JP2001255271A - Ozone water concentration continuous measuring method and its device and operation control method and device of ozone water manufacturing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ozone water concentration measuring technology having a simple structure. SOLUTION: In this ozone water concentration continuous measuring method, ozone water is made to flow continuously into a measuring cell 3, and simultaneously an ultraviolet ray is transmitted, and the ozone water concentration is measured based on the ultraviolet ray absorption quantity by ozone. In the method, just before manufacturing operation of ozone water by an ozone water manufacturing device 10, only raw water is made to flow into the device, and the ultraviolet ray absorption quantity of the raw water including no ozone substantially supplied to the measuring cell 3 is measured, and the obtained ozone water concentration is memorized as a zero value, and after start of ozone water manufacturing operation, the ozone water concentration is measured by using the zero value as the standard.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for continuously measuring the concentration of ozone water in an apparatus for producing ozone water which mainly produces ozone water by electrolysis of water, the apparatus, and an apparatus for producing ozone water using the method for measuring ozone water. More specifically, the present invention relates to a simple ozone water concentration measurement system.

[0002]

2. Description of the Related Art There are several methods for measuring ozone, but an ultraviolet absorption method is generally used as an on-line measurement method used in an ozone water producing apparatus. This ultraviolet absorption method utilizes the characteristic that ultraviolet light having a wavelength of 254 nanometers (nm) is absorbed only by ozone molecules and not absorbed by other molecules. The ultraviolet absorption amount and the ozone concentration are expressed by the following equation (1) according to Lambert-Beer's law. Io = Ii × exp (-kcd) (1) where I0 is the transmission intensity of ultraviolet rays, Ii is the incident intensity of ultraviolet rays, and k is absorption. Degree coefficient (depends on the measurement wavelength and the measurement object) c: Ozone concentration d: Thickness of measurement ozone layer In the above formula (1), the measurement object is ozone water, and 2
Absorbance coefficient (k) if the measurement wavelength is 54 nm ultraviolet light
Is a constant, the layer thickness (d) of the ozone water is a constant determined by the measuring device, and since the incident intensity (Ii) of the ultraviolet light is also a value determined by the ultraviolet generating device, the transmission intensity (Io) of the ultraviolet light is It can be seen from the measurement that the ozone concentration (c) in the ozone water can be obtained by calculation.

[0003] However, in the case of a continuous type ozone water concentration measuring device which is attached to an ozone water producing device and measures ozone water, the ultraviolet light is deteriorated due to deterioration of a light source (ultraviolet ray generating device) and an ultraviolet ray detector during continuous measurement. Incident intensity (Ii
) And the transmission intensity (Io) change with time, so that their correction is necessary.

Therefore, as a method of this correction, the transmitted ultraviolet intensity is measured using a comparative sample whose ozone water concentration is known, and the transmitted ultraviolet intensity is compared with the transmitted ultraviolet intensity of the measurement sample. A method for stably measuring the water concentration has been proposed. That is, Is is the transmitted ultraviolet intensity when the measured ozone water is passed through the measurement cell, In is the transmitted ultraviolet intensity when the non-ozone water containing no ozone water is passed through the measurement cell, and the logarithm of the ratio is E. When, from the equation (1), E = log (is / In ) = logIs - logIn = log ((Ii × exp (-kcd)) / logI i) = logIi -kcd- logIi = kcd ............ Equation (2) As is apparent from equation (2), according to this method, the intensity of the incident ultraviolet light (Ii) due to the deterioration of the ultraviolet ray generator and the ultraviolet ray detector is canceled, and the change with the passage of time. To eliminate the effects of Therefore, the above measured Is
By calculating the logarithmic value of In and In and dividing this by k × d, the ozone water concentration c can be obtained stably.

FIG. 7 is a conceptual diagram showing this method, in which a UV light connected to a stabilizing power supply 2 for stably generating a predetermined 254 nm ultraviolet ray (hereinafter simply referred to as an ultraviolet ray).
The ultraviolet light generated by 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 the non-ozone water is passed, and the ozone water for measurement is passed. The ultraviolet light transmitted through the measuring cell 3 is detected by an ultraviolet sensor 4 and transmitted as an electric signal as a transmitted ultraviolet intensity Is through a preamplifier 5 and a logarithmic amplifier 6 to a computer unit (CPU) 7. The ultraviolet light transmitted through the comparison cell 3 ′ through which water is passed is:
Similarly, an electric signal is transmitted to the CPU 7 through the preamplifier 5 'and the logarithmic amplifier 6' as the transmitted ultraviolet intensity In detected by the ultraviolet sensor 4 '.
Is calculated and the ozone water concentration c is calculated by dividing by k × d, and the ozone concentration of the ozone water is displayed on the display 8 in a digital or analog manner.

