JP5182257B2 - Total organic carbon measuring device - Google Patents

Description

  The present invention mainly relates to a total organic carbon (TOC) measuring apparatus for evaluating organic contamination of water with less impurities called pure water or ultrapure water. Samples to be analyzed are pharmaceutical water, semiconductor manufacturing process water, cooling water, boiler water, tap water, and the like.

  The all-organic carbon constant apparatus includes a combustion type oxidation method in which organic substances are burned and oxidized in a high-temperature furnace, and a wet oxidation method in which organic substances are oxidized in an organic substance oxidative decomposition unit using ultraviolet light. The latter wet oxidation method is generally used for high-sensitivity measurement using pure water or ultrapure water as a measurement target. The present invention is also directed to an all-organic carbon apparatus using the latter wet oxidation method.

  As a method for measuring total organic carbon in the wet oxidation method, a carbon dioxide separation unit using a gas permeable membrane that allows carbon dioxide to pass through is provided after the organic oxidative decomposition unit, and the carbon dioxide in the sample water is composed of deionized water. A method of measuring the conductivity of measurement water by moving it to measurement water is known (see Patent Document 1).

  Furthermore, there has been proposed a total organic carbon measurement device that integrates devices using microfabrication technology to achieve both reduction in sample and reagent consumption and reduction in elution and permeation from piping (Patent Document 2). 3). The total organic carbon measuring device oxidizes the organic matter in the supplied sample water by ultraviolet irradiation and converts it into carbon dioxide, carbon dioxide in the sample water that has passed through the organic matter oxidative decomposition portion passes through the gas permeable membrane. A carbon dioxide separator that is moved into the measurement water consisting of deionized water, and a detector that determines the carbon dioxide concentration by measuring the conductivity of the measurement water that has passed through the carbon dioxide separator. In the separation unit, the sample water flows through a minute flow path formed in the chip.

  In order to move the carbon dioxide in the sample water to the measurement water through the gas permeable membrane, the sample water is kept acidic to make the carbon dioxide in the sample water into a gas state. Therefore, usually, an inorganic acid not containing a carbon component is added to the sample water, and the pH of the sample water is kept at a strong acidity of about 2, for example. As such an acid, phosphoric acid or sulfuric acid is used.

  In addition, the inorganic carbon (IC) dissolved in the sample water from the beginning is removed to measure the TOC concentration. For this purpose, acid is added to the sample water supplied to the organic oxidative decomposition unit, and the inorganic carbon component is removed by venting with a carrier gas not containing the carbon component, and then the sample water is supplied to the organic oxidative decomposition unit. I am doing so.

US Pat. No. 5,131,094 JP 2006-300353 A International Publication WO2008 / 047405 JP-A-10-90134 JP 2000-187027 A

  Such a TOC measuring device may be stored without being used for a long period of time, for example, about one month after measurement for a certain period. At that time, if the flow path for collecting the sample water or the flow path through which the sample water flows in the TOC measuring device is wet with the sample, in the case of acid added to the sample water, especially phosphoric acid, The viscosity of the phosphoric acid remaining in the flow path increases, causing the flow path to become clogged. If sample water remains, organic components in the sample water decay and organic matter grows, causing a TOC measurement error when measurement is started thereafter.

  In general, in an analysis apparatus for trace components in sample water, the flow path is usually washed with washing water after the analysis is completed (see Patent Document 4). In that case, the purpose of washing the flow path is to prevent contamination when the next sample is measured, and it is only washed with washing water and not dried. This is because cleaning is sufficient to prevent contamination, and if drying is desired, a separate flow path for flowing purge gas for drying is required.

  However, the inside of the flow path is wet only by washing with the washing water, and if it is stored without being used for a long time in that state, a trace amount of organic substances remaining in the flow path may also grow.

  As another analysis apparatus, there is also an apparatus in which a flow path is dried by flowing an inert gas in a direction opposite to that at the time of sample collection through a flow path for collecting a sample after completion of analysis (see Patent Document 5). However, since the inert gas of such an analyzer is not used for the purpose of analysis, a purge gas flow path that is not required for analysis must be separately provided to supply the purge gas for drying the flow path. In addition, the cost of the analyzer is increased accordingly.

