JP3405707B2 - Method and apparatus for continuous measurement of ozone water concentration and operation control method and apparatus in electrolytic ozone water production apparatus - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a continuous method for measuring the concentration of ozone water in the electrolytic ozone water production equipment for producing ozone water by <br/> Ri anode side to electrolysis of water and its apparatus and the The present invention relates to an operation control method and an apparatus for an electrolytic ozone water producing apparatus using an ozone water measuring method, and specifically,
The present invention relates to a simple ozone water concentration measuring system.

[0002]

2. Description of the Related Art Although there are several methods for measuring ozone, an ultraviolet absorption method is generally used as an on-line measuring method used in an ozone water producing apparatus. This ultraviolet ray absorption method utilizes the characteristic that ultraviolet rays having a wavelength of 254 nanometers (nm) are absorbed only by ozone molecules and not by other molecules. The ultraviolet absorption amount and the ozone concentration are represented by the following equation (1) according to Lambert-Beer's law.

[0003]

## EQU1 ## I _o = I _i × exp (-kcd) ----------------------------------- -Equation (1) where I ₀ : UV transmission intensity I _i : UV incident intensity k: Absorption coefficient (depending on measurement wavelength and measurement object) c: Ozone concentration d: Measurement ozone layer thickness

In the above equation (1), if ozone water is used as the object to be measured, and ultraviolet ray of 254 nm is used as the measurement wavelength, the absorption coefficient (k) becomes a constant, and the layer thickness (d) of ozone water is measured by a measuring device. Since it is a constant that is determined, and the incident intensity of ultraviolet light (I _i ) is also determined by the ultraviolet ray generator, if the transmitted intensity of ultraviolet light (I _o ) is measured, the ozone concentration (c) in ozone water is calculated. I understand what is required.

However, in the case of a continuous ozone water concentration measuring device attached to an ozone water producing device to measure ozone water, ultraviolet rays may be generated due to deterioration of a light source (ultraviolet ray generator) or an ultraviolet ray detector during continuous measurement. Incident intensity (I
_{Since i} ) and the transmission intensity (I _o ) change with time, it is necessary to correct them.

Therefore, as a method of this correction, the intensity of transmitted ultraviolet light is measured using a comparative sample of which the concentration of ozone water is known, and the intensity of transmitted ultraviolet light of the sample for measurement is compared to obtain the ozone. A method of stably measuring the water concentration has been proposed. That is, the transmission ultraviolet intensity I _s of when passed through the measurement ozone water in the measurement cell, the transmission intensity of ultraviolet light when passed through a non-ozone water containing no ozone water in the measurement cell and I _n, the logarithm of the ratio Let E be E, from the above equation (1),

[0007]

[Number 2] _{E = log (I s / I} n) = logI s - logI n = log ((I i × exp (-kcd)) / logI i) = logI i -kcd- logI i = kcd --- --------------- Equation (2)

As is apparent from the equation (2), according to this method, the incident ultraviolet ray intensity (I _i ) due to the deterioration of the ultraviolet ray generator and the ultraviolet ray detector is canceled and the influence of the change with time is eliminated. It has become like. Therefore, by _obtaining the logarithmic value of the measured I _s and I _n and dividing this by k × d, the ozone water concentration c can be stably obtained.

FIG. 7 is a conceptual diagram showing this system, in which a UV connected to a stabilizing power source 2 for stably generating a predetermined 254 nm ultraviolet ray (hereinafter simply referred to as ultraviolet ray).
The ultraviolet light emitted from the lamp 1 is applied to both the measurement cell 3 through which the ozone water for measurement is passed and the comparison cell 3 ′ through which ozone-free water is passed, and the ozone water for measurement is passed through. The ultraviolet ray transmitted through the measuring cell 3 is detected by the ultraviolet ray sensor 4 and becomes an electric signal as a transmitted ultraviolet ray intensity I _s , which is transmitted to the computer unit (CPU) 7 through the preamplifier 5 and the logarithmic amplifier 6, while The ultraviolet rays transmitted through the comparison cell 3 ′ through which ozone water is passed are
The transmitted ultraviolet ray intensity I _n detected by the ultraviolet ray sensor 4 ′ is similarly converted into an electric signal and transmitted to the CPU 7 through the preamplifier 5 ′ and the logarithmic amplifier 6 ′, and the above I _s and I _n are transmitted.
Is calculated and the ozone water concentration c is calculated by division by k × d, and the ozone concentration of the ozone water is digitally or analogically displayed on the display 8.

Another method is to control so that the intensity of ultraviolet rays emitted from the UV lamp 1 is always constant.
This example is shown in FIG. In the figure, the ultraviolet rays emitted from the UV lamp 1 are reflected by the half mirror 20.
The pre-amplifier 22 divides the ultraviolet rays toward the measuring cell 3 and the ultraviolet rays toward the comparison sensor 21 into equal parts, detects the intensity of the incident ultraviolet rays by the comparison sensor 21, and converts the intensity into an electric signal.
To the comparison circuit 23. In the comparison circuit, the power of the power source 2'is controlled so that the intensity of the incident ultraviolet ray is compared with the initial intensity of the incident ultraviolet ray. As a result, the incident intensity of the ultraviolet rays incident on the measuring cell 3 is UV.
The concentration of ozone water is kept constant regardless of the change with time of the lamp 1, and the ozone water concentration can be stably measured.