Another method is to control the intensity of the ultraviolet light emitted from the UV lamp 1 to be always constant.
This example is shown in FIG. In FIG. 1, ultraviolet light emitted from a UV lamp 1 is reflected by a half mirror 20.
The ultraviolet light directed to the measurement cell 3 and the ultraviolet light directed to the comparison sensor 21 are equally divided, the intensity of the incident ultraviolet light is detected by the comparison sensor 21, and the intensity is converted into an electric signal to be converted into a preamplifier 22.
, And is input to the comparison circuit 23. In the comparison circuit, the power is compared with the initial intensity of the incident ultraviolet light, and the power supply 2 'is controlled so that the intensity of the incident ultraviolet light is constant. As a result, the incident intensity of the ultraviolet light incident on the measurement cell 3 is UV
The ozone water concentration is stably measured regardless of the temporal change of the lamp 1 so that the ozone water concentration can be stably measured.

[0007]

By the way, in the method shown in FIG. 7, two measuring systems, namely, two measuring systems, are used.
Two cells 3, 3 ', two preamplifiers 5, 5' and two
Two logarithmic amplifiers 6, 6 'are required, and the ozone water concentration measurement system becomes expensive. As a result, in the ozone water generator equipped with the ozone water concentration measurement device,
The ratio of the ozone water concentration measurement device in the price was a considerable part, and was unreasonable as an ozone water generation device. In addition, the non-ozone water must be constantly passed through the comparison cell 3 ', and the raw water softened for the production of ozone water is wasted. Furthermore, it is premised that the contamination of the measurement cell 3 passing the ozone water and the comparison cell 3 ′ passing the non-ozone water progress equally, but when the contamination degree of both cells is different, In principle, it was unavoidable that an error would occur. When a difference occurs in the degree of deterioration of the ultraviolet sensors 4, 4 ', an error similarly occurs in the measured value.

On the other hand, in the system shown in FIG. 8, the transmitted ultraviolet intensity measuring system is simplified to only one system, which contributes to cost reduction by that amount. The comparison sensor 21, the preamplifier 22, and the comparison circuit 23 are required, and there is a limit in cost reduction.

As a result, it is no exaggeration to say that the high price of the ozone water concentration measuring apparatus has hindered the spread of the ozone water producing apparatus, and it is a simple and inexpensive ozone water concentration apparatus which can be incorporated in the ozone water producing apparatus. At present, there is a need for a measurement system. In view of the above situation, an object of the present invention is to provide an inexpensive method for continuously measuring ozone water concentration with a simple configuration. The purpose is to enable control of the device.

[0010]

SUMMARY OF THE INVENTION The present invention has been made on the basis of the above-mentioned point of view, and it is characterized by transmitting ultraviolet light while continuously passing ozone water through a measuring cell. In an ozone water concentration continuous measurement method for measuring ozone water concentration based on the amount of ultraviolet light absorbed by ozone, in the ozone water production device, immediately before the operation of producing ozone water, only raw water is passed through the device. The apparatus is configured to measure an ultraviolet absorption amount of the raw water substantially free of ozone supplied to the measurement cell, store the obtained ozone water concentration as a zero point, and store the ozone water in the ozone water production apparatus. The point is that the concentration of ozone water supplied from the apparatus to the measurement cell after the start of the production operation is measured based on the zero point. That is, just before the operation of the ozone water producing apparatus, only the raw water is passed, and ozone-free water containing substantially no ozone is discharged from the ozone water outlet of the apparatus. Measure the concentration,
Since the measured concentration of the ozone-free water is set to a zero point, and after the start of the ozone water production operation, the concentration of the generated ozone water is continuously measured based on the zero point. This system enables continuous measurement of ozone water using only the system.

It is preferable that the measurement of the ozone water concentration after the operation of the ozone water producing apparatus is started is started after a certain time has passed since the start of the ozone water producing apparatus. It is possible to prevent the unstable operation of the device control system due to the measurement of the ozone water concentration under the condition where the water concentration is unstable.

Further, since the intensity of the ultraviolet ray generated by the ultraviolet ray generator varies somewhat depending on the environmental temperature of the ultraviolet ray generator, it is preferable to measure the environmental temperature to correct the zero point. is there.

