WO2023243535A1

WO2023243535A1 - Device for measuring hypochlorite concentration, and device for generating hypochlorite

Info

Publication number: WO2023243535A1
Application number: PCT/JP2023/021386
Authority: WO
Inventors: 弘士小原; 祥文渡部
Original assignee: パナソニックＩｐマネジメント株式会社
Priority date: 2022-06-17
Filing date: 2023-06-08
Publication date: 2023-12-21

Abstract

A hypochlorite concentration measurement device (100) for measuring the concentration of a hypochlorite produced by subjecting water containing chlorine to electrolysis in an electrolytic bath (210), said device being equipped with a measurement means (110) for measuring electric conductivity information, which expresses the electric conductivity of aqueous hypochlorite stored in the electrolytic bath (210), and a measurement control device (120) for controlling the measurement means (110), and being configured in a manner such that: the measurement control device (120) is equipped with a measurement information acquisition unit (121) for acquiring electric conductivity information, a conversion information acquisition unit (122) for acquiring conversion information, and a concentration calculation unit (123) for calculating the hypochlorite concentration on the basis of the measured electric conductivity information and the conversion information.

Description

Hypochlorous acid concentration measurement device and hypochlorous acid water generation device

The present invention relates to a hypochlorous acid concentration measuring device and a hypochlorous acid water generating device equipped with the hypochlorous acid concentration measuring device.

For example, Patent Document 1 describes a so-called ultraviolet absorption measurement technique that measures the concentration of hypochlorous acid water based on the absorption attenuation caused by the absorption of ultraviolet rays by hypochlorite ions.

Additionally, Patent Document 2 describes a so-called Polaro measurement technique that measures the concentration of hypochlorous acid water based on the electrochemical reduction current of hypochlorous acid.

Japanese Patent Application Publication No. 2000-343080 Japanese Patent Application Publication No. 2011-7508

In the ultraviolet absorption type measurement technology, the light source that emits ultraviolet light for measurement deteriorates in a relatively short period of time, and the measured value of the concentration of hypochlorous acid water fluctuates. Therefore, handling becomes complicated, as correction work is required to stabilize the measured values. Furthermore, the ultraviolet components are expensive, which poses a cost problem.

In the Polaro-type measurement technique, the measured value of the concentration of hypochlorous acid water fluctuates due to contamination of the electrodes used for measurement. For this reason, handling becomes complicated, such as cleaning of the electrodes, etc., in order to stabilize the measured values. Since the material of the electrode is a noble metal, the measuring device itself is expensive and there is a cost problem.

As a result of intensive research and experiments based on the above-mentioned problem, the inventor discovered that the electrical conductivity of hypochlorous acid water, which can be stably measured, is a relatively accurate indicator of the concentration of hypochlorous acid water. Ta. The present invention was made based on the knowledge of the inventor, and provides a hypochlorous acid concentration measuring device, a space sterilization device, and a hypochlorous acid concentration measuring device that can measure the concentration of hypochlorous acid water with a simple configuration. The purpose is to provide a method for measuring acid concentration.

In order to achieve the above object, a hypochlorous acid concentration measuring device according to one aspect of the present invention measures the concentration of hypochlorous acid generated by electrolyzing chlorine-containing water stored in an electrolytic cell. A hypochlorous acid concentration measuring device for measuring, comprising a measuring means for measuring conductivity information indicating the conductivity of hypochlorous acid water stored in the electrolytic cell, and a measurement control device for controlling the measuring means. , the measuring means is configured to apply an AC voltage or an AC voltage with a predetermined AC cycle between a pair of measuring electrodes that are arranged in a separated state in the hypochlorous acid water stored in the electrolytic tank, and a pair of the measuring electrodes. an application measurement device that applies an alternating current; a conversion information acquisition unit that acquires conversion information indicating a relationship between the acid concentration and the conductivity information; and a conversion information acquisition unit that calculates the hypochlorous acid concentration based on the conductivity information corresponding to a plurality of alternating current cycles and the conversion information. and a concentration calculation unit that calculates the concentration.

Further, the hypochlorous acid water generating device according to one aspect of the present invention includes an electrolytic cell that stores water containing chlorine, an electrolytic electrode that is inserted into the electrolytic cell, and a voltage applied to the electrolytic electrode. an electrolysis device that applies chlorine and electrolyzes the water containing chlorine to generate hypochlorous acid water, the above-mentioned hypochlorous acid concentration measuring device, and a main control device that controls the electrolysis device. The measurement control device includes: an electrolysis execution acquisition unit that acquires execution information indicating execution of electrolysis; and an electrolysis execution acquisition unit configured to cause the measuring means to measure conductivity information when electrolysis is not being executed based on the execution information. a measurement instructing section to cause the electrolysis to be carried out; , an electrolysis control section that outputs electrolysis information such that the concentration of hypochlorous acid in the electrolytic cell becomes a target concentration to the electrolysis device, based on information on the hypochlorous acid concentration calculated by the concentration calculation section.

According to the present invention, hypochlorous acid concentration can be efficiently measured.

It is a figure showing a space sterilization device simply from the side. FIG. 2 is a block diagram showing the functional configuration of a measurement control device. It is a graph showing the relationship between the hypochlorous acid concentration and the conductivity of hypochlorous acid water during the generation period. It is a graph showing the relationship between the accumulation of differences in electrical conductivity during the generation period and the hypochlorous acid concentration. FIG. 2 is a block diagram of a liquid resistance value measuring circuit included in the measuring means. It is a flowchart showing the flow of the space sterilization device operation during the generation period of hypochlorous acid. It is a flow chart showing the flow of operation of the space sterilization device during the decay period of hypochlorous acid. It is a graph showing the relationship between the hypochlorous acid concentration and the conductivity of hypochlorous acid water in the decay period. It is a graph showing the relationship between the accumulation of differences in conductivity during the decay period and the hypochlorous acid concentration. FIG. 2 is a block diagram showing the functional configuration of a main controller. It is a graph showing temporal changes in hypochlorous acid concentration during the production period and the decay period. It is a graph which shows the relationship between the AC waveform on the output side detected by the liquid resistance value measuring device and the acquisition period. FIG. 3 is a diagram for explaining an update mode of an acquisition cycle. 2 is a graph showing temporal changes in hypochlorous acid concentration during a generation period for stabilizing the hypochlorous acid concentration and a decay period.

Hereinafter, embodiments of a hypochlorous acid concentration measuring device, a hypochlorous acid water generating device, a space sterilization device, and a hypochlorous acid concentration measuring method according to the present invention will be described with reference to the drawings. Note that the following embodiments are provided as an example to explain the present invention, and are not intended to limit the present invention. For example, the shapes, structures, materials, components, relative positional relationships, connection states, numerical values, formulas, contents of each step in the method, order of each step, etc. shown in the following embodiments are merely examples. It may contain content not listed. Furthermore, although geometric expressions such as parallel and perpendicular are sometimes used, these expressions do not indicate mathematical rigor and include substantially permissible errors, deviations, and the like. Furthermore, expressions such as "simultaneously" and "identical" also include a substantially permissible range.

Furthermore, the drawings are schematic diagrams with emphasis, omission, or ratio adjustment as appropriate to explain the present invention, and the actual shapes, positional relationships, and ratios differ from the drawings. Further, the X-axis, Y-axis, and Z-axis that may be shown in the drawings indicate orthogonal coordinates arbitrarily set for the purpose of explaining the drawings. In other words, the Z-axis is not necessarily an axis along the vertical direction, and the X-axis and Y-axis are not necessarily in a horizontal plane.

Further, below, multiple inventions may be comprehensively described as one embodiment. Further, some of the contents described below are explained as optional components related to the present invention.

Further, the flowchart is an example, and even if the process flow is different, such as a different order of processing, multiple processes being integrated, or one process being separated, it is included in the embodiment of the present invention.

FIG. 1 is a diagram simply showing the space sterilization device 200 from the side. The space sterilization device 200 releases at least hypochlorous acid in the hypochlorous acid water into the space. Moreover, the space sterilization device 200 introduces the atmosphere in the space into the hypochlorous acid water. The target space is a closed space such as an indoor space of a building. Specifically, examples of the space include a living space in a general home, an indoor space in a hospital or a nursing care facility, and the like. Note that the space does not need to be a completely closed space, and may be connected to the outdoors. Further, the space may be not only a space inside a building but also a space inside a moving body such as a train or a car.