[0011]

By the way, in the method shown in FIG. 7, there are two measurement systems, that is, two measurement systems.
One cell 3, 3 ', two preamplifiers 5, 5', 2
Since two logarithmic amplifiers 6 and 6'are required, the ozone water concentration measuring system becomes expensive. As a result, in the ozone water generator equipped with the ozone water concentration measuring device,
The ratio of the ozone water concentration measuring device in the price occupies a considerable portion, which is unreasonable as an ozone water generating device. In addition, the ozone-free water must be constantly passed through the comparison cell 3 ', which results in waste of raw water softened for the production of ozone water. Further, it is premised that the measurement cell 3 that passes ozone water and the comparison cell 3 ′ that passes non-ozone water progress evenly, but if the degree of contamination of both cells is different, In principle, it was inevitable that an error would occur. Even if there is a difference in the degree of deterioration of the ultraviolet sensors 4 and 4 ', an error will similarly occur in the measured value.

On the other hand, in the method shown in FIG. 8, the transmission ultraviolet intensity measuring system is simplified to only one system, which contributes to the cost reduction, but instead of this, the half mirror 20, Since the comparison sensor 21, the preamplifier 22, and the comparison circuit 23 are required, there is a limit to cost reduction.

As a result, it is no exaggeration to say that the high price of the ozone water concentration measuring device has hindered the spread of the ozone water producing device, and it is a simple and inexpensive ozone water concentration that can be incorporated into the ozone water producing device. At present, there is a strong demand for measurement systems. Therefore, in view of the present situation, an object of the present invention is to provide a method capable of continuously measuring the ozone water concentration at a low cost with a simple configuration, and further, by the signal from the ozone water concentration measuring device, generate ozone water. The purpose is to enable control of the device.

[0014]

The present invention has been made on the basis of such a viewpoint, and is characterized in that ozone water is continuously passed through a measuring cell while ultraviolet rays are transmitted. Te, in concentration of ozone water continuous measurement method for measuring the concentration of ozone water based UV absorption by ozone, water
Immediately before the production operation of the ozone water by the electrolytic type ozone water production apparatus that electrolyzes water to generate ozone water on the anode side, only the raw water is passed through the apparatus, thereby The ultraviolet absorption amount of the raw water that does not substantially contain ozone supplied to the measurement cell is measured, and the obtained ozone water concentration is stored as a zero point, and the ozone water manufacturing operation of the electrolytic ozone water manufacturing apparatus is performed. The point is that the concentration of ozone water supplied from the apparatus to the measuring cell after the start is measured with reference to the zero point. That is, just before the operation of the electrolytic ozone water production apparatus, only raw water is passed to discharge ozone-free water that does not substantially contain ozone from the ozone water discharge port of the apparatus. Measure the concentration of ozone water, and set the measured concentration of ozone-free water as the zero point,
After the start of the ozone water production operation, the concentration of the generated ozone water is continuously measured based on this zero point, so it is possible to continuously measure the ozone water using only one ultraviolet intensity detection system. It is what you have done.

[0015] Incidentally, the ozone water concentration measurement after the start of operation of the electrolytic ozone water production apparatus, is preferably started after the lapse of a predetermined time after the ozone water production start, thereby collecting
It is possible to prevent the unstable operation of the device control system due to the measurement of ozone water concentration under the condition where the ozone water concentration is unstable immediately after the operation of the solution type ozone water production device.

Further, since the intensity of the ultraviolet rays generated by the ultraviolet ray generator slightly changes depending on the environmental temperature of the ultraviolet ray generator, it is also preferable to measure the environmental temperature and correct the zero point. is there.

Next, as an ozone water concentration continuous measuring apparatus according to the present invention, a UV lamp which emits ultraviolet rays and the UV lamp
A stabilized power source for generating a predetermined ultraviolet ray from the lamp, and an ultraviolet ray from the UV lamp are transmitted and water is absorbed .
A measuring cell for continuously passing ozone water supplied from an electrolysis type ozone water producing device that electrolyzes to generate ozone water on the anode side , and an ultraviolet sensor for measuring the intensity of transmitted ultraviolet light transmitted through the measuring cell. A computer for calculating the concentration of ozone water based on the intensity of the transmitted ultraviolet light, wherein the computer only passes the raw water immediately before the production operation of the ozone water by the electrolytic ozone water producing apparatus, Zero point storage means for storing the ozone water concentration calculated based on the transmitted ultraviolet intensity measured by the sensor as a zero point, and the ozone water manufacturing operation of the electrolytic ozone water manufacturing apparatus is started with reference to the zero point. It further comprises ozone water concentration calculating means for calculating the concentration of ozone water afterward. With such a configuration, the concentration of ozone water can be continuously measured by one system of transmitted ultraviolet intensity measurement system.

The voltage signal set in proportion to the transmitted UV intensity transmitted from the UV sensor to the computer is amplified by a preamplifier and then transmitted to the computer via a logarithmic amplifier. There is a method of transmitting to a computer without passing through a logarithmic amplifier as it is amplified.In the latter case, the logarithmic amplifier is omitted by adopting a simple method in which the exponential function is linearly approximated to calculate an approximate value. There are advantages.

Further, temperature measuring means for measuring the temperature in the vicinity of the UV lamp is provided, and the computer is provided with a zero point correcting means for correcting the zero point on the basis of the environmental temperature measured by the temperature measuring means. It is also a preferable aspect to provide.

Further, the ozone water supplied from the electrolysis type ozone water producing apparatus is first supplied to a gas-liquid separator to separate the gas phase component, and only the liquid phase component is supplied to the measuring cell. The preferred method is to accurately measure the ozone concentration in ozone water.