  Therefore, in the TOC analyzer, in particular, in the TOC analyzer, when storing without using a new purge gas flow channel for a long period of time after the analysis is completed, the flow channel is cleaned and further dried. It is intended to prevent acid and organic matter from remaining on the surface.

  The TOC measurement device of the present invention includes a TOC measurement unit that measures the TOC concentration in the supplied sample water, a sample introduction unit that supplies sample water to the TOC measurement unit, and a control that controls operations of the TOC measurement unit and the sample introduction unit. Equipment.

  The TOC measurement unit oxidizes the organic matter in the supplied sample water by ultraviolet irradiation to convert it into carbon dioxide, and deionizes the carbon dioxide in the sample water that has passed through the organic matter oxidative decomposition portion through a gas permeable membrane. A carbon dioxide separation unit that is moved into measurement water made of water, and a detection unit that determines the carbon dioxide concentration by measuring the conductivity of the measurement water that has passed through the carbon dioxide separation unit. The flow path through which the sample water flows is a micro flow path formed in the chip.

  The sample introduction unit is connected to a flow path switching valve capable of switching and connecting a common port to each of the plurality of ports, a syringe connected to the common port of the flow path switching valve, and each of the plurality of ports. Opened to a sample water sampling channel for supplying sample water, an acid addition channel for supplying inorganic acid not containing carbon, a cleaning water channel for supplying cleaning water, a TOC measurement channel connected to the organic matter oxidative decomposition unit, and a drain The drain flow path is provided. The syringe is composed of a cylinder and a piston that slides inside the cylinder. The cylinder has a distal end connected to the common port, and a proximal end of the cylinder is retracted toward the proximal end of the cylinder. A gas pipe for supplying a carrier gas containing no carbon component is connected.

  The control device includes a measurement unit control unit that controls the conductivity measurement operation by the TOC measurement unit, a valve control unit that controls the operation of the flow path switching valve, a syringe control unit that controls the operation of the syringe, and the valve control unit And a sample introduction control unit for controlling the operation of the sample introduction unit via the syringe control unit, cleaning for storage in a state where the acid addition channel and the sample water sampling channel are set to suck pure water, respectively. When the storage cleaning button is instructed from the storage cleaning button, the following cleaning and drying processes (A), (B) and (C) are performed via the valve control unit and the syringe control unit. A storage cleaning means for performing the process is provided.

  (A) The acid addition flow path is washed by sucking pure water from the acid addition flow path into the syringe and discharging it from the drain flow path, and then the carrier gas from the gas pipe is added to the acid by the syringe. Operation for supplying to the flow path and drying the acid addition flow path.

  (B) The sample water sampling channel is washed by sucking pure water from the sample water sampling channel into the syringe and discharging it from the drain channel, and then the carrier gas from the gas pipe is An operation of supplying the sample water sampling channel and drying the sample water sampling channel.

  (C) Flow through which the sample water of the organic matter oxidative decomposition section flows by sucking the wash water from the wash water flow path into the syringe and supplying the sample water of the organic matter oxidative decomposition section from the TOC measurement flow path The operation of washing the channel and then supplying the carrier gas from the gas pipe to the channel through which the sample water of the organic matter oxidative decomposition unit flows by the syringe to dry the channel through which the sample water of the organic matter oxidative decomposition unit flows.

  Storage cleaning means cleaning for long-term storage.

  An example of an inorganic acid that does not contain carbon supplied from the acid addition channel is phosphoric acid. Since the viscosity of the phosphoric acid solution increases when dried, it is likely to cause clogging of fine flow paths, and thus the significance of applying the present invention is particularly great. Examples of other acids include sulfuric acid.

  Of the steps (A), (B) and (C), the step (A) is first processed. The process to be processed subsequently may be either (B) or (C). That is, the order of the process is (A) → (B) → (C) or (A) → (C) → (B).

  In the step (C), when the flow path through which the sample water of the organic matter oxidative decomposition section flows is washed with washing water, the flow path may be irradiated with ultraviolet rays. Thereby, even if organic matter remains in the flow path, it is decomposed by ultraviolet rays, and a state without organic matter can be created.

  Further, in the step (C), after washing the flow path through which the sample water in the organic matter oxidative decomposition section is washed, the tip of the wash water flow path on the washing water container side is opened, The washing water channel may be dried together with the drying. Thereby, a washing water channel can also be made into a dry state.

