP sensor during this reverse electrolysis. During this period, the control unit 19-1 operates and the switching member 18 causes the ORP sensor application power source 29.
Therefore, the above voltage can be applied to the ORP sensor electrode. The applied voltage and the applied time to the ORP sensor are compared with the reference value based on the experimental result shown in FIG. Therefore, when the rise time is slow, the application time (t ₁ ) may be set during the reverse electrolysis, and when the rise time is relatively fast, a part of the reverse electrolysis time may be applied (t _2). ) Is good. In either case, a favorable result can be obtained when the ORP sensor is displayed immediately after the application time is over.

FIG. 5 is an embodiment of a flow chart showing a case in which the result of the above experiment is adapted to operate at the start of operation of the electrolyzed water generator.

That is, when the rise of the ORP sensor is judged to be slow, a negative potential is automatically applied to the comparison electrode and a positive potential is applied to the indicator electrode, whereby the rise of water discharge is secured in a short time.

In the figure, the device power supply is turned on 101, and the response speed investigation 102 of the ORP sensor is performed. Then, within a short time, the time / instruction ORP shown in FIG.
It is confirmed whether the coefficient dθ / dt of the curve is within the range of the appropriate value stored in the ROM, that is, the indicated value range 103. When it is within the indicated value range, the water flow starts 104. When it is out of the indicated value range, water flow is not started, the response speed inspection circuit is disconnected 105, the above-mentioned DC voltage is applied 106 to both electrodes, and then the response speed inspection 102 of the ORP sensor is performed.

As described above, according to the present invention, the predetermined ORP
The value of electrolyzed water is measured quickly and can be easily and continuously produced.

[0034]

In order to shorten the rise time of the ORP sensor of the strong electrolyzed water discharged from the electrolytic cell, the reference electrode of the ORP sensor and the Ag / AgCl electrode of the ORP sensor are immediately after the electrolysis water discharge suspension period such as backwash time or immediately after the device is driven. A negative potential is applied to the indicator electrode, and a positive potential is applied to the Pt electrode to activate the surfaces of both electrodes and improve the familiarity of the electrode surfaces with strongly electrolyzed water, thereby shortening the rise time. it can. By activating the electrode surface by applying the above voltage to both electrodes, the rise time is shortened even when the ORP sensor is in contact with air for a long time after the use is stopped.
The true ORP value of electrolyzed water can be measured quickly.
As a result, it is economical because wasteful drainage does not have to be performed at the beginning of use of the device.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram related to an experiment for shortening the rise time of an ORP sensor according to the present invention.

FIG. 2 is a diagram showing the relationship between the applied voltage and the rise time of the ORP sensor according to the present invention.

FIG. 3 is an embodiment showing the arrangement and operation of an electrolyzed water generator according to the present invention and an ORP sensor used for measuring anode water.

FIG. 4 Electrolysis / reverse electrolysis and ORP measurement / O relating to the present invention
It is a figure which shows the relationship of the voltage application to an RP measurement electrode.

FIG. 5 is an embodiment of a flow chart showing an example adapted to operate at the time of starting the operation of the electrolyzed water generator according to the present invention.

FIG. 6 is a diagram illustrating a configuration of a conventional strongly electrolyzed water generator and an operation of an ORP sensor.

FIG. 7: OR used in a conventional strong electrolyzed water generator
It is a figure which shows the structure of a P sensor.

[Explanation of symbols]

 2 reference electrode 3 indicator electrode 9 ORP sensor 18 switching member 19-1 control unit 29 ORP sensor application power source 35 storage means

Claims (5)

[Claims] 1. An electrolytic cell is divided into a cathode chamber and an anode chamber by an ion-permeable diaphragm, and a positive and negative electrode is provided in each of the electrode chambers, and an electrolytic power source for applying a predetermined direct current is provided between the electrodes to provide the electrolytic cell. In producing the cathode water in the cathode chamber and the anode water in the anode chamber by electrolyzing the raw water supplied to the inside by energization between the electrodes, a supply means for supplying the chlorine-based electrolyte aqueous solution to the raw water to be supplied to the electrolytic cell is provided. As a reference electrode for detecting the degree of electrolysis on the discharge side of the electrolyzer of the strong electrolyzed water generating apparatus, which is configured to electrolyze while supplying raw water to which the chlorine-based electrolyte aqueous solution is added and mixed by the supply means to the electrolyzer. An ORP sensing member made of Ag / AgCl and Pt as an indicator electrode is provided, wherein a negative potential is applied to the reference electrode of the ORP sensing member and a positive potential is applied to the indicator electrode prior to electrolysis. That strongly electrolytic water measuring ORP sensor device. 2. The ORP sensor device for measuring strong electrolyzed water according to claim 1, wherein a negative potential is applied to the reference electrode and a positive potential is applied to the indicator electrode during power-on or during a period during which electrolytic water discharge is suspended. An ORP sensor device for measuring strong electrolyzed water. 3. The ORP sensor device for measuring strong electrolyzed water according to claim 1, wherein when the rise of the ORP sensor is judged to be slow, a negative potential is automatically applied to the reference electrode and a positive potential is applied to the indicator electrode. ORP for measuring strong electrolyzed water characterized by
Sensor device. 4. The ORP sensor device for measuring strong electrolyzed water according to claim 1, claim 2 or claim 3, wherein the voltage applied to the reference electrode and the indicator electrode is 10V to 20V and the application time is 30 seconds to. An ORP sensor device for measuring strong electrolyzed water, which is 3 minutes. 5. An electrolytic cell is divided into a cathode chamber and an anode chamber by an ion-permeable diaphragm, and a positive and negative electrode is provided in each of the electrode chambers, and an electrolytic power source for applying a predetermined direct current is provided between the electrodes to provide the electrolytic cell. In producing the cathode water in the cathode chamber and the anode water in the anode chamber by electrolyzing the raw water supplied to the inside by energization between the electrodes, a supply means for supplying the chlorine-based electrolyte aqueous solution to the raw water to be supplied to the electrolytic cell is provided. As a reference electrode for detecting the degree of electrolysis on the discharge side of the electrolyzer of the strong electrolyzed water generating apparatus, which is configured to electrolyze while supplying raw water to which the chlorine-based electrolyte aqueous solution is added and mixed by the supply means to the electrolyzer. In a case where an ORP sensing member composed of Ag / AgCl and Pt as an indicator electrode is arranged, a negative potential is applied to the reference electrode of the ORP sensing member and a positive potential is applied to the indicator electrode, and then the ORP sensing member is operated. Strong ORP measuring method of the electrolytic water, characterized in that.