Next, as an apparatus for continuously measuring ozone water concentration according to the present invention, a UV lamp for generating ultraviolet rays,
A stabilized power supply for generating predetermined ultraviolet light from the lamp, a measurement cell that transmits ultraviolet light from the UV lamp and continuously passes ozone water supplied from an ozone water production device, and a measurement cell. An ultraviolet sensor for measuring the intensity of the transmitted ultraviolet light, and a computer for calculating the ozone water concentration based on the transmitted ultraviolet light intensity. Zero-point storage means for performing only water passage, and storing the ozone water concentration calculated based on the transmitted ultraviolet light intensity measured by the ultraviolet sensor as a zero point,
Ozone water concentration calculating means for calculating the ozone water concentration after the start of the ozone water production operation of the ozone water production apparatus based on the zero point. With this configuration, the ozone water concentration can be continuously measured by one system of the transmitted ultraviolet intensity measurement system.

A voltage signal set in proportion to the intensity of the transmitted ultraviolet light transmitted from the ultraviolet sensor to the computer is amplified by a preamplifier and then transmitted to the computer via a logarithmic amplifier. There is a method in which the signal is amplified and transmitted to the computer without passing through the logarithmic amplifier.In the latter case, the logarithmic amplifier is omitted by adopting a simple method in which the exponential function is linearly approximated and the approximate value is calculated in the computer. There are advantages that can be done.

[0015] Further, a temperature measuring means for measuring a temperature near the UV lamp is provided, and the computer has a zero point correcting means for correcting the zero point based on the environmental temperature measured by the temperature measuring means. It is also a preferred embodiment to provide.

Further, the ozone water supplied from the ozone water producing apparatus is first supplied to a gas-liquid separator to separate a gas phase component, and only the liquid phase component is supplied to the measurement cell. Is a preferable method because the ozone concentration in the ozone water is accurately measured.

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

The operation control device of the ozone water producing apparatus according to the present invention includes an ozone water device that continuously transmits ozone water, transmits ultraviolet light, and calculates an ozone concentration based on an amount of absorbed ultraviolet light by ozone. The ozone water concentration of the raw water substantially free of ozone passed through the concentration measuring means and the ozone water producing apparatus by the electrolytic ozone water producing apparatus immediately before the operation is measured by the ozone concentration measuring means. Zero point storage means for setting and storing the measured value as a zero point of the ozone concentration; zero setting confirmation means for confirming the presence / absence of the zero point setting; and The energization start means for starting energization of the electrolysis apparatus of the water production apparatus and the ozone water concentration generated by the ozone water production apparatus are continuously measured by the ozone concentration measurement means. Concentration determining means for determining whether or not the measured ozone water concentration is within a predetermined range; and when the concentration determining means determines that the concentration is outside the predetermined range, the control element to be controlled is a control limit. 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 determination means; When it is determined by the determining means that the control element has reached the control limit, the process shifts to a preset process such as a regeneration process for the solid polymer electrolyte membrane of the electrolytic ozone water producing apparatus. It is. The control element includes a current value,
There are 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.

After the production of the ozone water by the ozone water producing apparatus is started by the energization starting means, a measurement inhibiting means for inhibiting the measurement of the ozone water concentration by the ozone concentration measuring means until a predetermined time elapses. It is also a preferable embodiment that the provision of such an arrangement prohibits control under unstable conditions at the beginning of the production of ozone water.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. FIG. 1 is a system diagram showing an embodiment of a method for continuously measuring ozone water concentration according to the present invention. In the figure, prior to the operation of the electrolytic ozone water producing apparatus 10, all the measuring instruments of the ozone water concentration measuring apparatus M are started up to be in a measurable state.
From 5, supply of raw water subjected to water softening is started. At this time, only the water flow line of the ozone water production device 10 is operating, and no electricity is supplied for electrolysis. Therefore, the water discharged from the ozone water discharge line 16 still contains ozone. And discharged in raw water. A part of the raw water (non-ozone water) is branched to the measurement line 11 and supplied to the gas-liquid separator 9. At this stage, since the gas supplied to the water supplied from the line 11 contains no 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, the gas is discharged from the discharge line 14 through the upper chamber 9a of the gas-liquid separator 9 to the outside of the apparatus.

In the measuring cell 3, the ultraviolet rays incident from the UV lamp 1 pass through the raw water flowing through the cell 3, but do not contain ozone. The transmitted ultraviolet light sensor 4 detects the transmitted ultraviolet light intensity at the same level as the incident ultraviolet light intensity, converts the transmitted ultraviolet light intensity into an electric signal, and transmits the electric signal to the computer unit (CPU) 7 via the preamplifier 5 and the logarithmic amplifier 6 to obtain the above equation. Ozone water concentration (c) = 0 based on (1)
Is calculated as From this calculation result, the intensity of the incident ultraviolet light (Ii) is determined as the intensity of the transmitted ultraviolet light (Io) = the intensity of the incident ultraviolet light (Ii). That is, the transmitted ultraviolet light intensity (Io) corresponding to the incident ultraviolet light intensity (Ii) is used as a reference as the zero point of the ozone water concentration.

