JP6609489B2 - Electrolyte analyzer - Google Patents

Description

  The present invention relates to an electrolyte analyzer mounted on an automatic analyzer.

  Biochemical automatic analyzers analyze samples containing proteins such as blood samples and urine samples.

  The electrolyte analyzer is an apparatus that analyzes electrolyte components such as sodium (Na), potassium (K), and chlor (Cl) in a sample. Currently, many devices use a method called ion selective electrode method (ISE method). In the ISE method, the electrolyte concentration in the specimen is measured by measuring the potential difference between the ion selective electrode (ISE) and the reference electrode that generates the reference potential. The ISE electrode is attached with an ion-sensitive film that generates a potential difference in response to an ion component, and the potential varies depending on the electrolyte concentration in the specimen. In order to maintain the reference potential, the reference electrode comes into contact with a solution called a reference electrode solution. In many cases, a high concentration KCL solution is used as the reference electrode solution. In many electrolyte analyzers, in order to achieve high throughput, analysis is performed by a flow method in which a specimen to be examined is continuously sent.

  In order to clean the flow path of the flow type electrolyte analyzer, a cleaning liquid containing hypochlorite is used. In order to avoid damage to the ion sensitive membrane, it is desirable that the cleaning solution for the electrolyte analyzer does not contain a surfactant component. As a component of the cleaning solution, it is desirable to contain 0.01% or more of hypochlorite ions in order to decompose proteins and kill bacteria.

  However, hypochlorite ions are unstable due to heat and light. Therefore, in order to avoid fluctuations in the effective chlorine concentration in the cleaning liquid due to decomposition or concentration of hypochlorous acid, it was essential to strictly observe the storage temperature and the deadline. Moreover, the hypochlorous acid component and the alkali component have a great influence on the human body, and care must be taken by the user. In order to avoid the labor required for such maintenance, it is desired to automate cleaning in the apparatus.

  For example, Patent Document 1 is known as a method for generating a cleaning liquid in a biochemical automatic analyzer. In Patent Document 1, an acidic solution containing hypochlorous acid or an alkaline solution generated by electrolyzing tap water containing a small amount of sodium chloride in a diaphragm type electrolytic cell is used as a sample contact site of a biochemical automatic analyzer. The method used for cleaning is described.

JP-A-11-153604

  In order to automate cleaning in the apparatus, it is conceivable to generate a cleaning liquid containing hypochlorite ions by electrolysis in the apparatus. However, as in Patent Document 1, when tap water is used to generate a cleaning liquid, tap water may contain impurities such as metal ions, or variations in the chlorine ion concentration of tap water may be large. It is difficult to produce a cleaning liquid. As another method, an aqueous solution containing hydrochloric acid may be used for electrolysis. However, when a user installs an aqueous solution containing chlorine ions, the user needs to be careful in handling and requires troublesome installation.

  Therefore, an object of the present invention is to provide an electrolyte analyzer capable of generating a cleaning solution containing hypochlorous acid having a stable concentration by simple handling.

In order to solve the above problems, the present invention generates a hypochlorous acid solution by electrolysis using a comparative electrode solution provided in advance in the electrolyte analyzer. More specifically, the electrolyte analyzer of the present invention includes a sample container for holding a sample, a dilution tank for diluting a sample injected from the sample container, an ion selection electrode, and a comparison electrode, An ion selection electrode portion for measuring the concentration of an electrolyte contained in the sample by a potential difference between the ion selection electrode and the comparison electrode; a first flow path for feeding the sample to the ion selection electrode; and a comparison electrode A comparison electrode solution bottle for storing the solution; an electrolytic cell for electrolyzing the comparison electrode solution to generate a hypochlorous acid solution; and a second flow path for supplying the comparison electrode solution to the electrolytic cell. And at least one of the following features. That is, the apparatus further includes a third flow path for introducing the hypochlorous acid solution generated in the electrolytic cell into the dilution tank, or the hypochlorous acid solution generated in the electrolytic cell is added to the sample container. Or a transport mechanism for transporting the sample container holding the hypochlorous acid solution, or the comparison electrode solution bottle, the electrolytic cell, and the first or the flow path of which is connected hermetically, that having a least one of the characteristics of the.