Hypochlorous acid water has sterilization and deodorizing effects. Specifically, hypochlorous acid water has an oxidizing effect, and sterilizes and deodorizes by decomposing floating bacteria in the space, bacteria adhering to objects, or odor substances through oxidation. Note that the term "sterilization" is used for convenience in the present specification and claims, and includes meanings such as "sterilization." In addition, "bacteria" is described as including viruses, molds, etc.

As shown in FIG. 1, the space sterilization device 200 includes an electrolytic cell 210, an electrolytic electrode 220, an electrolytic device 230, a hypochlorous acid concentration measuring device 100, a diffusion means 240, and a main controller 250. , is equipped with.

The electrolytic cell 210 is a water tank that stores water containing chlorine, and hypochlorous acid water is generated by electrolyzing the water containing chlorine in the electrolytic cell 210. Examples of water containing chlorine include water in which salt is dissolved.

The electrolytic electrodes 220 are a pair of conductive members inserted into the chlorine-containing water stored in the electrolytic tank 210. Although the shape of the electrolytic electrode 220 is not particularly limited, in the case of this embodiment, it is a rectangular plate shape (band shape). The pair of electrolytic electrodes 220 are arranged so that their respective main surfaces (the surfaces with the largest area) face each other. The material of the electrolytic electrode 220 is not particularly limited as long as it is conductive. For example, the electrolytic electrode 220 may have a structure in which the surface of a conductive base material is coated with a catalyst layer. Examples of the conductive base material include simple metals such as titanium, iron, copper, niobium, and tantalum, or alloys thereof. In consideration of ease of processing during manufacturing or manufacturing cost, the material of the conductive base material is preferably titanium or a titanium alloy. The catalyst layer can be exemplified by a catalyst containing platinum, iridium, or the like. Other mixtures contained in the catalyst layer may be in any metal state such as metals, alloys, metal oxides, etc., such as lead, gold, nickel, copper, silver, iron, palladium, ruthenium, rhodium, carbon, etc. can be mentioned.

The electrolysis device 230 is a DC power supply device that applies a predetermined DC voltage between a pair of electrolysis electrodes 220. In the electrolytic device 230, whether or not to apply a voltage to the pair of electrolytic electrodes 220, that is, whether to apply voltage to the pair of electrolytic electrodes 220, is selected on or off under the control of the main controller 250.

The diffusion means 240 is a cylindrical member that rotates around the tube axis (in the left-right direction in FIG. The water is immersed in the hypochlorous acid solution, and the water is lifted above the level of the hypochlorous acid solution using capillary action. By passing air between the hypochlorous acid water lifted above the liquid level, at least the hypochlorous acid in the hypochlorous acid water is diffused into the atmosphere. Bacteria (including viruses, mold, etc.) existing in the atmosphere are sterilized (including inactivation of viruses, mold, etc.) by contacting with the hypochlorous acid water lifted up by the diffusion means 240. Bacteria can also be sterilized by contact with at least the hypochlorous acid in the hypochlorous acid solution diffused into the atmosphere.

Note that the diffusion means 240 is a device that atomizes the hypochlorous acid water in the electrolytic device 230 by centrifugal crushing or the like and releases it into the space, and diffuses at least the hypochlorous acid in the hypochlorous acid water into the space. It doesn't matter.

The main control device 250 is a device that includes a processor and controls the space sterilization device 200 by causing the processor to execute a program. In the case of this embodiment, the main controller 250 acquires the hypochlorous acid concentration in the electrolytic cell 210 from the hypochlorous acid concentration measuring device 100, which will be described later, and performs electrolysis so that the hypochlorous acid concentration is constant. Control device 230. Note that the technique for keeping the hypochlorous acid concentration constant will be described later. Here, the hypochlorous acid concentration means the total concentration of hypochlorous acid and hypochlorite ions. The main controller 250 also acquires water level information indicating the water level from a water level sensor 260 provided in the electrolyzer 210, and if the water level in the electrolyzer 210 has not reached a predetermined water level threshold, the main controller 250 control so that it does not operate.

The hypochlorous acid concentration measuring device 100 is a device that measures the concentration of hypochlorous acid generated by electrolyzing chlorine-containing water stored in an electrolytic cell 210, and includes a measuring means 110, a measuring means 110, A control device 120 is provided.

The measuring means 110 is a device for measuring conductivity information indicating the conductivity of hypochlorous acid water stored in the electrolytic cell 210, and includes a pair of measuring electrodes 111 and an application measuring device 112. . In the case of this embodiment, the measuring means 110 includes a water temperature sensor 113 that measures temperature information indicating the temperature of water stored in the electrolytic cell 210. The measuring means 110 acquires conductivity information with a predetermined time resolution. The time resolution of the measurement means 110 is, for example, on the order of nanoseconds.

The measurement electrodes 111 are a pair of conductive members that are placed apart from each other in the hypochlorous acid water stored in the electrolytic tank 210. Although the shape of the measurement electrode 111 is not particularly limited, in the case of this embodiment, it is a rectangular plate shape (band shape) and is smaller than the electrolytic electrode 220. The pair of measurement electrodes 111 are arranged so that their respective main surfaces face each other. The material of the measurement electrode 111 is not particularly limited as long as it is conductive. Note that the material of the measurement electrode 111 is not particularly limited, but a conductive material with corrosion resistance is preferable. Specifically, examples of the material of the measurement electrode 111 include titanium, titanium alloy, stainless steel, and the like. These materials can be easily processed into the measurement electrode 111 and can reduce manufacturing costs.

The application and measurement device 112 includes an AC power supply device 131 (see FIG. 5) that applies a predetermined AC voltage between the pair of measurement electrodes 111. Further, the application measuring device 112 includes a liquid resistance value measuring device 132 (see FIG. 5) that measures the liquid resistance value between the pair of measurement electrodes 111 as conductivity information. For example, the liquid resistance value measuring device 132 measures the liquid resistance value using electrochemical impedance spectroscopy. The liquid resistance value is determined by detecting the output side AC current (AC voltage) generated between the pair of measurement electrodes 111 due to the input side AC voltage (AC current) applied by the AC power supply 131, and calculating the input waveform and output waveform. Measured based on Electrochemical impedance spectroscopy is a method of measuring the impedance of a solution and analyzing its state. It measures the real and imaginary parts of the impedance and uses Nyquist diagrams etc. to calculate the liquid resistance of the solution. can be measured. The application and measurement device 112 selects whether or not to apply an AC voltage to the pair of measurement electrodes 111, that is, whether to apply an AC voltage to the pair of measurement electrodes 111, under the control of the measurement control device 120. The frequency of the AC voltage applied between the pair of measurement electrodes 111 by the application and measurement device 112 is not limited. For example, the frequency of the alternating current voltage is preferably selected from a range of 1 kHz or more and 100 kHz or less. Furthermore, the application and measurement device 112 may be one that can arbitrarily adjust the applied frequency. By applying the AC voltage in the relatively high frequency range, the liquid resistance value measurement device calculates the liquid resistance value without an imaginary term when calculating the liquid resistance value of hypochlorous acid water using the AC impedance method. value can be measured. Although the application and measurement device 112 includes an AC power supply device 131 that applies an AC voltage, the application and measurement device 112 may also include an AC power supply device 131 that applies an AC current. In this case, the measurement control device 120 may control the alternating current.

FIG. 2 is a block diagram showing the functional configuration of the measurement control device 120. The measurement control device 120 includes a processor, and controls the timing at which the application and measurement device 112 applies an AC voltage to the pair of measurement electrodes 111 by causing the processor to execute a program. Furthermore, conductivity information indicating the conductivity of hypochlorous acid water obtained by applying an alternating current voltage is acquired. The measurement control device 120 includes a measurement information acquisition section 121, a conversion information acquisition section 122, and a concentration calculation section 123 as processing sections. In the case of this embodiment, the measurement control device 120 includes an electrolysis execution acquisition section 125, a measurement instruction section 124, a correction information acquisition section 126, a measurement adjustment section 127, and a cleaning section 128.