There is also a system in which an operation control command for the electrolytic ozone water producing apparatus is issued from the computer so that the concentration of generated ozone water falls within a predetermined range based on the calculation result in the computer. The control elements in this case include the supply current value, voltage value, raw water supply amount, and pressing force of the electrode against the solid polymer electrolyte membrane in the electrolytic ozone water producing apparatus.

Further, as the operation control device of the electrolytic ozone water producing apparatus according to the present invention, the ozone concentration is calculated based on the ultraviolet absorption amount of ozone by continuously transmitting the ozone water and transmitting the ultraviolet rays. and ozone water concentration measurement means, before
The concentration of ozone water whose serial does not contain substantial ozone was passed through to the device production runs immediately before the ozone water by electrolysis ozone water production apparatus raw water is measured by the ozone concentration measuring means, the measured value Is set as the zero point of the ozone concentration and zero point storing means for storing this, zero setting confirming means for confirming the presence or absence of the zero point setting, and confirming the zero point setting, the electrolytic ozone water producing apparatus An energization starting means for starting energization of the electrolyzer and the ozone water concentration produced by the electrolytic ozone water producing apparatus are continuously measured by the ozone concentration measuring means, and the measured ozone water concentration is within a predetermined range. If the density determination means determines that the control element to be controlled is within the control limit, the density determination means determines whether the control element to be controlled is within the control limit. Limit determining means, a control signal output means for outputting a predetermined control signal when the control element is determined to be within the control limit by the limit determining means, and the control element is controlled by the limit determining means. If it is determined to have reached the is made in the manner moves to a preset process of the reproduction processing or the like to the solid polymer electrolyte membrane of the electrolytic ozone water production apparatus. The control element includes a current value, a voltage value, a raw water supply amount, and a pressing force of the electrode against the solid polymer electrolyte membrane, and one or more of these are controlled within a predetermined range.

The ozone water concentration is measured by the ozone concentration measuring means until a predetermined time elapses after the production of ozone water by the electrolysis type ozone water producing apparatus is started by the energization starting means. It is also a preferable embodiment that the measurement prohibiting means is provided to prohibit the control under unstable conditions at the beginning of the ozone water production.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to the drawings. FIG. 1 is a system diagram showing an embodiment of a continuous ozone water concentration measuring method according to the present invention. In the figure, prior to the operation of the electrolytic ozone water producing apparatus 10, all the measuring devices of the ozone water concentration measuring apparatus M are started up to be in a measurable state, and the electrolytic ozone water producing apparatus 10 is supplied with the soft water from the raw water line 15. The supply of raw water that has been subjected to chemical treatment is started.
At this point in time, only the water passage line of the electrolysis-type ozone water producing device 10 is operating, and electricity is not supplied for electrolysis. Therefore, the water discharged from the ozone water discharge line 16 still contains ozone. Not, it is discharged in the state of raw water. A part of this raw water (no ozone water) is measured line 1
It is branched to 1 and supplied to the gas-liquid separator 9. At this stage, since the water supplied from the line 11 does not contain gas, the raw water enters the lower chamber 9b of the gas-liquid separator 9 and is supplied into the measurement cell 3 via the line 12 and the line 13 Then, it is discharged to the outside of the apparatus through the discharge line 14 through the upper chamber 9a of the gas-liquid separator 9.

In the measuring cell 3, the ultraviolet rays incident from the UV lamp 1 are transmitted through the raw water flowing through the cell 3, but since they do not contain ozone, the incident ultraviolet rays are not absorbed and remain as they are. The transmitted ultraviolet ray intensity of the incident ultraviolet ray is detected by the ultraviolet ray sensor 4 and converted into an electric signal, which is transmitted to the computer unit (CPU) 7 via the preamplifier 5 and the logarithmic amplifier 6, Ozone water concentration (c) = 0 based on (1)
Is calculated as From this calculation result, the incident ultraviolet ray intensity (I _i ) can be obtained as the transmitted ultraviolet ray intensity (I _o ) = incident ultraviolet ray intensity (I _i ). That is, the transmitted ultraviolet ray intensity (I _o ) corresponding to the incident ultraviolet ray intensity (I _i ) is used as a reference as the zero point of the ozone water concentration.

This standard setting (zero point setting) is performed immediately before the start of the ozone water producing operation of the electrolytic type ozone water producing apparatus 10.
That is, before the energization operation, only the raw water that does not substantially contain ozone is passed, and the concentration is measured about 100 times per second, and the average value is taken to smooth the noise. And the average value is further calculated by repeating this average value calculation a plurality of times to improve the zero point setting accuracy. Therefore, several tens of seconds is sufficient as the zero point setting time. From this meaning, when the power of the device is turned on, first, only the ozone water concentration measuring device M starts up, and when it becomes a measurable state, only water flow is started and the above-mentioned zero point setting is performed. It is also possible to automatically control a series of steps by the CPU 7 so that the electrolysis device is energized to start the production of ozone water upon completion.