  According to the present invention, a cleaning solution containing hypochlorous acid having a stable concentration can be generated by simple handling in an electrolyte analyzer.

1 is a schematic diagram illustrating an overall configuration of Embodiment 1. FIG. FIG. 6 is a schematic diagram illustrating an overall configuration of Embodiment 2. The schematic diagram of a diaphragm type electrolytic cell. The schematic diagram of a diaphragm type electrolytic cell.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  In this embodiment, an electrolyte analyzer mounted on an automatic analyzer will be described as an example. Examples of the automatic analyzer include a biochemical automatic analyzer and an immune automatic analyzer. However, this is merely an example of the present invention, and the present invention is not limited to the embodiments described below. For example, a mass spectrometer used for clinical examinations and a coagulation analyzer for measuring blood coagulation time are also included. Further, the present invention can be applied to a combined system of these with a biochemical automatic analyzer and an immune automatic analyzer, or an automatic analysis system using these systems. Alternatively, the electrolyte analyzer may be used alone.

  In this specification, “specimen” is a general term for analysis objects collected from a living body of a patient, such as blood and urine. Analyzes for which a predetermined pretreatment has been performed on these are also included in the “sample”. The “specimen” may also be referred to as “sample”.

  FIG. 1 is an overall schematic diagram of the electrolyte analyzer of this embodiment.

  The electrolyte analyzer is roughly divided into four parts: a sample dispensing part, an ISE electrode part, a reagent part and a mechanism part. The sample dispensing unit includes a sample probe 14 and a sample container 15. A sample such as a patient specimen held in the sample container 15 is dispensed by the sample probe 14 and drawn into the apparatus.

  The ISE electrode section includes a dilution tank 11, a shipper nozzle 13, a dilution nozzle 24, an internal standard solution nozzle 25, a waste solution nozzle 26, an ISE electrode 1, a comparison electrode 2, a pinch valve 23, a voltmeter 27, an amplifier 28, and a computer 29. The specimen dispensed by the sample dispensing unit is discharged into the dilution tank 11, and diluted and stirred with a diluent discharged from the dilution nozzle 24 into the dilution tank 11. The sipper nozzle 13 is connected to the ISE electrode 1 through a flow path, and the sample sucked from the dilution tank 11 is sent to the ISE electrode 1 through the flow path. The comparison electrode solution stored in the comparison electrode solution bottle 5 is fed to the comparison electrode 2 by operating the sipper syringe 10 with the pinch valve 23 closed. The diluted sample solution sent to the ISE electrode channel and the comparison electrode solution sent to the comparison electrode channel come into contact with each other, whereby the ISE electrode 1 and the comparison electrode 2 are electrically connected. The ISE electrode unit measures the concentration of a predetermined electrolyte contained in the sample based on the potential difference between the ISE electrode 1 and the comparison electrode 2.

More specifically, the electromotive force of the ISE electrode 1 varies depending on the concentration of a specific ion (for example, sodium (Na ⁺ ), potassium ion (K ⁺ ), chlor ion (Cl ⁻ ), etc.) in the sample. An ion sensitive film having properties is attached, and the ion selective electrode outputs an electromotive force corresponding to each ion concentration in the specimen. An electromotive force between the ISE electrode 1 and the comparison electrode 2 is acquired by the voltmeter 27 and the amplifier 28, and the ion concentration in the specimen is calculated and displayed by the computer 29. After the sample is fed from the dilution tank to the ISE electrode, the waste liquid remaining in the dilution tank is sucked by the waste liquid nozzle 26 and discharged. In order to correct the potential fluctuation due to the influence of temperature change or the like, the internal standard solution is discharged from the internal standard solution nozzle 25 into the dilution tank 11 after the sample measurement and before the next sample measurement, and the measurement is performed in the same manner as the sample. It is preferable to perform correction according to the amount of variation using the internal standard solution measurement results measured between the samples.