The measurement information acquisition unit 121 acquires conductivity information from the measurement means 110. The electrical conductivity information acquired from the measuring means 110 is not particularly limited, and may be information such as the electrical conductivity (electrical conductivity) of hypochlorous acid water or information from which the electrical conductivity can be derived by calculation. For example, the conductivity information may be a liquid resistance value of hypochlorous acid water. The measurement information acquisition unit 121 may obtain the liquid resistance value measured by the measurement control device 120 using the AC impedance method, and derive the conductivity by calculating the reciprocal of the obtained liquid resistance value. In the case of this embodiment, the measurement information acquisition unit 121 acquires conductivity information at an acquisition period 302 (see FIG. 12) that is slower than the time resolution of the measurement means 110. For example, the acquisition cycle 302 of the measurement information acquisition unit 121 is a microsec order. Conductivity information is sampled while being thinned out at a relatively slow cycle, and conductivity information including phase information is simply acquired. Thereby, even if the measurement control device 120 operates at a low operating speed, the conductivity can be derived, and cost reduction can be realized. The acquisition period 302 is coprime to the division time, which is a time corresponding to one of the predetermined divisions of the AC cycle of the AC voltage (AC current) applied by the application and measurement device 112, and the division number. A product of an integer of 3 or more is preferable. Specifically, for example, as shown in FIG. 12, the AC cycle 300 applied by the voltage application and measurement device 112 is 10 μs (100 kHz), the number of divisions is 10, and the division time 301 corresponding to one of the 10 equal divisions is 1 μs. In this case, the acquisition period 302 becomes 3 μs, which is the product of 10, which is the number of divisions, and 3, which is one of the integers that are mutually prime and greater than or equal to 3. Therefore, the measurement information acquisition unit 121 acquires conductivity information in the phase indicated by the arrow in FIG. 12.

In the case of this embodiment, the measurement information acquisition unit 121 also acquires temperature information from the water temperature sensor 113 included in the measurement means 110.

The conversion information acquisition unit 122 acquires conversion information indicating the relationship between the hypochlorous acid concentration and the conductivity information. The inventor stored water containing chlorine (hereinafter referred to as water in this paragraph) in an electrolytic cell 210, and electrolyzed the water at a predetermined voltage for a predetermined time. When electrolysis is not performed at all (0 times), the hypochlorous acid concentration and the conductivity of water are measured, and each time water electrolysis is performed under the above conditions, the hypochlorous acid concentration is and the conductivity of water. Based on the above experiments, the inventors have found that the hypochlorous acid concentration and the conductivity of water are in an inversely proportional relationship, as shown in FIG. 3. Note that n in FIG. 3 is an integer. Moreover, description of specific numerical values of hypochlorous acid concentration and electrical conductivity is omitted.

From the above, the inventor created conversion information as a function, which shows the relationship between hypochlorous acid concentration and electrical conductivity, as shown in the graph of FIG. 4. In the case of this embodiment, the conversion information acquisition unit 122 acquires the function stored in the storage device 102 included in the measurement control device 120 as conversion information. Note that FIG. 4 shows production period conversion information that is conversion information used in the production period of hypochlorous acid. Moreover, the vertical axis of the graph shown in FIG. 4 is the difference in electrical conductivity. The difference in conductivity will be described later.

The concentration calculation unit 123 calculates the hypochlorous acid concentration based on the conductivity information acquired from the measuring means 110 and the conversion information acquired by the conversion information acquisition unit 122. The concentration calculation unit 123 outputs the calculated hypochlorous acid concentration to the main controller 250. Note that a specific description of the concentration calculation section 123 will be given later. Furthermore, the hypochlorous acid concentration calculated by the concentration calculation unit 123 does not have to be an accurate (absolute) concentration of hypochlorous acid in the aqueous solution. For example, relative concentrations such as lower than the reference concentration and higher than the reference concentration are also included in the hypochlorous acid concentration, using a preset reference concentration or a previously calculated concentration as the reference concentration. Furthermore, even if the difference (numerical difference) from the standard concentration is not clear, it is included in the hypochlorous acid concentration.

The electrolysis execution acquisition unit 125 acquires execution information indicating the execution state of electrolysis executed by the electrolysis device 230 and the electrolysis electrode 220 from the main controller 250. Thereby, the electrolysis execution acquisition unit 125 can grasp from the execution information whether electrolysis is being executed or not being executed in the electrolytic cell 210.

The measurement instruction unit 124 controls the measuring means 110 to measure conductivity information when electrolysis is not being performed based on the execution information acquired by the electrolysis execution acquisition unit 125. Thereby, conductivity information can be accurately measured without strongly insulating the electrolytic device 230 and the measurement control device 120, and the number of parts can be reduced, contributing to miniaturization of the device.

The correction information acquisition unit 126 acquires correction information indicating temperature correction when calculating the hypochlorous acid concentration from the measured conductivity information. The correction information may be created by experimentally changing the temperature of the water in the electrolytic cell 210 and measuring the relationship between the temperature and concentration of the hypochlorous acid water. Further, the temperature coefficient of conductivity may be used as correction information.

The temperature coefficient of conductivity is expressed by the following formula 1.

t: Temperature of hypochlorous acid water (temperature information)
K: Conductivity α: Temperature coefficient

α varies depending on the type of solute dissolved in water. The inventor has found that the temperature coefficient (226*10^(-4)) of NaCl water (dilute salt water) is suitable for temperature correction of hypochlorous acid concentration. Note that *, and * indicate multiplication, and ^ indicates exponentiation.

The concentration calculation unit 123 calculates the hypochlorous acid concentration using two pieces of conductivity information measured before and after one electrolysis run performed for a predetermined time and at a predetermined voltage. This makes it possible to exclude the influence of the hardness of water containing chlorine on the conversion information. Specifically, for example, when tap water is used to create water containing chlorine, the hardness of the water varies depending on regional differences, but by using conductivity information before and after a single electrolysis process, it is possible to determine where the water is. Hypochlorous acid concentration can be calculated using common conversion information even in different regions.

As a specific calculation method, the difference in conductivity information after replacing the water in the electrolytic cell 210 and before the first electrolysis is set to zero, as shown in FIG. 4, and the hypochlorous acid concentration is also set to zero. shall be. Note that the conductivity information may be obtained by actually performing the measurement.

Next, after performing one electrolysis, the measurement instruction unit 124 operates the application measurement device to perform measurement. The measurement information acquisition unit 121 acquires conductivity information (liquid resistance value) and converts it into conductivity. For the obtained conductivity, a corrected conductivity corresponding to the temperature is derived based on the temperature information acquired by the measurement information acquisition section 121 and the correction information acquired by the correction information acquisition section 126. Here, when the measurement information acquisition unit 121 acquires the conductivity information at an acquisition period 302 that is slower than the time resolution of the measurement means 110, the measurement information acquisition unit 121 acquires the conductivity information for a plurality of alternating current cycles applied by the application measurement device 112. The conductivity is derived based on the Specifically, for example, one cycle of the AC current (output side) generated between the measurement electrodes 111 by the AC voltage (input side) applied by the AC power supply device 131 is generated from conductivity information for a plurality of AC cycles. The electrical conductivity is thereby derived. Alternatively, the maximum value and the minimum value may be specified from the conductivity information for a plurality of alternating current cycles, and the conductivity may be derived from these values. According to this, the process of generating a waveform from scattered information becomes unnecessary, and the load on the measurement control device 120 can be suppressed. Next, as shown in Equation 2 below, the corrected conductivity derived in the previous round is subtracted. Accumulate the differences obtained by subtraction.

n indicates the number of times of electrolysis during the production period.
The electrical conductivity (n) means the electrical conductivity after the n-th electrolysis.
N indicates the total number of electrolysis during the production period.

The concentration calculation unit 123 calculates the hypochlorous acid concentration from the cumulative difference in conductivity based on the conversion information shown in FIG. 4.

The measurement adjustment unit 127 changes the gain of the output power of the AC power supply device 131 included in the application measurement device 112 so that the conductivity information measured by the measurement means 110 falls within a predetermined range ((a) in FIG. 5). (see step (b) in FIG. 5), and changing the gain of the liquid resistance value measuring device 132 (see step (b) in FIG. 5). According to this, conductivity can be measured with high accuracy. The gain adjustment method is not particularly limited, but an example may be a method in which the gain is gradually increased from a small gain and set to a gain just before the liquid resistance value, which is the output, is saturated. Further, the measurement adjustment unit 127 may change the gain at least once in the initial stage of filling the electrolytic cell 210 with water containing chlorine.

The cleaning unit 128 determines that the entire measuring electrode 111 is immersed in chlorine-containing water stored in the electrolytic cell 210 based on water level information measured by a water level sensor 260 provided in the electrolytic cell 210. After confirming this, the application and measurement device 112 is operated to clean the measurement electrode 111. Cleaning is performed by applying an alternating current voltage to the measurement electrode 111 at the maximum output allowed by the application and measurement device 112. Thereby, dissolution of salt crystals etc. deposited on the surface of the measurement electrode 111 can be promoted.