Next, when the standard setting is completed, the electrolysis type ozone water producing apparatus 10 is turned on to start the production of ozone water by electrolysis, and the generated ozone water is discharged from the line 16. To be done. Most of this ozone water is sent to the demand destination from the supply line 17, but part of it is on the line 1 described above.
1 is fed to the lower chamber 9b of the gas-liquid separator 9 which is divided into the upper chamber 9a and the lower chamber 9b. Electrolytic ozone water production equipment
The ozone water is fed from the location of the line 11, the ozone gas of the oxygen and undissolved caused by electrolysis of water is also a gas-liquid mixed phase stream which contains slightly, is supplied to the left measurement cell 3 As a result, ozone in the gas phase also absorbs ultraviolet rays, and the diffused reflection of ultraviolet rays by the bubbles makes it impossible to accurately measure the amount of ultraviolet rays absorbed by ozone in ozone water. Therefore, in the present invention, by flushing into the gas-liquid separator 9, the gas phase component is discharged from a gas hole 9d formed in the partition wall 9c that defines the upper chamber 9a and the lower chamber 9b by an ejector action described later. The liquid is sucked into the upper chamber 9a and only the liquid phase component flows into the measuring cell 3 through the line 12.

In the measuring cell 3, as described above, the ultraviolet rays incident from the UV lamp 1 are absorbed by the ozone molecules in the ozone water, and as a result, the transmitted ultraviolet intensity detected by the ultraviolet sensor 4 decreases in proportion to the ozone water concentration. The strength is measured. The transmitted ultraviolet intensity (I _o ) is converted into an electric signal (voltage signal) by a known method, transmitted to the CPU 7 through the preamplifier 5 and the logarithmic amplifier 6, and as described above, the equation (1) and the setting described above are performed. The ozone water concentration (c) is calculated based on the reference value (I _i ) of the zero point,
The result is displayed on the display unit 8 as analog or digital as required. Also in this ozone water concentration measurement, a large number of concentration measurements are made at a minute time interval within a certain period, the average value of many concentration measurement values within the certain period is calculated, and this average value is used as the ozone water for that period. The density is set so that the influence of noise is smoothed.

The ozone water used for ozone measurement is supplied to the upper chamber 9a of the gas-liquid separator 9 through the line 13.
It is discharged from the line 14 to the outside of the system. At this time, the upper chamber 9a of the gas-liquid separator 9 is set to have a smaller flow passage area than the lower chamber 9b, and the upper chamber 9a of the gas-liquid separator 9 is connected from the line 14.
The measured ozone water flowing into a is designed to pass through the upper chamber 9a and reach the line 14 at high speed. As a result, the pressure in the upper chamber 9a becomes lower than the pressure in the lower chamber 9b, and the gas phase component in the ozone water including the gas phase component supplied from the line 11 to the lower chamber 9b is formed in the partition wall 9c. The gas is discharged from the gas hole 9d into the upper chamber 9a by the ejector action, and the measured ozone water and the line 14
Is discharged from the system.

The intensity of the ultraviolet rays generated by the UV lamp 1 is slightly changed depending on the environmental temperature T near the UV lamp 1. That is, the incident ultraviolet ray intensity I _i is expressed as a function “I _i = f (T)” of the environmental temperature T. Therefore, the environmental temperature T is measured by the temperature measuring device 18, this is transmitted as an electric signal to the CPU 7, and the zero point is set by performing a function operation of I _i = f (T) in the CPU 7. It is possible to correct the temperature of the set zero point according to the change with the temperature at that time, but the zero point setting is performed at the time when the UV lamp is stabilized, and the ozone water manufacturing apparatus is not operating. However, it is not always necessary when a system that does not change the ambient temperature of the UV lamp 1 is adopted.

FIG. 2 is a flow chart showing another embodiment of the electrolytic ozone water concentration measuring method according to the present invention.
1 is different from that in FIG. 1 in that the electric signal inputted to the CPU 7 is logarithmically converted by the logarithmic amplifier 6 and inputted in FIG. 1, whereas it is still amplified by the preamplifier 5 in the system of FIG. Since the only difference is that it is input in this state, and the other configurations are the same, only the differences relating to the following will be described, the same configurations will be assigned the same reference numerals, and detailed description will be omitted.

As is clear from the equation (1), the relationship between the ozone concentration and the intensity of transmitted ultraviolet rays is an exponential relationship. Therefore, even if the transmitted ultraviolet intensity is converted into a voltage signal as an electric signal proportional to this, the relationship between the voltage (V) and the ozone concentration (x) is an exponential relationship, so in the example of FIG.
This exponential relationship is converted into a linear relationship (linear relationship) by the logarithmic amplifier 6 and input to the CPU 7. The CPU 7 calculates the ozone concentration corresponding to the input voltage value based on the programmed primary expression. It is supposed to do. On the other hand, in the method of FIG. 2, since the logarithmic amplifier 6 is omitted, the input voltage (V) and ozone concentration (X) are input.
The relationship with and is an exponential function relationship as shown in FIG. Therefore, this exponential function is approximated by a straight line (linear expression) of ~, and the approximate expression of ~ is stored in the CPU 7, and when the input voltage value is V1 or more (V≥V1).
When the input voltage value is V2 or more and less than V1 (V = aX + b)
When 2 ≦ V <V1), the ozone concentration is calculated by the formula (V = a′X + b ′), and when the input voltage value is less than V2 (V <V2), the formula (V = a ″ X + b ”is calculated. By calculating the ozone concentration by (1), the ozone water concentration can be obtained by a simple method and the logarithmic amplifier 7 can be omitted, which contributes to cost reduction. It should be noted that, if an approximate value calculation of this degree is performed, there will be no practical problem at all in the range used for normal sterilization or cleaning, except for special cases such as tests for which a strict ozone water concentration is required.

Further, in the present invention, it is also possible to control the operation of the electrolytic ozone water producing apparatus based on the result of the calculation of the ozone concentration in the CPU 7. Therefore, first, an outline of the electrolytic ozone water producing apparatus used in the present invention will be described. The electrolytic ozone water producing apparatus used in the present invention is disclosed in JP-A-8-134677 and JP-A-11-
It is an electrolytic ozone water producing apparatus shown in No. 1724832 and the like, and the structure thereof is not particularly limited, but
An example is shown.