This reference setting (zero point setting) is performed immediately before the start of the ozone water production operation of the ozone water production apparatus 10, that is,
Before the energization operation, the flow is performed by passing only the raw water substantially free of ozone, and the density is measured about 100 times per second, and the average value is taken to smooth the noise. In addition, the average value calculation is repeated a plurality of times to further calculate the average value, thereby improving the zero point setting accuracy. Therefore, several tens of seconds are sufficient as the zero point setting time. In this sense, when the power of the apparatus is turned on, only the ozone water concentration measuring apparatus M first starts up, and when the apparatus is in a measurable state, only the flow of water is started, and the above-described zero point setting is performed. When the process is completed, a series of steps can be automatically controlled by the CPU 7 so that the electrolysis apparatus is energized and the production of ozone water is started.

Next, when the above-mentioned standard setting is completed, the energization of the ozone water producing apparatus 10 is started, the production of ozone water by electrolysis is started, and the generated ozone water is discharged from the line 16. Most of this ozone water is sent to the demand destination from the supply line 17, but part of the ozone water is sent to the lower chamber 9 b of the gas-liquid separator 9 divided into the upper chamber 9 a and the lower chamber 9 b via the line 11. Be paid. In the case of the electrolytic ozone water producing apparatus, the ozone water supplied from the line 11 is a gas-liquid multiphase flow in which oxygen generated by the electrolysis of water and undissolved ozone gas are slightly contained. When supplied to the measurement cell 3, ozone in the gas phase also absorbs ultraviolet light, and the amount of ultraviolet light absorbed by ozone in ozone water cannot be accurately measured due to irregular reflection of ultraviolet light by bubbles. Therefore, in the present invention, by flushing the gas into the gas-liquid separator 9, the gas phase component is discharged from a gas hole 9d formed in a partition wall 9c defining an upper chamber 9a and a lower chamber 9b by an ejector action described later. Inhaled into the upper chamber 9a,
Only the liquid phase component flows into the measuring cell 3 via the line 12.

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

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

It should be noted that the intensity of the ultraviolet light generated by the UV lamp 1 varies slightly depending on the environmental temperature T near the UV lamp 1. That is, the incident ultraviolet intensity Ii is represented as a function of the ambient temperature T, "Ii = f (T)". Therefore, when the environmental temperature T is measured by the temperature measuring device 18 and transmitted to the CPU 7 as an electric signal, and the CPU 7 performs a function operation of Ii = f (T), the zero point is set. It is also possible to perform the temperature correction of the set zero point by the change with the temperature of, but the zero point setting is performed at the time when the UV lamp is stabilized, and even during the stop of the ozone water producing apparatus. This is not always necessary when a system that does not change the environmental temperature of the UV lamp 1 is employed.

FIG. 2 is a flowchart showing another embodiment of the ozone water concentration measuring method according to the present invention. The difference from FIG. 1 is that the electric signal input to the CPU 7 is 1 is logarithmically converted by the logarithmic amplifier 6 and input, whereas the method of FIG. 2 is different only in that the input is made while being amplified by the preamplifier 5, and other configurations are the same. Therefore, only the following differences will be described, and the same components will be denoted by the same reference numerals and detailed description thereof will be omitted.

As is apparent from the above equation (1), the relationship between the ozone concentration and the intensity of transmitted ultraviolet light is in an exponential relationship. Therefore, even if the transmitted ultraviolet light intensity is converted into a voltage signal as an electric signal proportional to the transmitted ultraviolet light intensity, the relationship between the voltage (V) and the ozone concentration (x) is an exponential relationship.
This exponential relationship is converted into a linear relationship (primary expression relationship) by a logarithmic amplifier 6 and input to a CPU 7, which calculates an ozone concentration corresponding to the input voltage value based on a previously programmed primary expression. It is supposed to. On the other hand, in the system of FIG. 2, the logarithmic amplifier 6 is omitted, so that the input voltage (V) and the ozone concentration (X)
Has an exponential function relationship as shown in FIG. Therefore, this exponential function is approximated by a straight line (linear expression), and the approximate expression is stored in the CPU 7, and when the input voltage value is equal to or more than V1 (V ≧ V1).
Calculates the ozone concentration by the equation (V = aX + b), and when the input voltage value is equal to or more than V2 and less than V1, (V
For 2 ≦ V <V1, the ozone concentration is calculated by the equation (V = a′X + b ′). When the input voltage value is less than V2 (V <V2), the equation (V = a ”X + b”) is calculated. By calculating the ozone concentration according to (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 this approximate value calculation is performed, there is no practical problem at all in the range where it is used for normal sterilization and cleaning, except for special cases such as a test requiring a strict ozone water concentration.