  The reagent unit includes an internal standard solution bottle 3 that stores an internal standard solution, a dilution solution bottle 4 that stores a dilution solution, a comparison electrode solution bottle 5 that stores a comparison electrode solution, a degassing mechanism 7, a filter 16, and an electrolytic cell 6. It supplies reagents necessary for measurement and cleaning. The internal standard solution bottle 3 and the diluting solution bottle 4 are connected to the internal standard solution nozzle 25 and the diluting solution nozzle 24 through the flow path through the filter 16, and each nozzle is installed in a shape in which a tip is introduced into the diluting tank 11. Has been. The comparative electrode liquid bottle 5 is connected to the comparative electrode 2 through a flow path. A degassing mechanism 7 is connected to the flow path between the diluent bottle 8 and the dilution tank 11 and the flow path between the comparative electrode liquid bottle 5 and the comparative electrode 2, and the degassed solution is put into the dilution tank. Discharged. A pure water production apparatus 30 is connected to the electrolytic cell 6 by a flow path. Moreover, in order to supply a comparative electrode solution as an electrolytic solution in the electrolytic cell 6, the electrolytic cell 6 and the comparative electrode solution bottle 5 are connected by a flow path. In the electrolytic cell 6, the comparative electrode solution is electrolyzed to produce a hypochlorous acid solution. Further, the electrolytic bath 6 sends the generated hypochlorous acid solution to the dilution bath 11, so that the internal standard solution flow path including the internal standard solution syringe 8 or the dilution solution including the dilution syringe 9 and the degassing mechanism 7 is used. The flow path is connected to the dilution nozzle 24 or the internal standard solution nozzle 25 installed in the dilution tank 11 via the flow path. The comparative electrode solution bottle 5, the electrolytic cell 6, and the flow path through which the hypochlorous acid solution is fed are sealed. Thereby, it can prevent that a user contacts a hypochlorous acid solution accidentally.

  The mechanism section includes an internal standard solution syringe 8, a diluent syringe 9, a sipper syringe 10, electromagnetic valves 17, 18, 19, 20, 21, 22, and a preheat 12, and is responsible for the operation of each mechanism such as liquid feeding.

  The internal standard solution and the diluted solution are sent to the dilution tank by the operation of the internal standard solution syringe 8 and the diluted solution syringe 9 and the electromagnetic valve. Since the ISE electrode 1 is likely to be affected by temperature, the temperature of the internal standard solution and the diluting solution reaching the ISE electrode 1 is controlled within a certain range through the preheat 12. When the hypochlorous acid solution generated in the electrolytic cell 6 is sent to the diluent flow path, the electromagnetic valve 19 is closed, and the mixture of the hypochlorous acid solution into the diluent bottle 4 is prevented. The valve 17 is closed and the solenoid valve 18 is opened, and the hypochlorous acid solution is fed by the diluent syringe 9. Similarly, when liquid is sent to the internal standard solution flow path, the solenoid valves 18 and 20 are closed, and the hypochlorous acid solution is sent by the internal standard solution syringe 8.

  The flow path for feeding the hypochlorous acid solution can be selected according to the site that needs to be cleaned. When the ISE electrode 1 flow path is cleaned through the dilution tank 11, any flow path may be used.

  One of the features of the apparatus shown in FIG. 1 is that the apparatus includes an electrolytic cell 9 to which a reference electrode solution bottle 5 for ISE measurement is connected. By using the comparative electrode solution, the channel cleaning can be performed without the user's operation of adjusting the solution.

  First, an outline of the sample measurement operation will be described.