FIG. 4 is a cross-sectional view of an essential part showing an example of the electrolytic ozone water producing apparatus used in the present invention. In FIG. 4, the electrolytic ozone water producing apparatus is a fluorine having corrosion resistance to ozone. A solid polymer electrolyte membrane (hereinafter simply referred to as “membrane” or “electrolyte membrane”) 35 is disposed between the anode side casing 31 and the cathode side casing 32, which are coated with resin or glass on the inner surface thereof, Inside the side casing 31 and the cathode side casing 32, the anode chamber 36 and the cathode chamber 3
It is divided into seven. On the surface of the electrolyte membrane 35 on the side of the anode chamber 36, an anode electrode 33 provided with a noble metal catalyst 46 such as platinum having a function of generating ozone is arranged so as to press the electrolyte membrane. On the other hand, on the surface of the electrolyte membrane 35 on the cathode chamber 37 side, a cathode electrode 34 having a contact surface 50 of a noble metal such as platinum or silver is arranged so as to press the electrolyte membrane 35. Further, raw water inlets 38 and 39 and outlets 40 and 41 are formed in the anode chamber 36 and the cathode 37, respectively, and a DC power source 54 is provided between the electrodes 33 and 34.
A DC voltage is applied via the electrode rods 49 and 53. Each of the electrode rods 49 and 53 is arranged so as to penetrate through the through hole 42 of the anode side casing 31 and the through hole 43 of the cathode side casing 32, and the ends thereof are connected to the fluid pressure cylinder devices 44 and 45. .., respectively. In other words, the pressing force of the electrode surface against the electrolyte membrane 35 is adjustable.

In the apparatus having such a structure, when water is passed through the anode chamber 36 and the cathode chamber 37 and a direct current is passed between both electrodes, water is electrolyzed with the electrolyte membrane 35 sandwiched between the electrodes and the anode electrode 33 side. Generates ozone, and hydrogen is generated on the cathode electrode 34 side. The ozone generated on the side of the anode 33 is dissolved in water to become ozone water, and is discharged from the outlet 40 as ozone water.

Here, in order to efficiently generate ozone water, as disclosed in Japanese Patent Laid-Open No. 8-134677, the portions of both electrodes 33, 34 which are in contact with the electrolyte membrane 35 are
The wire nets 46 and 50 are made of noble metal, and lath nets 47 and 51 made of titanium or the like having corrosion resistance to ozone and electrode plates 48 and 52 are sequentially laminated on the back surface of the wire nets and brazed. The electrode structure has an integrated structure. As a result, the raw water causes a violent turbulent flow and a vortex during the flow through the flow path composed of the wire net and the lath net, and the ozone generated on the anode electrode side is instantly dissolved in the water immediately after the generation, resulting in a high concentration. It is configured to obtain ozone water.

When ozone water is produced using such an apparatus, it is general that the operation is controlled so that the concentration of ozone water as a product falls within a predetermined range. In this case, the performance of the electrolyte membrane deteriorates as the operation continues, and as a method of compensating for this and controlling the ozone water concentration to fall within a predetermined range, there is the following method. (1) The current value control method is a method in which the ozone water concentration is continuously measured, and when the lower limit value of a predetermined concentration range is reached, the current value is gradually increased until it reaches a predetermined upper limit value to promote ozone generation. . (2) The pressing force change method continuously measures the ozone water concentration, and when the lower limit value of the predetermined concentration range is reached, the pressing force of the electrode against the electrolyte membrane is gradually increased until it reaches a predetermined upper limit value. In this method, the contact surface between the electrode and the electrolyte membrane is renewed to promote ozone generation. In this case, there is also a method that is used in combination with the above current value control method.

Further, since the electrolyte membrane itself gradually deteriorates during use, it is necessary to regenerate it periodically. The following methods are available as this reproduction processing method. (B) As a result of continuous operation of the electrolyte membrane regeneration system by the system of (1) or (2) above, when the control system reaches its limit,
In this method, the pressing force of the electrode against the electrolyte membrane is released for a predetermined time to release the stress of the electrolyte membrane for regeneration. (B) The pressing force change method is a short time (about several seconds) so that the discharged ozone water concentration is not affected after each operating time of 10 to 20 minutes or when the ozone water concentration reaches a predetermined lower limit value. In this method, a pressing force change for releasing / pressurizing the electrode pressing force against the electrolyte membrane is applied to the electrolyte membrane, and the regeneration treatment is performed before the deterioration of the electrolyte membrane progresses. There is also a method in which this method is used in combination with the above (1) and (2) to dramatically extend the continuous operation time.

In the present invention, among these control operations, the control operation based on the ozone water concentration is the CP
Based on the calculation result of ozone water concentration performed in U7, the CP
It is possible to output a control signal from U7 to the electrolysis-type ozone water producing device. The control elements are the current value (current density) and the voltage value (the higher the voltage, the higher the current. Significance), there is a pressing force on the electrolyte membrane of the electrode.