Next, the operation of the space sterilization device 200 will be explained. FIG. 6 is a flowchart showing the operation flow of the space sterilization device 200 during the generation period of hypochlorous acid. First, the main controller 250 confirms that the electrolytic cell 210 is full of water (S101). The cleaning unit 128 of the measurement control device 120, which has acquired the information indicating that the water is full from the main control device 250, controls the application measurement device 112 to apply an AC voltage of a predetermined power to the measurement electrode 111. 111 cleaning is performed (S102). Thereafter, the process waits until an electrolytic treatment start signal is generated (S103). In the case of this embodiment, the electrolytic treatment start signal is output by the electrolytic control unit 251 (see FIG. 10) included in the main controller 250.

When the electrolytic treatment start signal is generated, before the first electrolytic treatment, the AC power supply device 131 of the application and measurement device 112 applies a predetermined AC voltage to the measurement electrode 111, and the liquid resistance value measurement device 132 applies a predetermined AC voltage to the measurement electrode 111. Measure the liquid resistance value of water in 210. Furthermore, the water temperature sensor 113 measures the water temperature (S104). The measurement information acquisition unit 121 of the measurement control device 120 acquires a liquid resistance value as conductivity information and also acquires temperature information. After converting the liquid resistance value into conductivity, the concentration calculation unit 123 corrects the conductivity based on correction information using temperature information. The concentration calculation unit 123 stores the corrected conductivity together with the number of calculations (S105). Note that the first measurement after filling the electrolytic cell 210 with water may be omitted. If omitted, the electrical conductivity may be stored as the initial value of electrical conductivity equivalent to tap water containing a predetermined amount of salt.

Next, the electrolyzer 230 applies a DC voltage to the electrolytic electrode 220 at a predetermined output for a predetermined time to perform electrolysis of the water containing chlorine in the electrolytic cell 210 (S106). This produces hypochlorous acid water.

When the measurement instruction section 124 determines that electrolysis has ended based on the execution information acquired by the electrolysis execution acquisition section 125, the measurement instruction section 124 controls the measurement means 110 to measure the liquid resistance value. The measurement information acquisition unit 121 also acquires temperature information (S107). The concentration calculation unit 123 takes the reciprocal of the liquid resistance value, converts it into conductivity, and calculates the conductivity based on the correction information. Then, the difference between the previously calculated conductivity and the currently calculated conductivity is calculated. Further, the obtained differences are accumulated as shown in Equation 2 (S109). The concentration calculating unit 123 calculates the hypochlorous acid concentration using the accumulated difference and the conversion information (S110), and outputs the calculated hypochlorous acid concentration to the main controller 250 (S111).

The above steps from electrolysis (S106) to output of hypochlorous acid concentration (S111) are repeated until the electrolytic treatment end signal is generated (until the end of the production period). For example, when the main controller 250 determines that the hypochlorous acid concentration exceeds a predetermined concentration threshold (see FIG. 11), the electrolysis control unit 251 may generate an end signal for the electrolysis process.

As described above, according to the hypochlorous acid concentration measuring device 100 according to the present embodiment, the concentration of hypochlorous acid water obtained by electrolyzing chlorine-containing water can be provided as an inexpensive module. be able to. Further, the hypochlorous acid concentration measuring device 100 has a relatively simple structure and can stably measure the hypochlorous acid concentration over a long period of time.

In addition, by calculating the hypochlorous acid concentration using the difference in conductivity before and after one electrolysis, it is possible to calculate the hypochlorous acid concentration when water containing chlorine contains various hardness components or when the content ratio of hardness components is different. Even in this case, the difference in conductivity can be used to offset the information related to the hardness component. Therefore, even if the water hardness component differs due to regional differences, the hypochlorous acid concentration can be calculated stably and with high accuracy using one conversion information.

Furthermore, by adopting the AC impedance method in which the liquid resistance value is measured by applying an AC voltage, the circuit configuration of the application and measurement device 112 can be made relatively simple. Furthermore, by selecting the frequency of the applied alternating current voltage from a range of 1 kHz or more and 100 kHz or less, the liquid resistance value can be stably measured.

Furthermore, by adding temperature correction to the conductivity based on the water temperature in the electrolytic cell 210, it is possible to calculate the hypochlorous acid concentration more accurately and with high precision.

In addition, highly accurate concentration measurement is possible by adjusting the gain of at least one of the AC power supply device and the liquid resistance value measuring device 132 to provide a large output that does not saturate the output in the initial stage.

Furthermore, by promoting the dissolution of salt crystals attached to the measurement electrode 111 through the cleaning process, fluctuations in measurement results due to deposits on the measurement electrode 111 are suppressed, and highly accurate concentration measurement becomes possible.

FIG. 7 is a flowchart showing the operation flow of the space sterilization device 200 during the decay period of hypochlorous acid. Upon receiving the end signal of the electrolytic treatment indicating the end of the production period, the concentration calculation unit 123 calculates the electrical conductivity information, which is the electrical conductivity measured before the last electrolysis in the production period, and the electrical conductivity after the electrolysis is performed. The hypochlorous acid concentration calculated based on the difference between the measured conductivity information and the post-conductivity information is stored in the storage device 102. Further, the post-conductivity information is stored in the storage device 102.

After receiving the electrolysis treatment end signal, the measurement instruction unit 124 waits for a predetermined time (S202) based on information from a timer (not shown), and then controls the measurement means 110 to measure the liquid resistance value. . Furthermore, the measurement information acquisition unit 121 acquires temperature information (S203). The concentration calculation unit 123 takes the reciprocal of the liquid resistance value, converts it into conductivity, and calculates the conductivity based on the correction information. Then, the difference between the conductivity based on the conductivity information stored in the storage device 102 and the conductivity calculated this time is calculated. Further, the obtained differences are accumulated as shown in Equation 3 (S205). Note that the difference becomes a positive value in the decay period.

m indicates the number of times the liquid resistance value is measured during the decay period.
The electrical conductivity (m) means the electrical conductivity at the m-th measurement.
M indicates the total number of liquid resistance measurements during the decay period.

The concentration calculation unit 123 uses the accumulated difference and the conversion information to calculate the hypochlorous acid concentration (S206). In the case of the present embodiment, the conversion information acquisition unit 122 acquires as conversion information decay period conversion information that is different from generation period conversion information that is conversion information used in the generation period.

The inventor believes that the relationship between the hypochlorous acid concentration and the conductivity of water during the decay period, as shown in FIG. 8, is different from that during the production period shown in FIG. However, the cumulative relationship between the hypochlorous acid concentration and the difference in conductivity between the generation period and the decay period is a proportional relationship as shown in FIGS. 4 and 9. Note that m in FIG. 8 is an integer. Moreover, description of specific numerical values of hypochlorous acid concentration and electrical conductivity is omitted. From the above, the inventor has created decay period conversion information as a function, which shows the relationship between hypochlorous acid concentration and electrical conductivity, as shown in the graph of FIG. 9. In the case of this embodiment, the conversion information acquisition unit 122 acquires the function stored in the storage device 102 included in the measurement control device 120 as decay period conversion information.

The concentration calculation unit 123 calculates the hypochlorous acid concentration using the decay period conversion information. Concentration calculation unit 123 outputs the calculated hypochlorous acid concentration to main controller 250 (S207).

FIG. 10 is a block diagram showing a processing unit realized by causing a processor included in the main control device 250 to execute a program. When the hypochlorous acid concentration obtained from the concentration calculation unit 123 of the hypochlorous acid concentration measurement device 100 falls below a predetermined lower limit threshold (S208, Yes), the electrolysis control unit 251 included in the main control device 250 starts the decay period. The electrolysis device 230 is controlled by outputting a start signal for the electrolytic treatment so that the electrolytic treatment is terminated and transitions to the generation period in which hypochlorous acid is generated (S209). On the other hand, if the hypochlorous acid concentration is not below the lower limit threshold (S208, No), after waiting for a predetermined time (S202), a series of processes (S203-S207) for outputting the hypochlorous acid concentration is executed. be done.