  In the sample dispensing unit, the sample dispensed from the sample container 15 by the sample probe 14 is discharged to the dilution tank 11 of the ISE electrode unit. After the sample is dispensed into the dilution tank 11, the diluent is discharged from the dilution bottle 4 by the operation of the diluent syringe 9 from the dilution nozzle 24, and the specimen is diluted. In order to prevent bubbles from being generated due to changes in the temperature and pressure of the diluent in the flow path, a degassing process is performed by a degassing mechanism 7 attached in the middle of the diluent flow path. The diluted specimen is sucked into the ISE electrode 1 by the operation of the sipper syringe 10 and the electromagnetic valve 22.

  Further, the comparison electrode solution is fed from the comparison electrode solution bottle 5 into the comparison electrode 2 by the pinch valve 23 and the sipper syringe 10. The reference electrode solution is composed of an aqueous solution of potassium chloride (KCl) having a predetermined concentration, and the ISE electrode 1 and the comparison electrode 2 are electrically connected when the sample and the reference electrode are in contact with each other. The concentration of the reference electrode solution is preferably high to suppress the influence of concentration fluctuations while the sample is being fed, but it may crystallize near the saturated concentration and cause clogging of the flow path. , Preferably between 0.5 mmol / L and 3.0 mmol / L. The fluctuation of the ISE electrode potential with reference to the comparison electrode potential is measured using a voltmeter 27 and an amplifier 28. Further, before and after the sample measurement, the internal standard solution in the internal standard solution bottle 3 of the reagent part is discharged to the dilution tank 11 by the internal standard solution syringe 8, and the internal standard solution is measured by the same operation as the sample measurement. Calculation is performed by the computer 29 using the measured potential difference to calculate the electrolyte concentration in the sample.

  Next, a mechanism for generating the cleaning liquid in this embodiment will be described.

  As a method of generating a solution containing hypochlorous acid in the apparatus, a method of generating hypochlorous acid water by electrolyzing an aqueous solution containing chlorine ions and using it for cleaning and sterilization can be considered. The principle is shown by the following equation.

[陰極]

[anode]

[cathode]

As a method for performing electrolysis, there are a diaphragm type in which a diaphragm is provided between an anode and a cathode, and a non-diaphragm type in which no diaphragm is provided. As an example using the diaphragm type, there is a method in which a solution containing chlorine ions prepared in advance is electrolyzed and a solution containing hypochlorous acid obtained from the compartment on the anode side is extracted. In the diaphragm type, an acidic solution is generated by hydrochloric acid generated simultaneously with hypochlorous acid on the anode side, and hydroxide ions are generated on the cathode side to generate an alkaline solution.
On the other hand, as an example using the non-membrane type, there is a method of generating hypochlorous acid in a neutral pH state by electrolyzing a solution containing chlorine ions.

  3 and 4 are schematic views of the electrolytic cell. FIG. 3 shows a diaphragm type electrolytic cell, and FIG. 4 shows a membrane type electrolytic cell in which a membrane 43 made of a cation exchange membrane is provided between the negative and anode. In the present embodiment, both a diaphragm type electrolytic cell and an electrolytic type electrolytic cell can be used. Desirably, an acidic solution produced on the anode side and an alkaline solution produced on the cathode side are mixed to obtain a hypochlorous acid solution close to neutrality, rather than a diaphragm type in which the anode side solution containing hypochlorous acid is acidic. A diaphragm-type electrolytic cell is desirable.

  3 includes an electrolytic cell container 34, an anode 35, a cathode 36, and a power source 37. An anode 35 and a cathode 36 are installed in the electrolytic cell container 34, and the comparison electrode solution and pure water are fed to the electrolytic cell container 34 by a pump 40 or 41, respectively. When the comparison electrode solution or pure water is introduced from the comparison electrode solution bottle 38 or the pure water production apparatus 39, the electrodes are electrically connected. When a predetermined voltage is applied by a power source 37 connected to the anode 35 and the cathode 36, a hypochlorous acid solution is generated by the above-described chemical reaction.