In the present invention, it is also possible to control the operation of the ozone water producing apparatus based on the calculation result of the ozone concentration in the CPU 7. Therefore, first, the 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-11-172.
No. 4832 and the like, and the structure thereof is not particularly limited, but an example is shown below.

FIG. 4 is a sectional view of an essential part showing an example of an electrolytic ozone water producing apparatus used in the present invention. In FIG. 4, the ozone water producing apparatus is made of a fluorine resin or a resin 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 whose inner surfaces are coated with glass or the like. 3
1 and the inside of the cathode side casing 32 are divided into an anode chamber 36 and a cathode chamber 37.
And it is defined. On the surface of the electrolyte membrane 35 on the anode chamber 36 side, an anode electrode 33 provided with a noble metal catalyst 46 such as platinum having a catalytic 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. An inlet 38, 39 and an outlet 40, 41 of raw water are formed in the anode chamber 36 and the cathode 37, respectively. A direct-current voltage is applied via the. Each of the electrode rods 49 and 53 is disposed so as to pass 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, electrolyte membrane 3
5, the pressing force of the electrode surface against the electrolyte membrane 35 can be adjusted freely.

In the apparatus having the above configuration, when water is supplied to the anode chamber 36 and the cathode chamber 37 and a DC current is applied between both electrodes, electrolysis of water occurs with the electrolyte membrane 35 interposed therebetween. Generates ozone, and hydrogen is generated on the cathode electrode 34 side. The ozone generated on the anode electrode 33 side 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, the portions of both electrodes 33 and 34 that are in contact with the electrolyte membrane 35 are disclosed in Japanese Patent Application Laid-Open No. 8-134677.
Wire meshes 46 and 50 made of noble metals are respectively provided, and lath meshes 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 of the wire mesh and brazed. The electrode structure has an integrated structure. As a result, the raw water generates a violent turbulence and a vortex while flowing 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 generation, and the high concentration Ozone water is obtained.

When producing ozone water using such a device, the operation is generally 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 decreases as the operation continues, and the following method is used to compensate for this and control the ozone water concentration to be within a predetermined range. (1) The current value control method is a method of continuously measuring the concentration of ozone water, and when reaching a lower limit value of a predetermined concentration range, gradually increasing the current value until reaching a predetermined upper limit value to promote ozone generation. . (2) The pressing force change method measures the ozone water concentration continuously, and when it reaches a lower limit value of a predetermined concentration range, gradually increases the pressing force of the electrode against the electrolyte membrane 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 a method used in combination with the above current value control method.

Further, the electrolyte membrane itself gradually deteriorates during use, so that it is necessary to periodically regenerate the electrolyte membrane. As the reproduction processing method, there is the following method. (A) As a result of the continuous operation of the electrolyte membrane regeneration method (1) or (2), when the control method reaches the 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 and regenerate. (B) The pressing force change method is a short time (about several seconds) that does not affect the discharged ozone water concentration every time the operation time elapses from 10 to 20 minutes or when the ozone water concentration reaches a predetermined lower limit. In this method, a change in pressing force for releasing / pressing the pressing force of the electrode 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 of using this method in combination with the above (1) and (2) to dramatically increase the continuous operation time.

In the present invention, among these control operations, the control operation performed based on the ozone water concentration is the above-mentioned CP operation.
Based on the calculation result of the ozone water concentration performed in U7, the CP
It is possible to output a control signal from U7 to the electrolytic ozone water producing apparatus. The control elements include a current value (current density) and a voltage value (the current increases as the voltage increases, the same as the current value control). Significance), there is a pressing force on the electrolyte membrane of the electrode.

Next, a control example of the electrolytic ozone water producing apparatus according to the present invention will be described with reference to FIG. FIG.
This shows an example of the control flow of the electrolytic ozone water producing apparatus according to the present invention. First, when the power of the apparatus is turned on and started, as shown in a block 61, the 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 at this time, the electrolysis apparatus is not energized. Next, it is determined by the zero setting confirmation means whether the zero point setting (reference setting) of the ozone water in the measurement system is performed (S2). At the start of normal operation, the zero point has not been set as described above (S2, NO). Therefore, an ozone concentration measurement is performed on raw water that is non-ozone water (S3), and the measured concentration of the ozone-free water is set to zero. Zero point setting for the point is performed (S4), and the preparation for measuring the ozone water concentration is completed. When the preparation for measuring the ozone water concentration is completed, energization of the electrolysis apparatus is started to start production of ozone water (S5).