In addition, in the production period after the decay period, the hypochlorous acid concentration that determines the end of the production period is different from the concentration threshold that determines the end of the first electrolytic treatment (end of the first generation period) (in this implementation) In the case of morphology, the determination may be made using an additional density threshold value (higher than the density threshold value) (see FIG. 11). Furthermore, the data at the end of the decay period may be used for measuring the liquid resistance value of the water in the electrolytic cell 210, measuring the water temperature (S104), and correcting the conductivity water temperature (S105) after outputting the electrolytic treatment start signal. do not have.

As described above, during the decay period, the hypochlorous acid concentration can be measured at predetermined intervals by using the configuration for generating hypochlorous acid as is. Thereby, the hypochlorous acid concentration in the electrolytic cell 210 can be maintained between the lower limit threshold and the additional concentration threshold. Therefore, the effect of the space sterilization device 200 can be maintained for a long period of time.

Further, the electrolysis control unit 251 may stabilize the hypochlorous acid concentration in the electrolytic cell 210 over time as shown in FIG. 14. Specifically, the electrolysis control unit 251 acquires the hypochlorous acid concentration calculated by the concentration calculation unit 123, and when the hypochlorous acid concentration is below the lower limit threshold, the concentration of hypochlorous acid in the electrolytic cell 210 is The electrolysis device 230 may be controlled based on electrolysis information that provides a target concentration that is greater than or equal to the lower limit threshold, at least less than the additional concentration threshold, and preferably less than the concentration threshold.

Here, the electrolysis information includes information regarding the amount of applied charge, which is the amount of charge required to change the current concentration of hypochlorous acid to the target concentration. The amount of applied charge is proportional to the product of the current value applied to the electrolytic electrode 220 during electrolysis and the duration time, which is the time during which the current is applied, as shown in Equation 4 below.

Applied charge amount = current value * duration time...Equation 4

In the case of this embodiment, the electrolysis information includes current value and duration. The electrolysis control unit 251 calculates electrolysis information that makes the concentration of hypochlorous acid the target concentration, but the electrolysis control unit 251 calculates the electrolysis information that makes the concentration of hypochlorous acid the target concentration by changing at least one of the current value and duration. calculate.

Further, the electrolysis control unit 251 may divide the duration included in the electrolysis information into multiple periods. Specifically, the following equation 5 holds true.

S: Number of divisions Total applied charge: Amount of charge required to reach the target concentration Current value (s): sth current value Duration (s): Sth duration

Further, the electrolysis control unit 251 calculates electrolysis information including interval information indicating that a predetermined first time interval is to be left between execution of electrolysis corresponding to the acquired execution information and execution of the next electrolysis. Good too. Here, the first time is specifically a time of 30 minutes or more. The inventor has obtained from experience that by leaving an interval of 30 minutes or more, the load on the electrolytic electrode 220 can be reduced and the life of the electrolytic electrode 220 can be extended. Alternatively, the first time may be a short time of 10 minutes or less. The inventor has obtained from experience that the concentration of hypochlorous acid in the electrolytic cell 210 becomes uniform by performing electrolysis at intervals of 10 minutes or less.

Further, if the hypochlorous acid concentration calculated by the concentration calculation unit 123 immediately after the end of the generation period is higher than the target concentration, the electrolysis control unit 251 controls the electrolysis control unit 251 after a predetermined second time has elapsed from the execution of the electrolysis corresponding to the execution information. Measurement instruction information that causes conductivity information to be measured is output to the measurement control device 120, and after the second time has elapsed, the hypochlorous acid concentration calculated by the concentration calculation unit 123 is acquired, and the hypochlorous acid concentration in the electrolytic cell 210 is Electrolysis information including a concentration reduction time at which the acid concentration reaches a lower threshold value lower than the target concentration is calculated, and the electrolyzer 230 is controlled to start electrolysis when the concentration reduction time has elapsed. Further, the electrolysis control unit 251 outputs measurement instruction information to the measurement control device 120 to execute measurement of conductivity information after a predetermined third time has elapsed from the elapse of the second time, and calculates the concentration after the third time has elapsed. The accuracy of the concentration reduction time may be improved by acquiring the hypochlorous acid concentration calculated by the department and updating the concentration reduction time during which the concentration of hypochlorous acid in the electrolytic cell becomes lower than the target concentration.

Aspect (1-1) of the hypochlorous acid concentration measuring device 100 that can be derived from the above embodiment is to measure the concentration of hypochlorous acid generated by electrolyzing chlorine-containing water stored in the electrolytic tank 210. A hypochlorous acid concentration measuring device 100 for measuring, comprising a measuring means 110 for measuring conductivity information indicating the conductivity of hypochlorous acid water stored in an electrolytic cell 210, and a measurement control for controlling the measuring means 110. The measurement control device 120 includes a measurement information acquisition unit 121 that acquires conductivity information from the measurement means 110, and a conversion unit that acquires conversion information indicating the relationship between the hypochlorous acid concentration and the conductivity information. It includes an information acquisition section 122 and a concentration calculation section 123 that calculates the hypochlorous acid concentration based on the measured conductivity information and conversion information.

Thereby, hypochlorous acid concentration can be calculated accurately with a simple configuration.

Further, aspect (1-2) includes aspect (1-1), in which the measurement control device 120 includes an electrolysis execution acquisition unit 125 that acquires execution information indicating execution of electrolysis, and an electrolysis execution acquisition unit 125 that acquires execution information indicating execution of electrolysis; a measurement instruction unit 124 that causes the measuring means 110 to measure the conductivity information when the electrolysis is not performed, and the concentration calculation unit 123 calculates the difference in the conductivity information measured before and after the electrolysis is performed. Calculate the hypochlorous acid concentration based on

According to this, the hardness of the water put into the electrolytic cell 210 can be offset by measurements before and after electrolysis, and it is possible to calculate a stable hypochlorous acid concentration independent of the hardness of the water put into the electrolytic cell 210. can.

Further, the aspect (1-3) includes the aspect (1-1) or the aspect (1-2), in which the measuring means 110 is arranged in a separated state in the hypochlorous acid water stored in the electrolytic cell 210. A pair of measurement electrodes 111 are connected to each other, an application measurement device 112 applies an AC voltage selected from a range of 1 kHz or more to 100 kHz or less, and the liquid resistance value between the measurement electrodes 111 is determined as conductivity. A concentration calculation unit 123 calculates the hypochlorous acid concentration based on the measured liquid resistance value.

According to this, the liquid resistance value can be calculated without an imaginary term, and the calculation process can be facilitated.

Further, aspect (1-4) includes any one of aspects (1-1) to (1-3), and the measuring means 110 measures temperature information indicating the temperature of water stored in the electrolytic cell 210. The measurement control device 120 includes a water temperature sensor 113 for measurement, and a correction information acquisition unit 126 for acquiring correction information indicating temperature correction when calculating the hypochlorous acid concentration from the measured conductivity information, and performs concentration calculation. The unit 123 calculates the hypochlorous acid concentration by correcting it based on the temperature information and correction information acquired by the measurement information acquisition unit 121.

According to this, it is possible to correct an error in the hypochlorous acid concentration due to the temperature inside the electrolytic cell 210, and it is possible to improve the accuracy of the calculated hypochlorous acid concentration.

Further, aspect (1-5) includes any one of aspects (1-1) to (1-4), and the measurement control device 120 is configured to ensure that the conductivity information measured by the measuring means is within a predetermined range. A measurement adjustment unit 127 is provided to adjust at least one of the output power of the application measurement device 112 and the gain of the liquid resistance value measurement device 132 so as to be within the range.

According to this, the liquid resistance value can be measured accurately, and it can contribute to accurate calculation of hypochlorous acid concentration.

Further, aspect (1-6) includes any one of aspects (1-1) to (1-5), in which the measurement information acquisition unit 121 acquires a predetermined value from the water level sensor 260 provided in the electrolytic cell 210. After acquiring water level information indicating the water level and confirming that the measurement electrode 111 is placed in the chlorine-containing water stored in the electrolytic tank 210 based on the water level information, the measurement control device 120 moves the application measurement device 112 to the water level information indicating the water level. A cleaning section 128 is provided which operates to clean the measurement electrode 111.

According to this, the cleanliness of the measurement electrode 111 can be maintained constant, and the hypochlorous acid concentration can be calculated stably and accurately.

Further, aspect (2-1) includes any one of aspects (1-1) to (1-6), and the measurement control device 120 executes electrolysis to obtain execution information indicating execution of electrolysis. The measurement instruction section 124 includes an acquisition section 125 and a measurement instruction section 124 that causes the measurement means 110 to measure conductivity information when electrolysis is not executed based on the execution information. , conductivity information is repeatedly measured at predetermined intervals before the next electrolysis is performed, and the concentration calculation unit 123 calculates each hypochlorous acid concentration based on the plurality of measured conductivity information.