  In the present invention, when it is known that the sample is not used for a long period of time after the analysis is completed, the sample water in the oxidative decomposition unit is activated from the acid addition channel, the sample water sampling channel, and the TOC measurement channel by activating the storage and washing means. The acid and organic substances attached to the flow path are removed by washing the flow path through which the water flows, and then dried with a carrier gas. There is nothing to do. In particular, since the flow path through which the sample water flows in the oxidative decomposition part is a fine flow path formed in the chip, there is no possibility of clogging. Moreover, since the gas pipe for supplying the carrier gas to be flown for drying is originally provided in the sample introduction part for use in measurement with this TOC measuring device, it is necessary to separately provide a carrier gas pipe for drying. There is no.

It is the schematic which shows one Example. It is a block diagram which shows the structure of the Example. It is a block diagram which shows the control apparatus in the Example. It is a flowchart which shows the whole washing | cleaning operation | movement in the Example. It is a flowchart which shows the washing | cleaning operation | movement of the phosphoric acid addition flow path in the Example. It is a flowchart which shows the washing | cleaning operation | movement of the sample water sampling flow path in the Example. It is a flowchart which shows the washing | cleaning operation | movement of the TOC measurement flow path in the Example.

  FIG. 1 schematically shows an entire TOC measuring apparatus according to an embodiment. The TOC measurement unit 2 is connected to an autosampler that is the sample introduction unit 4, and sample water is automatically collected and supplied to the TOC measurement unit 2. In order to control the operation of the TOC measurement unit 2 and the sample introduction unit 4, a personal computer is connected as the control device 6. The control device 6 is not limited to a personal computer, and may be a microprocessor dedicated to this TOC measuring device.

  Detailed configurations of the TOC measurement unit 2 and the sample introduction unit 4 are shown in FIG. The TOC measurement unit 2 includes an organic matter oxidative decomposition unit 10, a carbon dioxide separation unit 14, and a detection unit 16.

  The organic matter oxidative decomposition unit 10 oxidizes organic matter in the sample water supplied from the sample introduction unit 4 through the TOC measurement channel 46 by ultraviolet irradiation from an ultraviolet lamp 12 such as a mercury lamp, and converts it into carbon dioxide. is there.

  The carbon dioxide separation unit 14 moves the carbon dioxide in the sample water that has passed through the organic matter oxidative decomposition unit 10 into measurement water composed of deionized water through a gas permeable membrane.

  The flow path through which the sample water of the carbon dioxide separator 14 flows is a micro flow path formed in the chip. When the organic matter oxidative decomposition unit 10, the carbon dioxide separation unit 14, and the detection unit 16 are integrated into a chip, a flow path through which sample water flows in the organic matter oxidative decomposition unit 10 is also formed in the chip. It becomes a minute channel. In the TOC measurement unit 2, if the sample water is a flow path through which the sample water flows, and the phosphoric acid remains in the flow path for a long time, the viscosity of the phosphoric acid increases and the flow path is increased. The risk of blockage increases.

  The detector 16 measures the conductivity of the measurement water that has passed through the carbon dioxide separator 14 to determine the carbon dioxide concentration. The detection unit 16 has a circulation channel 17 that absorbs carbon dioxide moving from the carbon dioxide separation unit 14 through the gas permeable membrane, and supplies deionized water used as measurement water to detect the conductivity of the measurement water. Is provided. Although the circulation flow path 17 is illustrated in a simplified manner, the circulation flow path 17 includes an ion exchange resin, and the measurement water whose conductivity is detected by the detection unit 16 is regenerated by the ion exchange resin and used again as measurement water.

  The specific structure of the TOC measurement unit 2 can be the one described in Patent Document 2 or 3.

  The sample introduction unit 4 includes a flow path switching valve 20 that can switch and connect the common port 22 to each of a plurality of ports. An 8-port valve is used as the flow path switching valve 20. Since all eight ports are not used in this embodiment, a six-port valve can be used here. A syringe 24 is connected to the common port 22 of the flow path switching valve. A sample water sampling channel 34 connected to the sample container 36 is connected to the port a of the plurality of ports, and the sample water can be sucked into the syringe 24 from the sample water sampling channel 34. The sample water sampling channel 34 can also directly inhale water from a line such as a semiconductor manufacturing process, and this TOC measuring device can be used for on-line measurement. In order to add phosphoric acid as an inorganic acid not containing carbon to the sample water, an acid addition passage 38 connected to the phosphoric acid cartridge 40 is connected to the port b, and the syringe is passed from the phosphoric acid cartridge 40 through the acid addition passage 38. The phosphoric acid is sucked into 24. A washing water channel 42 connected to a cartridge or bottle 44 containing pure water or deionized water as washing water is connected to the port c, and the washing water is sucked into the syringe 24 from the washing water container 44. Connected to the port d is a TOC measurement channel 46 that is connected to the organic oxidative decomposition unit 10 and supplies sample water to the organic oxidative decomposition unit 10. A drain flow path 48 that is open to the drain is connected to the port e.