In S2, when the zero point setting is completed (S2, YES), that is, after the stop period of the device due to the temporary stop of the current supply for the electrolyte membrane regeneration, the control of the device is completed. In the process, when the device is restarted after operation stop, the control system itself is continuously operating,
Since there is no need to set the zero point again, the energization of the electrolytic 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 determination means sets the predetermined time ts for which the elapsed time is set in advance. It is determined whether or not it has passed (S6),
When it is determined that the elapsed time t has reached a predetermined time or longer (t ≧ ts) (S6, YES), continuous measurement of the ozone water concentration is started in the manner described above (S7). This is because, at the beginning of the operation of the ozone water producing apparatus, the ozone water concentration is in a rising process but is in an unstable state, so that it is inappropriate to measure this state and control the apparatus. .
Therefore, for a certain period of time (for example, 10 seconds to several minutes) until the ozone water concentration is stabilized, a measurement prohibition period in which ozone water measurement is not performed is provided.

When the ozone water concentration is continuously measured, the value is sent to the next concentration judging means 68, where the ozone water concentration (X) is set to a predetermined allowable concentration range (Xmin ≦ X ≦ Xma).
x) is determined (S8), and if it is within the allowable range (S8, YES), the process returns to the ozone water concentration measurement (S7). When it is determined that the ozone water concentration is out of the predetermined allowable range (S8, NO), control for changing the operating conditions is performed to return the concentration to within the predetermined range.
Before that, it is judged by the limit judging means 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), and after performing predetermined control based on the signal (S11), the flow again shifts to the measurement of the ozone water concentration (S11). S7).

In S9, the case where the control limit has been reached means that in the case where the current value is increased in response to the decrease in the ozone water concentration due to the decrease in the performance of the electrolyte membrane, the current value is already in the device. Control when the current value cannot be increased any more, and the pressing force of the electrode against the electrolyte membrane is increased in response to the decrease in the concentration of ozone water due to the decrease in the performance of the electrolyte membrane. In this case, the pressing force has already reached the upper limit of the apparatus, and it is not possible to further increase the pressing force. In such a case, the limit determining means determines that the control element has reached the control limit (S9, YES), and shifts to the next step set in advance. The next step includes a case where the operation of the apparatus is stopped to regenerate the electrolyte membrane, a case where the pressing force of the electrode against the electrolyte membrane is released for a predetermined time to regenerate the electrolyte membrane, or the like. Is performed, and then the process returns to S1 and restarts.

[0041]

Next, an embodiment of the present invention will be described. The ozone water concentration measuring apparatus shown in FIG. 2 is attached to the electrolytic ozone water producing apparatus shown in FIG. 4, and the conventional ozone water concentration measuring apparatus shown in FIG. 8 is attached externally for comparison. Ozone water concentration measurement test was performed. First, in the method of the present invention, prior to the operation of producing ozone water, only the raw water is passed for about 2 minutes without power supply (without performing electrolysis) to the ozone water producing apparatus, and a zero point is set using ozone-free raw water. Thereafter, the ozone water production apparatus was energized to produce ozone water, the ozone water concentration was not measured for about 3 minutes after the start of the ozone water production operation, and the ozone concentration measurement was started about 3 minutes later. Incidentally, the ozone water concentration measurement was carried out from the beginning in the external conventional ozone water concentration measurement device. FIG. 6 shows the measurement results by both methods.

In FIG. 4, the intensity of transmitted ultraviolet light is converted into a voltage proportional to the value and is displayed. The higher the voltage value, the smaller the ultraviolet absorption (the smaller the ozone content). In the figure, t1 is a period during which only raw water flows (about 2 minutes), and the voltage output corresponding to the transmitted ultraviolet intensity during this period is 2.8 to 3.0 V. Based on the method of the present invention, a zero point is set. When the energization of the electrolysis apparatus is started after the passage of t1, the external measuring apparatus (conventional method) rapidly increases the ozone water concentration along with the start of the energization, and at the same time,
The output voltage corresponding to the transmitted ultraviolet intensity is 0.2 to 0.3.
V rapidly. The time t2 (approximately 3 minutes) after the start of energization of the electrolysis apparatus is a period during which the measurement of the ozone water concentration according to the method of the present invention is prohibited. The concentration is 17p
It can be seen that a level value of about pm is detected. As is clear 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 very similar. In addition, the measured value according to the method of the present invention has a variation of about 1 ppm compared to the measured value according to the conventional method. However, at the level where ozone water is used for normal sterilization and cleaning, there is no problem at all. confirmed. In this sense, it is also understood that the operation control of the ozone water producing apparatus can be performed based on the ozone water concentration measured by the ozone water concentration measuring method of the present invention.