According to this, it is possible to successively monitor the attenuation state of the hypochlorous acid concentration in the electrolytic cell 210 after electrolysis.

Further, aspect (2-2) includes any one of aspects (1-1) to (1-6), and aspect (2-1), and the conversion information acquisition unit 122 converts hypochlorous acid into The concentration calculation unit 123 obtains decay period conversion information, which is conversion information used in the decay period of hypochlorous acid, which is different from production period conversion information, which is information used in the production period, and the concentration calculation unit 123 calculates the measured conductivity information, Calculate the hypochlorous acid concentration based on the decay period conversion information.

According to this, it is possible to accurately calculate the hypochlorous acid concentration in the decay period, taking into account the evaporation of water contained in the electrolytic cell 210, etc.

Further, aspect (2-3) includes aspects (1-1) to (1-6), and either aspect (2-1) or aspect (2-2), and the measurement control device 120 , an electrolysis execution acquisition unit 125 that acquires execution information indicating execution of electrolysis, and a measurement instruction unit 124 that causes the measurement means 110 to measure conductivity information when electrolysis is not executed based on the execution information. , and the concentration calculation unit 123 includes: previous conductivity information that is conductivity information measured before performing electrolysis; and conductivity information that is the last conductivity information in the generation period that is measured after performing electrolysis. Based on the hypochlorous acid concentration calculated based on the difference between the post-conductivity information and the post-conductivity information, the conductivity information measured after the post-conductivity information in the generation period in the decay period and the calculated The absolute value of hypochlorous acid concentration is calculated based on the hypochlorous acid concentration information obtained. Note that the previous conductivity information measured before performing electrolysis may be conductivity information before performing electrolysis for the first time.

According to this, even during the decay period, the hardness of the water put into the electrolytic cell 210 can be offset by the measurement immediately after electrolysis and the measurement after the decay period has passed, and the stability is not dependent on the hardness of the water put into the electrolytic cell 210. The hypochlorous acid concentration can be calculated.

Further, the aspect (1-7) of the space sterilization device 200 that can be derived from the above embodiment includes an electrolytic cell 210 that stores water containing chlorine, and an electrolytic electrode 220 that is inserted into the electrolytic cell 210. , an electrolytic device 230 that applies a voltage to an electrolytic electrode 220 to electrolyze water containing chlorine to generate hypochlorous acid water, and measures the concentration of hypochlorous acid in the generated hypochlorous acid water. A space sterilization device 200 comprising a hypochlorous acid concentration measuring device 100 for measuring hypochlorous acid concentration, and a diffusion means 240 for diffusing at least hypochlorous acid in the generated hypochlorous acid water into the atmosphere. The acid concentration measuring device 100 includes a measuring means 110 that measures conductivity information indicating the conductivity of hypochlorous acid water stored in an electrolytic cell 210, and a measurement control device 120 that controls the measuring means 110. The measurement control device 120 includes a measurement information acquisition section 121 that acquires conductivity information from the measurement means 110, a conversion information acquisition section 122 that acquires conversion information indicating the relationship between hypochlorous acid concentration and conductivity information, and a measurement information acquisition section 122 that acquires conductivity information from the measurement means 110. and a concentration calculation unit 123 that calculates the hypochlorous acid concentration based on the conductivity information and conversion information.

According to this, hypochlorous acid water with a predetermined concentration can be generated, and the space sterilization effect can be efficiently exhibited.

Further, aspect (2-4) includes aspect (1-7), in which the measurement control device 120 includes an electrolysis execution acquisition unit 125 that acquires execution information indicating execution of electrolysis, and an electrolysis execution acquisition unit 125 that acquires execution information indicating execution of electrolysis; and a measurement instruction section 124 that causes the measurement means 110 to measure the conductivity information when the measurement means 110 is not performing the electrolysis. The conductivity information is repeatedly measured at predetermined intervals during the decay period in which conductivity information is not performed, and the concentration calculation unit 123 calculates each hypochlorous acid concentration based on the plurality of measured conductivity information.

According to this, it is possible to monitor changes over time in the hypochlorous acid concentration during the decay period, and the space sterilization effect can be effectively utilized.

Further, aspect (2-5) includes aspect (1-7) or aspect (2-4), in which the hypochlorous acid concentration obtained from the hypochlorous acid concentration measuring device 100 in the decay period exceeds the lower limit threshold. A main control device 250 is provided which has an electrolysis control section 251 that controls the electrolysis device 230 so as to generate hypochlorous acid when the amount of hypochlorous acid decreases.

Thereby, the hypochlorous acid concentration in the electrolytic cell 210 can be maintained within a predetermined range, and the space sterilization effect can be maintained constant.

Further, the aspect (1-8) of the hypochlorous acid concentration measuring method that can be derived from the above embodiment is the concentration of hypochlorous acid generated by electrolyzing chlorine-containing water stored in the electrolytic tank 210. The hypochlorous acid concentration measuring method includes a measurement information acquisition unit 121 that collects conductivity information from a measuring means 110 that measures conductivity information indicating the conductivity of hypochlorous acid water stored in an electrolytic cell 210. The conversion information acquisition unit 122 acquires conversion information indicating the relationship between hypochlorous acid concentration and conductivity information, and calculates the hypochlorous acid concentration based on the acquired conductivity information and conversion information. Calculated by the department.

According to this, the hypochlorous acid concentration can be accurately measured using a simple device.

Further, aspect (2-7) includes aspect (1-8), in which the measurement information acquisition unit 121 performs a predetermined measurement in a decay period in which electrolysis is not performed after performing electrolysis in the generation period of hypochlorous acid. Conductivity information is acquired from the measuring means 110 that measures conductivity information indicating the conductivity of hypochlorous acid water stored in the electrolytic cell 210 at intervals.

According to this, the attenuation state of the hypochlorous acid concentration can be accurately measured.

In addition, aspect (3-1) includes any of aspects (1-1) to (1-6) and aspects (2-1) to (2-3), and the measurement information acquisition unit 121 acquires the conductivity information from the measuring means 110 at an acquisition period 302 that is slower than the time resolution of the measuring means 110, and the concentration calculation unit 123 calculates the conductivity information based on the conductivity information corresponding to a plurality of alternating current cycles and the conversion information. Calculate the hypochlorous acid concentration.

According to this, conductivity can be derived even with the measurement control device 120 having a low operating speed, and cost reduction can be achieved.

In addition, aspect (3-2) includes any of aspect (3-1), aspect (1-1) to aspect (1-6), and aspect (2-1) to aspect (2-3). The measuring means 110 includes a liquid resistance value measuring device 132 that measures the liquid resistance value between the measuring electrodes 111 as conductivity information, and the concentration calculation unit 123 calculates hypochlorous acid based on the measured liquid resistance value. Calculate the concentration.

According to this, it becomes possible to accurately calculate the hypochlorous acid concentration with a simple configuration.

In addition, aspect (3-3) includes any of aspect (3-2), aspect (1-1) to aspect (1-6), and aspect (2-1) to aspect (2-3). The application measuring device 112 applies an alternating voltage or an alternating current between the pair of measuring electrodes 111 at a frequency at which the liquid resistance value measured by the liquid resistance value measuring device 132 does not have an imaginary component.

According to this, the hypochlorous acid concentration can be calculated by simple calculation, and the load on the hypochlorous acid concentration measuring device 100 can be reduced.

In addition, aspect (3-4) includes aspects (3-1) to (3-3), aspects (1-1) to (1-6), and aspects (2-1) to (2-2). -3), and the acquisition cycle 302 includes a division time that corresponds to one of the predetermined divisions of the AC cycle applied by the application and measurement device 112, and a division time that corresponds to one of the divisions and the division number. It is the product of a prime integer greater than or equal to 3.

According to this, even if the measurement control device 120 operates at a low operating speed, the conductivity can be accurately derived using the conductivity information corresponding to the AC cycles of an integer or more to be multiplied.

In addition, aspect (3-5) includes aspects (3-1) to (3-4), aspects (1-1) to (1-6), and aspects (2-1) to (2-2). -3), and the concentration calculation unit 123 calculates the hypochlorous acid concentration using the waveform calculated from the obtained conductivity information.

According to this, the liquid resistance value can be measured relatively accurately by electrochemical impedance spectroscopy.