Next, an example of control of the electrolytic ozone water producing apparatus according to the present invention will be described with reference to FIG. Figure 5
An example of a control flow of the electrolytic ozone water producing apparatus according to the present invention is shown. First, when the apparatus is turned on and started, as shown in block 61, energization of the ozone water concentration measuring system is started. At the same time, the supply of raw water to the ozone water producing apparatus is started (S1), but the electrolysis apparatus is not energized at this point. Next, the zero setting confirmation means 62 determines whether or not the zero point setting (reference setting) of the ozone water of the measurement system is performed (S).
2). At the start of normal operation, the zero point has not been set as described above (S2, NO), so ozone concentration in raw water that is ozone-free water is measured (S3), and the measured concentration of this ozone-free water is set to zero. The zero point setting to set the point is performed (S4), and the ozone water concentration measurement preparation is completed. When the preparation for measuring the concentration of ozone water is completed, electricity is supplied to the electrolyzer to start the production of ozone water (S5).

Incidentally, in S2, when the zero point setting is completed (S2, YES), that is, after the end of the device suspension period due to the temporary suspension of energization for electrolyte membrane regeneration, the device control is performed. At the time of restarting after the device is stopped in the process, the control system itself continues to operate,
Since it is not necessary to set the zero point again, the energization of the electrolysis device is immediately started (S5).

Next, when the production of the ozone water is started, the elapsed time t from the start of the production of the ozone water is measured, and the elapsed time determining means determines the predetermined period ts in which the elapsed time is preset. It is judged whether or not it has passed (S6),
When it is determined that the elapsed time t has reached the predetermined time or longer (t ≧ ts) (S6, YES), continuous ozone water concentration measurement is started in the above-described manner (S7). This is because at the beginning of the operation of the ozone water production device, the ozone water concentration is in the process of rising, but is in an unstable state, so it is inappropriate to measure this state and control the device. .
Therefore, a measurement prohibition period during which ozone water is not measured is provided for a certain period (for example, 10 seconds to several minutes) until the concentration of ozone water is stabilized.

When the ozone water concentration is continuously measured, the value is transmitted to the next concentration determination means 68, where the ozone water concentration (X) is within a predetermined allowable concentration range (Xmin≤X≤Xma).
(x8) is judged (S8), and if it is within the allowable range (S8, YES), the process returns to ozone water concentration measurement (S7). When it is determined that the ozone water concentration is outside the predetermined allowable range (S8, NO), control for changing the operating condition is performed in order to return the concentration to the predetermined range.
Before that, the limit determination means determines whether or not the control element to be controlled (increase / decrease in current value, increase / decrease in pressing force on the electrolyte membrane, etc.) has reached the limit (S9). If the limit has not been reached, a predetermined control signal is output from the block 69 (S10), predetermined control is performed based on the signal (S11), and then the ozone water concentration measurement is performed again ( S7).

Incidentally, in S9, when the control limit is reached, and when the current value is controlled so as to increase in response to the decrease in the concentration of ozone water due to the decrease in the performance of the electrolyte membrane, the current value has already been increased. Is reached when the current value cannot be increased any further, and the control is performed to increase the pressing force of the electrode against the electrolyte membrane in response to the decrease in ozone water concentration due to the performance deterioration of the electrolyte membrane. In the case of performing, it means that the pressing force has already reached the upper limit value of the device and the pressing force cannot be increased any more. In such a case, the limit determination means determines that the control element has reached the control limit (S9, YES), and proceeds to the next preset step. The next step may be a case where the operation of the device is stopped to regenerate the electrolyte membrane or a case where the pressing force of the electrode against the electrolyte membrane is released for a predetermined time to regenerate the electrolyte membrane. Then, the process is returned to S1 and restarted.

[0045]

EXAMPLES Next, examples of the present invention will be described. The ozone water concentration measuring device shown in FIG. 2 is attached to the electrolytic ozone water producing device shown in FIG. 4, and the conventional ozone water concentration measuring device shown in FIG. 8 is additionally attached for comparison. The ozone water concentration measurement test was performed. First, according to the method of the present invention, prior to the ozone water production operation, the electrolysis-type ozone water production apparatus is not energized (without electrolysis) for about 2 minutes.
Only the raw water is allowed to flow, the zero point is set by ozone-free raw water, and then the ozone water production device is turned on to produce ozone water, and the ozone water concentration is measured for about 3 minutes after the start of the ozone water production operation. Without performing, the ozone concentration measurement was started after about 3 minutes had elapsed. In the conventional external ozone water concentration measuring device, the ozone water concentration was measured from the beginning. The measurement results by both methods are shown in FIG.

In the figure, the intensity of transmitted ultraviolet rays is converted into a voltage proportional to the value and displayed, and the higher the voltage value, the smaller the ultraviolet absorption (the smaller the amount of ozone contained). In the figure, t1 is a period (about 2 minutes) during which only raw water is allowed to flow, and the voltage output corresponding to the intensity of transmitted ultraviolet light during this period is 2.8 to 3.0 V. Based on this, the zero point is set in the method of the present invention. When the energization of the electrolysis device is started after the lapse of t1, simultaneously with the start of the energization, the external measuring device (conventional method) promptly increases the ozone water concentration, and at the same time,
The output voltage corresponding to the transmitted ultraviolet intensity is 0.2 to 0.3.
It is rapidly decreasing to V. The time t2 (about 3 minutes) after the start of energization to the electrolyzer is a period during which the measurement of the concentration of ozone water according to the method of the present invention is prohibited. Concentration is 17p
It can be seen that the level value of about pm is detected. As is apparent from the figure, the ozone water concentration measured by the method of the present invention and the ozone water concentration measured by the conventional method are extremely close to each other. Incidentally, the measured value by the method of the present invention shows a variation of about 1 ppm as compared with the measured value by the conventional method, but at the level where ozone water is used for normal sterilization, cleaning, etc., it may be a level without any problem. confirmed. In this sense, it is also understood that it is possible to control the operation of the electrolytic ozone water producing apparatus based on the ozone water concentration measured by the ozone water concentration measuring method of the present invention.