[0043]

As described above, in the present invention, since the ozone concentration is measured only by one series of ozone water concentration measuring systems, only one measuring cell is required. Therefore, as compared with the conventional method using two cells shown in FIG. 7, not only does it contribute to cost reduction, but also in the conventional method, water having different properties is distributed to each cell.
During use, dirt gradually accumulates on the inner surface of the cell, and since the degree of dirt is different, the degree of absorption of ultraviolet light by dirt also changes, so that errors gradually occur in the comparison of the transmitted ultraviolet intensity of both cells. However, in the present invention, 1
Since only one measurement cell is used, even if dirt is generated on the inner surface of the cell, the influence of the transmitted ultraviolet intensity due to the dirt is the same under both the reference value setting and the ozone water measurement. It has become difficult. In this sense,
Reliability in long-term homes will be improved.

Also, as compared with the conventional method shown in FIG.
It is the same in that one cell is used, but the method of the present invention does not require an expensive half mirror, and requires only one ultraviolet sensor and further eliminates the need for a comparison circuit, thus significantly reducing cost. Becomes possible.

As described above, in the method of the present invention, the ozone concentration can be measured with only one series of measurement systems, so that the ozone water concentration measuring device can be supplied at a lower cost than the conventional method. . As a result, it can be used as an extremely effective measuring device as an online measuring device attached to the ozone water producing device, and is expected to greatly contribute to cost reduction of the ozone water producing device.

As a result of reducing the cost of the ozone water producing apparatus, it becomes possible to supply the ozone water producing apparatus to the market at a low cost, and the use of ozone water is dramatically spread in 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 beforehand, and will greatly contribute to the health and safety management of the people.

[Brief description of the 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. 2;

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 flowchart showing a control example of the electrolytic ozone water producing apparatus according to the present invention.

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

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

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 UV lamp 2 Power supply for UV lamps 3, 3 'Cell for measuring ultraviolet absorption 4, 4' Ultraviolet sensor 5, 5 'Preamplifier 6, 6' Logarithmic amplifier 7 CPU 8 Display 9 Gas-liquid separator 10 Ozone water producing apparatus

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C25B 15/02 302 C25B 15/02 302 G01N 21/33 G01N 21/33 F-term (Reference) 2G058 BA08 GA06 GB10 GD02 2G059 AA01 BB04 CC08 DD01 DD02 DD12 EE01 FF04 GG10 HH03 KK01 MM01 MM03 MM05 MM09 MM10 MM15 NN01 NN02 PP04 4D061 DB07 EA03 EB04 CA13 BC01 BC01 GC02 GC02 GC01 GC02 GC01 GC02 GC02 DB05 DB31 DB43 DC07

Claims (14)