In addition, aspect (3-6) includes aspects (3-1) to (3-4), aspects (1-1) to (1-6), and aspects (2-1) to (2-2). -3), and the concentration calculation unit 123 calculates the hypochlorous acid concentration using the maximum value and minimum value of the obtained conductivity information.

According to this, even if the measurement control device 120 operates at a low operating speed, the liquid resistance value can be relatively easily measured by electrochemical impedance spectroscopy.

Aspect (4-1) of the hypochlorous acid water generating device that can be derived from the above embodiment is a device in which the diffusion means 240 is excluded from the hypochlorous acid concentration measuring device 100, and the aspect (4-1) is a device that excludes the diffusion means 240 from the hypochlorous acid concentration measuring device 100. 1-6), from aspect (2-1) to aspect (2-3), and from aspect (3-1) to aspect (3-6), and the electrolysis control section 251 includes a concentration calculation section. The hypochlorous acid concentration calculated by 123 is acquired, and the electrolyzer 230 is controlled based on the electrolysis information that makes the concentration of hypochlorous acid in the electrolytic cell 210 the target concentration.

According to this, based on the hypochlorous acid concentration calculated by the concentration calculation unit 123, the hypochlorous acid concentration in the electrolytic cell 210 is stably adjusted to the target concentration using electrolytic information regarding the generated hypochlorous acid concentration. It can be done.

Further, aspect (4-2) includes aspect (4-1), and when the hypochlorous acid concentration calculated by the concentration calculation unit 123 is lower than the target concentration, the electrolysis control unit 251 controls the hypochlorous acid concentration. calculates electrolytic information including at least one of a current value and duration at which the target concentration is achieved.

According to this, the target concentration can be accurately achieved using the current value and duration, which are easily adjustable parameters.

Further, aspect (4-3) includes aspect (4-2), in which the electrolysis control unit 251 divides the duration into a plurality of parts and calculates electrolysis information including the divided duration.

According to this, it is possible to grasp the tendency of electrolysis, that is, the amount of increase in hypochlorous acid concentration due to the current and one of the divided durations, based on the previous duration of the divided durations. This allows the results to be fed back to the next electrolysis.

Further, the aspect (4-4) includes the aspect (4-2) or the aspect (4-3), and the electrolysis control unit 251 starts the next electrolysis from the execution of the electrolysis corresponding to the acquired execution information. Electrolysis information including interval information indicating that a predetermined first time interval is left until execution is calculated.

According to this, by providing the first time interval, it is possible to extend the life of the electrolytic electrode 220.

Further, aspect (4-5) includes any one of aspects (4-1) to (4-4), and the electrolysis control unit 251 is configured to perform electrolysis based on the hypochlorous acid concentration before and after performing electrolysis. Calculate electrolysis information.

According to this, parameters that affect the calculation of hypochlorous acid concentration, such as water hardness, can be excluded, and electrolysis information can be calculated based on accurate hypochlorous acid concentration.

Further, aspect (4-6) includes any one of aspects (4-1) to (4-5), and the electrolysis control unit 251 sets the hypochlorous acid concentration calculated by the concentration calculation unit 123 to the target level. If the concentration is higher than the concentration, measurement instruction information is output to the measurement control device 120 to cause the conductivity information to be measured after a predetermined second time has elapsed from the execution of electrolysis corresponding to the execution information, and the concentration is determined after the second time has elapsed. The calculation unit 123 acquires the calculated hypochlorous acid concentration, and controls the electrolyzer 230 based on electrolysis information including the concentration reduction time during which the concentration of hypochlorous acid in the electrolytic cell 210 becomes lower than the target concentration.

This makes it possible to stabilize the increase/decrease in the hypochlorous acid concentration within the electrolytic cell 210 within a narrow range. Note that the time period for the concentration to decrease below the target concentration may be the time period for the hypochlorous acid concentration to reach the lower limit threshold.

Further, aspect (4-7) includes aspect (4-6), in which the electrolysis control unit 251 provides measurement instruction information that causes conductivity information to be measured after a predetermined third time has elapsed from the elapse of the second time. is output to the measurement control device 120, and the concentration of hypochlorous acid calculated by the concentration calculation unit 123 is obtained after the third time has elapsed, and the concentration of hypochlorous acid in the electrolytic cell 210 is lower than the target concentration. The time is updated, and the electrolysis device 230 is controlled based on the electrolysis information including the updated concentration reduction time.

According to this, the concentration reduction time can be derived more accurately, and the hypochlorous acid concentration can be kept constant.

Aspect (4-8) of the space sterilization device that can be derived from the above embodiment is hypochlorous acid water produced by any of the hypochlorous acid water generation devices from aspect (4-1) to aspect (4-7). A diffusion means 240 is provided for diffusing chloric acid water into the atmosphere.

According to this, at least the hypochlorous acid in the hypochlorous acid water having a stable concentration can be diffused into the space, and the space sterilization effect can be stably exhibited.

Aspect (4-9) of the hypochlorous acid water generation method that can be derived from the above embodiments is hypochlorous acid water generation method in any of the hypochlorous acid water generation apparatuses from aspect (4-1) to aspect (4-7). In the chloric acid water generation method, a measurement information acquisition unit 121 acquires conductivity information from a measuring means 110, and a conversion information acquisition unit 122 acquires conversion information indicating the relationship between hypochlorous acid concentration and conductivity information. Then, the electrolysis execution acquisition unit 125 acquires execution information indicating the execution of electrolysis, and the measurement instruction unit 124 executes measurement of conductivity information by the measuring means 110 when electrolysis is not executed based on the execution information. Then, the concentration calculation unit 123 calculates the hypochlorous acid concentration based on the conductivity information measured before and after the execution of electrolysis and the conversion information, and obtains the hypochlorous acid concentration calculated by the concentration calculation unit 123. The electrolysis control section controls the electrolysis device 230 based on the electrolysis information that makes the concentration of hypochlorous acid in the electrolytic cell 210 the target concentration.

Note that the present invention is not limited to the above embodiments. For example, the embodiments of the present invention may be realized by arbitrarily combining the components described in this specification or by excluding some of the components. The present invention also includes modifications obtained by making various modifications to the above-described embodiments that a person skilled in the art can conceive without departing from the gist of the present invention, that is, the meaning of the words written in the claims. It will be done.

For example, in the above embodiment, a case has been described in which the difference in hardness components is canceled out using the difference in liquid resistance value (electrical conductivity). It is okay to calculate. In this case, multiple types of conversion information corresponding to differences in water hardness may be switched and applied.

Furthermore, it is not necessary to perform temperature correction on the liquid resistance value (conductivity). In this case, the measuring means 110 does not need to include the water temperature sensor 113 and does not need to acquire correction information.

Furthermore, by setting the gain appropriately in advance, for example, at the time of shipment, the measurement control device 120 may not need to adjust the gain.

Furthermore, cleaning may not be necessary by periodically replacing the measurement electrode 111.

Furthermore, although the main control device 250 and the measurement control device 120 have been described as separate bodies, the main control device 250 and the measurement control device 120 may be integrated. That is, the main control device 250, the measurement control device 120, and the electrolysis control section 251 may be realized by having one processor execute a program.

Furthermore, although a case has been described in which the hypochlorous acid concentration measuring device 100 is used in the space sterilization device 200, the hypochlorous acid concentration measuring device 100 may be applied to a hypochlorous acid water generating device.

Furthermore, the conversion information and correction information may be acquired through communication such as a network instead of being stored in the storage device 102 included in the measurement control device 120.

In addition, the measurement information acquisition unit 121 acquires the AC cycle 300 applied by the application measurement device 112 based on a plurality of conductivity information (for example, conductivity information of the same phase) that is assumed to have the same value in the AC cycle 300. It is also possible to detect a shift in the cycle 302 and update the acquisition cycle 302 to correspond to the actual AC cycle based on the detected shift. Specifically, as shown in the upper graph in FIG. zero). However, the value 311 of the acquired conductivity information may deviate. The measurement information acquisition unit 121 detects that a deviation has occurred when the difference 303 between the value of the conductivity information assumed in advance and the value of the conductivity information actually obtained is equal to or greater than a threshold value. Then, based on the difference 303, the acquisition cycle 302 may be updated as shown in the lower graph of FIG. 13 so that the values of the same phase become the same value (zero).