[0047]

As described above, according to the present invention, the electrolytic
Since the ozone concentration is measured by only one series of ozone water concentration measuring system in the ozone water producing apparatus , there is only one measuring cell. Therefore, as compared with the conventional method using two cells shown in FIG. 7, not only does it contribute to cost reduction, but the conventional method distributes water having different properties to each cell, so that it can be used during use. Contamination gradually accumulates on the inner surface of the cell, and since the degree of the contamination is different, the degree of ultraviolet absorption due to the contamination also changes, so that an error will gradually occur in the comparison of the transmitted ultraviolet intensities of both cells. However, since only one measurement cell is used, even if stains occur on the inner surface of the cell, the influence of the transmitted UV intensity due to the stains will be the same when setting the reference value and when measuring ozone water. Errors are less likely to occur. In this sense, the reliability in the process of long-term use will be improved.

Further, as compared with the conventional method shown in FIG.
Although it is the same in that one cell is used, an expensive half mirror is not required in the method of the present invention, and only one ultraviolet sensor is required, and further, a comparison circuit is not required. Is possible.

[0049] As described above, in the present invention method, since it is possible to measure the ozone concentration alone in the measurement system of the one line, electrolytic
It is possible to inexpensively provide relative formula ozone water concentration measuring apparatus with the conventional method. As a result, can be used as very effective measuring device as an online measuring device for attached to electrolytic ozone water production apparatus, it is expected to greatly contribute to cost reduction of the electrolytic ozone water production apparatus.

As a result of the cost reduction of the ozone water producing device, it is possible to inexpensively supply the electrolytic ozone water producing device to the market, and the use of ozone water is dramatically spread in the fields such as sterilization and cleaning. As a result, it is expected that the occurrence of food poisoning and the spread of pathogenic bacteria will be prevented, and that it will greatly contribute to the health and safety management of the people.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing an example of an ozone water concentration measuring method according to the present invention.

FIG. 2 is a conceptual diagram showing another example of the ozone water concentration measuring method according to the present invention.

FIG. 3 is an output-concentration graph showing an example of an ozone concentration calculation method in FIG.

FIG. 4 is a conceptual diagram of a main part of an electrolytic ozone water producing apparatus used in the present invention.

FIG. 5 is a flow chart showing a control example of the electrolytic ozone water producing apparatus according to the present invention.

FIG. 6 is a time chart showing an example of the present invention.

FIG. 7 is a conceptual diagram showing an example of a conventional ozone water concentration measuring method.

FIG. 8 is a conceptual diagram showing another conventional ozone water concentration measuring method.

[Drawing reference number]

1 UV lamp 2 UV lamp power source 3, 3'UV absorption measuring cell 4, 4 'UV sensor 5, 5' Preamplifier 6, 6'Logarithmic amplifier 7 CPU 8 Display 9 Gas-liquid separator 10 Electrolytic ozone water production apparatus

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI C25B 15/02 302 C25B 15/02 302 G01N 21/33 G01N 21/33 (58) Fields investigated (Int.Cl. ⁷ , DB Name) G01N 21/00-21/61 C02F 1/46 G01N 1/10 G01N 35/08 C01B 13/10 C25B 15/02 302 Practical file (PATOLIS) Patent file (PATOLIS)

Claims (14)