[Claims] 1. An ozone water concentration continuous measurement method for measuring the concentration of ozone water based on the amount of ultraviolet light absorbed by ozone, wherein ultraviolet light is transmitted while continuously passing ozone water through a measurement cell (3). Immediately before the operation of producing ozone water by the ozone water producing device (10), substantially only ozone is supplied from the device (10) to the measuring cell (3) by passing only raw water through the device. Measuring the ultraviolet absorption amount of the raw water that has not been performed, storing the obtained ozone water concentration as a zero point, and starting the ozone water production operation of the ozone water production device (10) from the device (10) to the measurement cell. (3) A method for continuously measuring the concentration of ozone water, wherein the concentration of ozone water supplied is measured based on the zero point. 2. The method for continuously measuring ozone water concentration according to claim 1, wherein the measurement of the concentration of ozone water after the start of the operation for producing ozone water is started after a predetermined time has elapsed after the start of the operation. 3. The method according to claim 1, wherein an environmental temperature near an ultraviolet ray generator for injecting ultraviolet light into the measuring cell is measured, and the zero point is corrected by a change in the environmental temperature. Ozone water concentration continuous measurement method. 4. A UV lamp (1) for generating ultraviolet light,
A stabilized power supply (2) for generating a predetermined ultraviolet ray from the UV lamp and an ozone water which transmits the ultraviolet ray from the UV lamp (1) and is supplied from an ozone water producing apparatus (10) continuously. A measuring cell (3) for passing water, an ultraviolet sensor (4) for measuring the intensity of transmitted ultraviolet light transmitted through the measuring cell (3), and a computer (7) for calculating an ozone water concentration based on the transmitted ultraviolet light intensity. The ozone water producing apparatus (1) is provided in the computer (7).
Immediately before the production operation of ozone water according to 0), only the raw water is passed through the device, and the ozone water concentration calculated based on the transmitted ultraviolet intensity measured by the ultraviolet sensor (4) is stored as a zero point. Point storage means, and calculates the concentration of ozone water supplied from the device (10) to the measurement cell (3) after the operation of the ozone water production device (10) is started based on the zero point. An ozone water concentration continuous measuring device comprising an ozone water concentration calculating means. 5. A preamplifier (5) amplifies a voltage signal set in proportion to the transmitted ultraviolet light intensity transmitted from the ultraviolet sensor (4) to the computer (7), and then a logarithmic amplifier (6). The continuous ozone water concentration measuring apparatus 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 set in proportion to the transmitted ultraviolet intensity transmitted from the ultraviolet sensor (4) to the computer (7). The continuous measurement apparatus for ozone water concentration according to claim 4. 7. A temperature measuring means (18) for measuring a temperature in the vicinity of the UV lamp (1), wherein the computer (7) has a temperature based on the temperature measured by the temperature measuring means (18). The ozone water concentration continuous measurement apparatus according to any one of claims 4 to 6, further comprising a zero point correction means for correcting the zero point. 8. The ozone water supplied from the ozone water producing device (10) is separated into a gas phase component through a gas-liquid separator (9), and only the liquid phase component is supplied to the measurement cell (3). The ozone water concentration continuous measuring device according to any one of claims 4 to 7, wherein 9. An ozone water producing apparatus (10) which continuously transmits ozone water through a measuring cell (3), transmits ultraviolet light, and continuously measures ozone water concentration based on the amount of ultraviolet light absorbed by ozone. In the operation control method of the ozone water producing apparatus for performing the operation control of 10), the apparatus (10) is provided with only the flow of the raw water to the apparatus immediately before the operation of producing the ozone water by the ozone water producing apparatus (10). ), The transmitted UV intensity of the raw water substantially free of ozone supplied to the measuring cell (3) is measured, and the computer (7) is operated based on the transmitted UV intensity.
The ozone water concentration calculated by the above is stored as a zero point. The ozone water concentration supplied from the device (10) to the measurement cell (3) after the ozone water production operation of the ozone water production device (10) is started. The calculation is performed by the computer (7) based on the transmitted ultraviolet intensity with reference to the zero point, and the operating condition of the ozone water producing apparatus (10) is changed based on the change of the ozone water concentration. An operation control method for an ozone water producing apparatus, characterized in that the ozone water concentration is controlled to be within a predetermined range. 10. The ozone water producing apparatus is an electrolytic ozone water producing apparatus, and the controlled operating conditions include one of a current value, a voltage value, a raw water supply amount, and a pressing force of an electrode against a solid polymer electrolyte membrane. The operation control method for an ozone water producing apparatus according to claim 9, which is as described above. 11. The electrolytic ozone water producing apparatus (10).
Before the production operation of ozone water by the above, it is determined whether or not a zero point has been set, and if the zero point has been set, this is determined and the electrolytic device of the ozone water production device is energized. The operation control method for an ozone water producing apparatus according to claim 10, wherein the operation is started. 12. An operation control device for continuously measuring the ozone concentration in ozone water by an ultraviolet absorption method and thereby controlling the operation of the electrolytic ozone water production device (10). An ozone water concentration measuring means (M) for calculating the ozone concentration based on the amount of ultraviolet light absorbed by ozone while transmitting ultraviolet light, and the device immediately before the operation of producing ozone water by the electrolytic ozone water production device (10) The ozone water concentration of the raw water which does not substantially contain ozone 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 storage means, and zero setting confirmation means (6) for confirming whether or not the zero point is set.
2), when the zero point setting is confirmed, an energization start means (65) for starting energization of the electrolysis apparatus of the electrolytic ozone water producing apparatus, and an ozone water concentration generated by the electrolytic ozone water producing apparatus (10). Is continuously measured by the ozone concentration measuring means (M), and the concentration determining means (68) determines whether or not the measured ozone water concentration is within a predetermined range.
A limit determining means (69) for determining whether the control element to be controlled is within a control limit when the density determining means (68) determines that the control element is out of the predetermined range; When it is determined by the means (69) that the control element is within the control limit, the control signal output means (70) for outputting a predetermined control signal, and the control element is controlled by the limit determination means (69). If it is determined that the temperature has reached the predetermined value, the process proceeds to a preset process (72) such as a regeneration process for the solid polymer electrolyte membrane of the electrolytic ozone water producing apparatus. 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 are controlled within a predetermined range. Item 13. An operation control device for an electrolytic ozone water producing apparatus according to Item 12. 14. After the production of ozone water by the ozone water production device is started by the energization start means, the ozone water concentration is measured by the ozone concentration measurement means (M) until a predetermined time (ts) elapses. The operation control device of the electrolytic ozone water producing apparatus according to claim 12 or 13, further comprising a measurement inhibiting means (66) for inhibiting the measurement.