Furthermore, the timing of the update process of the acquisition cycle 302 is not limited, and may be before the conductivity information acquisition for the initial measurement of liquid resistance value (S104) in the generation period shown in the flowchart of FIG. 6, or during the decay period. The updating process may be performed for calibration before acquiring the conductivity information for the liquid resistance value measurement (S203) in step S203. Further, the updating process may be performed every time conductivity information for measuring the liquid resistance value is acquired or every predetermined number of times.

100 Hypochlorous acid concentration measuring device 102 Storage device 110 Measuring means 111 Measuring electrode 112 Application measuring device 113 Water temperature sensor 120 Measurement control device 121 Measurement information acquisition section 122 Conversion information acquisition section 123 Concentration calculation section 124 Measurement instruction section 125 Electrolysis execution Acquisition section 126 Correction information acquisition section 127 Measurement adjustment section 128 Cleaning section 131 AC power supply device 132 Liquid resistance value measuring device 200 Space sterilization device 210 Electrolytic cell 220 Electrolytic electrode 230 Electrolytic device 240 Diffusion means 250 Main controller 251 Electrolytic control section 260 Water level sensor 300 AC cycle 301 Division time 302 Acquisition cycle 303 Difference 310 Preliminary AC cycle 311 Value of conductivity information

Claims

A hypochlorous acid concentration measuring device that measures the concentration of hypochlorous acid generated by electrolyzing chlorine-containing water stored in an electrolytic tank,
Measuring means for measuring conductivity information indicating the conductivity of the hypochlorous acid water stored in the electrolytic cell;
A measurement control device that controls the measurement means,
The measurement control device includes:
a measurement information acquisition unit that acquires conductivity information from the measurement means;
a conversion information acquisition unit that acquires conversion information indicating the relationship between hypochlorous acid concentration and the conductivity information;
a concentration calculation unit that calculates a hypochlorous acid concentration based on the measured conductivity information and the conversion information;
Hypochlorous acid concentration measuring device equipped with.
The measurement control device includes:
an electrolysis execution acquisition unit that acquires execution information indicating execution of electrolysis;
a measurement instruction unit that causes the measuring means to measure conductivity information when electrolysis is not being executed based on the execution information,
The concentration calculation unit includes:
The hypochlorous acid concentration measuring device according to claim 1, wherein a difference in hypochlorous acid concentration is calculated using conductivity information measured before and after performing electrolysis.
The measuring means includes:
a pair of measurement electrodes arranged in a separated state in hypochlorous acid water stored in the electrolytic tank;
An application measuring device that applies an AC voltage selected from a range of 1 kHz or more and 100 kHz or less between the pair of measurement electrodes;
a liquid resistance value measuring device that measures a liquid resistance value between the measurement electrodes as conductivity information;
The hypochlorous acid concentration measuring device according to claim 1, wherein the hypochlorous acid concentration is calculated based on the measured liquid resistance value.
The measuring means includes a water temperature sensor that measures temperature information indicating the temperature of water stored in the electrolytic cell,
The measurement control device includes:
comprising a correction information acquisition unit that acquires correction information indicating temperature correction when calculating hypochlorous acid concentration from measured conductivity information,
The concentration calculation unit includes:
The hypochlorous acid concentration measuring device according to claim 1, wherein the hypochlorous acid concentration is calculated by correcting it based on the temperature information acquired by the measurement information acquisition unit and the correction information.
The measurement control device includes:
Claim 3, further comprising a measurement adjustment section that adjusts at least one of the output power of the application and measurement device and the gain of the liquid resistance value measurement device so that the conductivity information measured by the measurement means falls within a predetermined range. The hypochlorous acid concentration measuring device described in .
The measuring means includes:
a pair of measurement electrodes arranged in a separated state in hypochlorous acid water stored in the electrolytic tank;
an application measuring device that applies an alternating current voltage or alternating current with a predetermined alternating cycle between the pair of measurement electrodes;
The measurement information acquisition unit includes:
acquiring conductivity information from the measuring means at an acquisition period slower than the time resolution of the measuring means;
The concentration calculation unit includes:
The hypochlorous acid concentration measuring device according to claim 1, wherein the hypochlorous acid concentration is calculated based on the conductivity information corresponding to a plurality of the alternating current cycles and the conversion information.
The measuring means includes:
A liquid resistance value measuring device that measures a liquid resistance value between the measurement electrodes as conductivity information,
The concentration calculation unit includes:
The hypochlorous acid concentration measuring device according to claim 6, wherein the hypochlorous acid concentration is calculated based on the measured liquid resistance value.
The application measurement device includes:
Hypochlorous acid concentration according to claim 7, wherein an alternating voltage or an alternating current is applied between the pair of measurement electrodes at a frequency at which the liquid resistance value measured by the liquid resistance value measuring device does not have an imaginary component. measuring device.
The measurement control device includes:
an electrolysis execution acquisition unit that acquires execution information indicating execution of electrolysis;
a measurement instruction unit that causes the measuring means to measure conductivity information when electrolysis is not being executed based on the execution information,
The measurement instruction section is
After performing electrolysis during the production period of hypochlorous acid, repeatedly measuring conductivity information at predetermined intervals during a decay period during which electrolysis is not performed;
The concentration calculation unit includes:
The hypochlorous acid concentration measuring device according to claim 1, wherein each hypochlorous acid concentration is calculated based on a plurality of pieces of measured conductivity information.
The conversion information acquisition unit includes:
Obtaining decay period conversion information, which is the conversion information used in the decay period of hypochlorous acid, which is different from the production period conversion information, which is the conversion information used in the production period of hypochlorous acid,
The concentration calculation unit includes:
The hypochlorous acid concentration measuring device according to claim 9, wherein the hypochlorous acid concentration is calculated based on the measured conductivity information and the decay period conversion information.
The measurement control device includes:
an electrolysis execution acquisition unit that acquires execution information indicating execution of electrolysis;
a measurement instruction unit that causes the measuring means to measure conductivity information when electrolysis is not being executed based on the execution information,
The concentration calculation unit includes:
Based on the difference between the previous conductivity information, which is the conductivity information measured before the electrolysis, and the last post-conductivity information in the generation period, which is the conductivity information measured after the electrolysis. Based on the calculated hypochlorous acid concentration and the post-conductivity information, conductivity information measured after the post-conductivity information in the production period in the decay period and the calculated hypochlorous acid concentration information The hypochlorous acid concentration measuring device according to claim 9, wherein the absolute value of the hypochlorous acid concentration is calculated based on the hypochlorous acid concentration.
An electrolytic tank that stores water containing chlorine,
an electrolytic electrode inserted into the electrolytic cell;
an electrolytic device that applies a voltage to the electrolytic electrode to electrolyze the water containing chlorine to generate hypochlorous acid water;
The hypochlorous acid concentration measuring device according to claim 1,
A main control device that controls the electrolyzer,
The measurement control device includes:
an electrolysis execution acquisition unit that acquires execution information indicating execution of electrolysis;
a measurement instruction unit that causes the measuring means to measure conductivity information when electrolysis is not being executed based on the execution information,
The concentration calculation unit includes:
Calculating the hypochlorous acid concentration based on the conductivity information measured before and after performing electrolysis and the conversion information,
The main control device includes:
Hypochlorite comprising an electrolysis control unit that outputs electrolysis information such that the concentration of hypochlorous acid in the electrolytic cell becomes a target concentration to the electrolysis device based on information on the concentration of hypochlorous acid calculated by the concentration calculation unit. Acid water generator.
The main control device includes:
Equipped with an execution information acquisition unit that acquires execution information,
The electrolysis control section is
If the hypochlorous acid concentration calculated by the concentration calculation unit is lower than the target concentration, the hypochlorous acid concentration is lower than the target concentration based on the current value and duration during electrolysis execution included in the execution information. The hypochlorous acid water generating device according to claim 12, wherein electrolytic information including at least one of a current value and a duration time is calculated.
The main control device includes:
Equipped with an execution information acquisition unit that acquires execution information,
The electrolysis control section is
If the hypochlorous acid concentration calculated by the concentration calculation unit is higher than the target concentration, measurement instruction information that causes conductivity information to be measured after a predetermined second time has elapsed from the execution of electrolysis corresponding to the execution information. A concentration at which the concentration of hypochlorous acid in the electrolytic cell is lower than the target concentration, based on information on the hypochlorous acid concentration output to the measurement control device and calculated by the concentration calculation unit after the second time period has elapsed. The hypochlorous acid water generating device according to claim 12, wherein electrolytic information including a drop time is output to the electrolytic device.