  The electrolytic cell of FIG. 4 has a diaphragm 43 that separates the inside of the electrolytic cell container 34 to the anode 35 side and the cathode 36 side in addition to the configuration of FIG. 3. The diaphragm 43 is an anion exchange type ion exchange membrane that suppresses the passage of anions. The deionized water production device 39 and the pump 41 are connected to the cathode side across the diaphragm 43 and supplied with deionized water. The comparison electrode solution bottle 42 and the pump 40 are connected to the anode side and supplied with the comparison electrode solution. . On the anode side, a flow path serving as an output for sending the generated solution to an automatic analyzer and using it for cleaning is installed. When a voltage is applied between the cathode 35 and the anode 36 by the power source 37, the cation contained in the reference electrode solution can move through the diaphragm, so that a current can flow between the anode 35 and the cathode 36. When electrolysis is performed as in FIG. 3, a solution containing hypochlorous acid is generated on the anode 35 side.

  Next, the generation of the cleaning liquid and the cleaning operation using the generated cleaning liquid in this embodiment will be described.

  The frequency of the cleaning operation is preferably performed at least once every 24 hours, but once every 24 hours is desirable in order to ensure time for sample measurement.

  The cleaning part has two channels, one for the internal standard solution and the other for the diluent. However, the two channels may be cleaned at the same time, and if necessary, the channel is dirty. Only cleaning may be performed.

The timing of cleaning can be performed at any timing without a sample measurement request.
After the conventional biochemical automatic analyzer is activated, a prime operation is required to replace the reagents that have accumulated and deteriorated in the flow path with the reagents in the bottle. In this example, after the cleaning process with hypochlorous acid generated as described later, the cleaning liquid remaining in the flow path is rinsed with a rinsing liquid, and the internal standard solution and the diluting liquid in the bottle are used. Replace the road. Therefore, it is more desirable to perform cleaning, rinsing and replacement in the flow path instead of the prime operation because the prime operation and the cleaning operation can be performed in one operation.
Cleaning can be performed automatically at a timing set in advance by the user, or an operator can manually request execution at an arbitrary timing.

  Since hypochlorous acid is unstable and easily decomposed, in order to perform washing with a hypochlorous acid solution having a stable concentration every time, the generation of hypochlorous acid in the electrolytic cell 6 is an amount necessary immediately before washing. It is desirable to do only.

  The concentration of hypochlorous acid required for cleaning the flow path is 0.01% or more. This is because a high concentration is desirable for shortening the cleaning time. However, in view of the remaining in the flow channel after cleaning and the damage to the flow channel material, it is preferably in the range of 0.05% to 0.1%.

  A cleaning solution is generated in the electrolytic cell 6 before cleaning. The solenoid valves 20 and 19 are closed, and the reference electrode solution is sucked into the electrolytic cell 6 by the internal standard solution syringe 8 and the diluent syringe 9. The amount of the reference electrode solution to be sucked can be set in the range of 0.5 mL to 20 mL according to the amount of the cleaning solution to be generated. However, the larger the amount, the longer it takes to obtain a predetermined concentration by the electrolytic reaction. Is 10 mL. The reference electrode solution is maintained at a predetermined concentration for measuring the electrolyte of the sample. Therefore, it is possible to always supply the comparison electrode solution having the same concentration to the electrolytic cell, and it is possible to stably produce a hypochlorous acid solution having the same concentration.

  The electrode material in the electrolytic cell must be stable against acidic and alkaline solutions. In addition to metal materials such as platinum, gold, and silver, carbon materials and composite materials of these materials should be used. However, platinum is preferable.