(57) [Claims] 1. A method for continuously measuring ozone water concentration, wherein ozone water is continuously passed through a measuring cell (3) while ultraviolet rays are transmitted, and the ozone water concentration is measured based on the amount of ultraviolet light absorbed by ozone. Immediately before the ozone water production operation of the electrolysis type ozone water production apparatus (10) that electrolyzes water to generate ozone water on the anode side, only the raw water is passed through the apparatus. The amount of ultraviolet absorption of the raw water containing substantially no ozone supplied from (10) to the measurement cell (3) is measured, and the obtained ozone water concentration is stored as a zero point, and the electrolytic ozone is used. After the ozone water producing operation of the water producing apparatus (10) is started, the concentration of ozone water supplied from the apparatus (10) to the measuring cell (3) is measured with reference to the zero point. Characteristic continuous measurement method of ozone water concentration . 2. The continuous ozone water concentration measuring method according to claim 1, wherein the ozone water concentration measurement after the start of the ozone water production operation is started after a lapse of a predetermined time after the start of the operation. 3. The zero point is corrected by measuring an environmental temperature in the vicinity of an ultraviolet ray generator that makes an ultraviolet ray incident on the measuring cell (3) and corrects the zero point according to a change in the environmental temperature. Continuous measurement method of ozone water concentration. 4. A UV lamp (1) for generating ultraviolet rays,
A stabilizing power source (2) for generating a predetermined ultraviolet ray from the UV lamp, and an ultraviolet ray from the UV lamp (1) that is transmitted and electrolyzes water to generate ozone water on the anode side.
Measuring cell (3) for continuously passing ozone water supplied from the electrolysis type ozone water producing apparatus (10), and an ultraviolet sensor (4) for measuring the intensity of transmitted ultraviolet light transmitted through the measuring cell (3) And a computer (7) that calculates the concentration of ozone water based on the intensity of the transmitted ultraviolet light. The computer (7) includes a computer (7) immediately before the ozone water production operation by the electrolytic ozone water production apparatus (10). Zero point storage means for storing only the raw water through the device and storing the ozone water concentration calculated based on the transmitted ultraviolet intensity measured by the ultraviolet sensor (4) as a zero point, and the zero point as a reference And an ozone water concentration calculating means for calculating the concentration of ozone water supplied from the device (10) to the measurement cell (3) after the ozone water producing operation of the electrolytic ozone water producing device (10) is started. Tena A continuous ozone water concentration measuring device characterized by 5. A logarithmic amplifier (6) after a voltage signal set in proportion to the transmitted ultraviolet intensity transmitted from the ultraviolet sensor (4) to the computer (7) is amplified by a preamplifier (5). The continuous ozone water concentration measuring device according to claim 4, wherein the ozone water concentration is continuously transmitted to the computer (7). 6. A preamplifier (5) amplifies and transmits a voltage signal, which is set in proportion to the transmitted ultraviolet intensity and is transmitted from the ultraviolet sensor (4) to the computer (7). The ozone water concentration continuous measuring device according to claim 4. 7. A temperature measuring means (18) for measuring a temperature in the vicinity of the UV lamp (1) is provided, and the computer (7) is based on the temperature measured by the temperature measuring means (18). 7. The ozone water concentration continuous measuring apparatus according to claim 4, further comprising a zero point correcting means for correcting the zero point. 8. Ozone water supplied from the electrolytic ozone water producing apparatus (10) is separated into a gas phase component through a gas-liquid separator (9), and only the liquid phase component is stored in the measurement cell (3). The ozone water concentration continuous measuring device according to any one of claims 4 to 7, which is configured to supply the ozone water concentration. 9. measuring cell (3) continuously while measuring the concentration of ozone water with an ozone water continuously by transmitting ultraviolet while passing water based UV absorption by ozone in the water
In electrolysis to operation control method of an ozone water production apparatus for performing operation control of the electrolytic ozone water production apparatus (10) for producing ozone water on the anode side, the ozone water by the electrolytic ozone water production apparatus (10) Immediately before the production operation, only the raw water is passed through the device to measure the transmitted UV intensity of the raw water that is supplied from the device (10) to the measurement cell (3) and contains substantially no ozone. Then, the ozone water concentration calculated by the computer (7) based on the transmitted ultraviolet intensity is stored as a zero point, and the ozone water production operation of the electrolytic ozone water production apparatus (10) is started from the apparatus (10). The concentration of ozone water supplied to the measuring cell (3) is calculated by the computer (7) based on the transmitted ultraviolet intensity with reference to the zero point, and the ozone water concentration is Based on the change in the electrolytic ozone water production apparatus (10) electrolytic <br/> ozone water production apparatus is generated ozone water concentration by changing the operating conditions and controls so as to be a predetermined range Operation control method. 10. The electrolytic type ozone water producing apparatus (10)
10. The operation control method for an electrolytic ozone water producing apparatus according to claim 9, wherein the controlled operating condition is 1 or more of a current value, a voltage value, a raw water supply amount, and a pressing force of the electrode with respect to the solid polymer electrolyte membrane. 11. The electrolytic ozone water producing apparatus (10)
Before a production run of the ozone water by, and determines whether or not the setting of the zero point has been made, if the zero-setting has been made, the electrolytic apparatus of the electrolytic ozone water production apparatus to determine this The operation control method for an electrolytic ozone water production apparatus according to claim 10, wherein energization is started. 12. An operation control device for continuously measuring the ozone concentration in ozone water by an ultraviolet absorption method, and controlling the operation of an electrolytic ozone water producing device (10) by the ozone absorption method. And an ozone water concentration measuring means (M) that transmits ultraviolet rays and calculates the ozone concentration based on the amount of ozone absorbed by the ozone, and the apparatus just before the ozone water production operation by the electrolytic ozone water production apparatus (10). The concentration of ozone water in the raw water that is substantially free of ozone that has been passed through is measured by the ozone concentration measuring means (M), and the measured value is set as a zero point of the ozone concentration and stored. Zero point storing means and zero setting confirming means (6
2), when the zero point setting is confirmed, energization starting means (65) for starting energization to the electrolyzer of the electrolytic ozone water producing apparatus, and the concentration of ozone water produced by the electrolytic ozone water producing apparatus (10) Is continuously measured by the ozone concentration measuring means (M), and a concentration determining means (68) for determining whether or not the measured ozone water concentration is within a predetermined range.
And a limit determination means (69) for determining whether or not the control element to be controlled is within the control limit when the concentration determination means (68) determines that the concentration is out of the predetermined range, and the limit determination When the control element determines that the control element is within the control limit, the control signal output means (70) that outputs a predetermined control signal, and the limit determination means (69) controls the control element to the control limit. When it is determined that the temperature has reached the limit, the electrolysis is characterized in that the solid polymer electrolyte membrane of the electrolytic ozone water producing apparatus is moved to a preset step (72) such as regeneration treatment. Operation control device for the ozone water production system. 13. The control element is a current value, a voltage value, a raw water supply amount, a pressing force of an electrode against a solid polymer electrolyte membrane, and one or more of these is controlled within a predetermined range. Item 13. An operation control device for an electrolytic ozone water production device according to item 12. 14. The ozone concentration measuring means (M) is used until a predetermined time (ts) elapses after the production of ozone water by the electrolytic ozone water producing apparatus is started by the energization starting means. The measurement prohibition means (66) for prohibiting measurement of ozone water concentration is provided.
The operation control device of the electrolytic ozone water production device according to item 1.