According to the above formulas 2 and 3, the amount of hypochlorous acid generated increases as the applied current value increases. Since the area where the electrode contacts the solution affects the current value, it is desirable that the electrode area be large in order to obtain hypochlorous acid efficiently. For example, considering the balance between electrolytic cell size, it is desirable that the range of 50mm ² ~1,000mm ^2. Examples of a method for obtaining a wide electrode area in the electrolytic cell include a method in which the electrode material has a honeycomb structure, and a method in which thin thin film electrodes are stacked with a predetermined interval. Since the current value affects the amount of hypochlorous acid produced, it varies depending on the amount of cleaning liquid required and the concentration of cleaning liquid, but is preferably in the range of 1A to 10A.

  The applied voltage only needs to be able to supply energy necessary for deoxidizing electrons from chlorine ions in the reference electrode solution on the anode side and to obtain a sufficient current value. Desirably, it is in the range of 2V to 20V.

  In accordance with the above, after the hypochlorous acid solution is generated in the electrolytic cell 6, the hypochlorous acid solution is fed to the flow path by the internal standard solution syringe 8 or the diluting solution syringe 9, and the internal standard solution nozzle 25, the diluting solution nozzle 24 is discharged to the dilution tank 11.

  Subsequently, the hypochlorous acid solution in the dilution tank 11 is fed from the sipper nozzle 13 to the ISE electrode side by the sipper syringe 10. Since the inside of the flow path is filled with the hypochlorous acid solution by the above operation, the flow path can be washed.

  The hypochlorous acid solution discharged to the dilution tank from the internal standard solution nozzle 25 or the dilution solution nozzle 24 is continuously supplied with pure water supplied from the pure water production apparatus 30 in order to reduce damage to the ISE electrode, After diluting with the diluent sent from the diluent bottle 4, the solution may be sent to the ISE electrode.

  Since the hypochlorous acid solution component is a solution containing hypochlorous acid obtained by decomposing the potassium chloride solution as the comparative electrode solution, after filling the ISE flow path with the hypochlorous acid solution, The concentration of the solution used for cleaning can be confirmed by measuring the electrolyte concentration in the hypochlorous acid solution with the ISE electrode portion by the same method as the sample measurement. That is, the concentration is measured by the ISE electrode part while flowing a solution containing hypochlorous acid through the flow path. If the measured amount of electrolyte is within a predetermined range, it can be confirmed that a cleaning liquid having an appropriate concentration is produced. Further, if the measured concentration is outside the predetermined range, an alarm may be issued or re-cleaning may be performed.

  After filling with the hypochlorous acid solution, the solution may be held for a certain period of time in order to perform cleaning effectively, or the solution may be fed multiple times.

  After washing the flow path with the hypochlorous acid solution, a rinsing liquid is sent to the flow path for the measurement operation to perform rinsing. The rinsing liquid is preferably pure water, for example. Pure water produced by the pure water production apparatus 30 connected to the electrolytic cell 6 is fed to the electrolytic cell, and is fed to the flow channel to which the ISE electrode 1 is connected in the same flow path as the hypochlorous acid solution. To do. The pure water, which is a rinsing liquid, continues to be sent to a concentration at which the concentration of the rinsing liquid in which the hypochlorous acid solution remaining in the flow path is dissolved does not affect the next measurement. For example, it is desirable that the amount of pure water delivered be three times or more the volume of the hypochlorous acid solution used for cleaning.

  In addition, in order to confirm that the hypochlorous acid solution has been sufficiently removed by the rinsing process with pure water, it is possible to confirm the remaining amount of the hypochlorous acid solution with the ISE electrode in the same manner as the sample measurement described above. I can do it. That is, the concentration of the electrolyte contained in the ISE electrode portion is measured while flowing the rinsing liquid through the flow path. In the rinsing step, if the amount of electrolyte measured by the ISE electrode is equal to or less than a predetermined threshold value, it is determined that the rinsing is sufficiently completed, and measurement of the next sample can be started. Further, if the measured concentration is outside the predetermined range, an alarm may be issued or re-cleaning may be performed.

  According to the present embodiment, it is possible to eliminate the work for the user to sequentially install the cleaning liquid. In addition, a cleaning solution having a stable concentration can be generated by simple handling.

  Next, another configuration example of the electrolyte analyzer will be described with reference to FIG. Hereinafter, description of the same parts as those in the first embodiment will be omitted.

  The structural difference between the present example and Example 1 is the position of the flow path for taking out and feeding the hypochlorous acid solution generated in the electrolytic cell 6. In this embodiment, the electrolytic cell is connected to the dilution tank via the hypochlorous acid syringe 33 and the hypochlorous acid nozzle 31, and the hypochlorous acid solution is directly discharged to the dilution tank by the operation of the hypochlorous acid syringe. The

  In this embodiment, a hypochlorous acid solution is supplied to the sample container 15. More specifically, a hypochlorous acid nozzle 31 is provided in a flow path connected to the sample container 15 from the electrolytic cell 6 and a position where a hypochlorous acid solution can be discharged. An empty sample container is installed at the time of cleaning, and the hypochlorous acid solution generated in the electrolytic cell 6 is discharged to the empty sample container through the hypochlorous acid nozzle 31. After the hypochlorous acid solution in the sample container is dispensed by the sample nozzle 14 and discharged to the dilution tank 11, cleaning is performed by sending the hypochlorous acid solution to the ISE electrode flow path by the sipper nozzle 13. After feeding the hypochlorous acid solution, pure water is fed from the pure water production apparatus 30 and rinsed.

  Furthermore, the electrolyte analyzer of the present embodiment may include a transport device that transports the sample container storing the hypochlorous acid solution to another analysis unit connected to the electrolyte analyzer. By transporting the sample container containing the hypochlorous acid solution to a place where cleaning is necessary, the sample container can be used for cleaning mechanisms other than the ISE electrode channel. For example, when the electrolyte analyzer of this embodiment is connected to an automatic branching device, it can also be used for washing mechanisms such as a colorimetric reaction cell and sample nozzle of the automatic analyzer.

1: ISE electrode, 2: Comparative electrode, 3: Internal standard solution bottle, 4: Dilution liquid bottle, 5, 38: Comparative electrode solution bottle, 6: Electrolyzer, 7: Degassing mechanism, 8: Internal standard solution syringe, 9: Diluent syringe, 10: Shipper syringe, 11: Dilution tank, 12: Preheat, 13: Shipper nozzle, 14: Sample nozzle, 15: Sample container, 16: Filter, 17, 18, 19, 20, 21, 22, 32: Solenoid valve, 23: Pinch valve, 24: Dilution liquid nozzle, 25: Internal standard liquid nozzle, 26: Waste liquid suction nozzle, 27: Voltmeter, 28: Amplifier, 29: Computer, 30, 39: Pure water production apparatus 31: Hypochlorous acid nozzle, 33: Hypochlorous acid syringe, 34: Electrolyzer vessel, 35: Anode, 36: Cathode, 37: Power supply, 40, 41: Pump, 42: Electrolyte analyzer, 43: Diaphragm

Claims (15)

A sample container for holding the sample;
A dilution tank for diluting the sample injected from the sample container;
An ion selection electrode unit that includes an ion selection electrode and a comparison electrode, and measures a concentration of an electrolyte contained in the sample by a potential difference between the ion selection electrode and the comparison electrode;
A first flow path for feeding a sample diluted in the dilution tank to the ion selective electrode;
A comparison electrode solution bottle for storing the comparison electrode solution;
An electrolytic cell for electrolyzing the comparative electrode solution to produce a hypochlorous acid solution;
A second flow path for supplying the comparison electrode solution to the electrolytic cell;
A third flow path for introducing the hypochlorous acid solution generated in the electrolytic tank into the dilution tank;
An electrolyte analyzer characterized by comprising: A sample container for holding the sample;
A dilution tank for diluting the sample injected from the sample container;
An ion selective electrode part that includes an ion selective electrode and a comparative electrode, and measures a concentration of an electrolyte contained in the sample by a potential difference between the ion selective electrode and the comparative electrode;
A first flow path for feeding a sample diluted in the dilution tank to the ion selective electrode;
A comparison electrode solution bottle for storing the comparison electrode solution;
An electrolytic cell for electrolyzing the comparative electrode solution to produce a hypochlorous acid solution;
A second flow path for supplying the comparison electrode solution to the electrolytic cell;
A fourth flow path for feeding the hypochlorous acid solution generated in the electrolytic cell to the sample container;
A transport mechanism for transporting the sample container holding the hypochlorous acid solution;
The electrolyte analyzing apparatus, characterized in that it comprises a. A sample container for holding the sample;
A dilution tank for diluting the sample injected from the sample container;
An ion selection electrode unit that includes an ion selection electrode and a comparison electrode, and measures a concentration of an electrolyte contained in the sample by a potential difference between the ion selection electrode and the comparison electrode;
A first flow path for feeding a sample diluted in the dilution tank to the ion selective electrode;
A comparison electrode solution bottle for storing the comparison electrode solution;
An electrolytic cell for electrolyzing the comparative electrode solution to produce a hypochlorous acid solution;
A second flow path for supplying the comparison electrode solution to the electrolytic cell;
With
The electrolyte analysis apparatus characterized in that the comparison electrode solution bottle, the electrolytic cell, and the first flow path are hermetically connected . The electrolyte analyzer according to any one of claims 1 to 3 ,
The electrolyte analyzer according to claim 2, wherein the second flow path connects the electrolytic cell and the reference electrode solution bottle . The electrolyte analyzer according to any one of claims 1 to 3 ,
The electrolyte analysis apparatus, wherein the reference electrode solution is a potassium chloride solution . The electrolyte analyzer according to claim 5, wherein
The electrolyte analysis apparatus, wherein the reference electrode solution has a concentration range of 0.5 mmol / L to 3.0 mmol / L. The electrolyte analyzer according to any one of claims 2 to 3 ,
An electrolyte analyzer comprising a third flow path for introducing a hypochlorous acid solution generated in the electrolytic tank into the dilution tank . The electrolyte analyzer according to claim 1,
The electrolyte analyzer , wherein the first flow path is washed with a hypochlorous acid solution generated in the electrolytic cell. The electrolyte analyzer according to claim 1,
An electrolyte analyzer, wherein the concentration of the hypochlorous acid solution is in the range of 0.05 to 0.1% . The electrolyte analyzer according to claim 1 or 3 ,
A fourth flow path for feeding the hypochlorous acid solution generated in the electrolytic cell to the sample container;
A transport mechanism for transporting the sample container holding the hypochlorous acid solution;
The electrolyte analyzing apparatus, characterized in that it comprises a. The electrolyte analyzer according to any one of claims 1 to 3 ,
The electrolyte analyzer characterized in that the voltage applied to the electrolytic solution in the electrolytic cell is 2 to 20 V, and the current value is 1A to 10A . The electrolyte analyzer according to any one of claims 1 to 3 ,
The ion selective electrode unit measures the concentration of the hypochlorous acid solution generated in the electrolytic cell,
An electrolyte analyzer that issues an alarm or re-washes when the concentration is outside a predetermined concentration range . The electrolyte analyzer according to claim 8 , wherein
Furthermore, it has a pure water production device,
The electrolyte analyzer characterized in that after the first flow path is washed, a rinsing liquid is sent from the pure water producing apparatus to the first flow path .   The electrolyte analyzer according to claim 13,
  The ion selective electrode unit measures the concentration of the electrolyte contained in the rinsing liquid that has flowed through the first flow path, and issues an alarm or performs pure water cleaning again when the concentration is equal to or higher than a predetermined concentration.
An electrolyte analyzer characterized by that.   The electrolyte analyzer according to any one of claims 1 to 2,
  The comparative electrode solution bottle, the electrolytic cell, and the first flow path are hermetically connected.
An electrolyte analyzer characterized by that.

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