  The syringe 24 includes a cylinder 26 and a piston 28 that slides inside the cylinder 26, and the cylinder 26 has a distal end connected to the common port e, and the piston 28 is retracted toward the proximal end of the cylinder 26 at the proximal end. In the state, a carrier gas supply channel 30 for supplying a carrier gas not containing a carbon component is connected to the cylinder 26. High purity air from which carbon dioxide stored in a cylinder 32 is removed as a carrier gas is supplied from the carrier gas supply channel 30. This carrier gas is used as a sparge gas for removing inorganic carbon (IC) at the time of TOC measurement, and is provided for the original analysis purpose in the TOC measurement apparatus. In the present invention, the carrier gas is used for purging the flow path.

  As shown in FIG. 3, the control device 6 includes a measurement unit control unit 50 that controls the conductivity measurement operation by the TOC measurement unit 2, a valve control unit 52 that controls the operation of the flow path switching valve 20, and the syringe 24. A syringe control unit 54 that controls the operation of the sample, a sample introduction control unit 56 that controls the operation of the sample introduction unit 4 via the valve control unit 52 and the syringe control unit 54, an acid addition channel 38, and a sample water sampling channel A storage cleaning button 60 for instructing cleaning for storage in a state where each of 34 is set to suck pure water, and when storage cleaning is instructed from the storage cleaning button 60, a valve control unit 52 and a syringe control unit 54 A storage cleaning means 58 for performing cleaning and drying processing steps is provided. The storage cleaning button 60 is a button displayed on a keyboard or a display screen, and activates the storage cleaning means 58.

  First, the procedure for performing TOC measurement using the TOC measuring apparatus of the embodiment of FIG. 2 will be described. The sample water sampling channel 34 and the syringe 24 are connected by the valve 20, and a fixed amount of sample water is collected in the syringe 24 by retracting the piston 28 of the syringe 24 to the proximal end side. Subsequently, the valve 20 is switched so that the syringe 24 and the phosphoric acid addition channel 38 are connected, and the piston 28 is further retracted to take phosphoric acid into the syringe 24. The pH of the sample water is adjusted to a strong acidity of about 2 by adding phosphoric acid. Next, the valve 20 is switched to connect the syringe 24 and the drain channel 48. In this state, when the piston 28 is located on the proximal end side with respect to the connection position between the carrier gas supply channel 30 and the syringe 24, in this state, the piston 28 is more than the connection position between the carrier gas supply channel 30 and the syringe 24. If it is also on the distal end side, the piston 28 is retracted so as to be closer to the proximal end side than the connection position between the carrier gas supply channel 30 and the syringe 24. In this state, the carrier gas is supplied from the cylinder 32 into the syringe 24, and the mixed solution of the sample water and phosphoric acid collected in the syringe is evacuated, so that the inorganic carbon dissolved in the sample water from the beginning is removed. Release to drain.

  Next, the supply of the carrier gas is stopped, the valve 20 is switched, the syringe 24 and the TOC measurement channel 46 are connected, and a certain amount of sample water in the syringe 24 is supplied to the TOC measurement unit 2. In the TOC measurement unit 2, the ultraviolet lamp 12 is turned on, and while the sample water passes through the decomposition unit 10, organic substances in the sample water are decomposed into carbon dioxide by irradiation with ultraviolet rays. Carbon dioxide in the sample water is in a gas state because phosphoric acid is added to the sample water to make it acidic. The sample water that has passed through the decomposition unit 10 is guided to the separation unit 14, and since the sample water is in contact with the deionized water that is the measurement water through the gas permeable membrane, the sample water passes through the gas permeable membrane into the measurement water. Moving. The conductivity of the water measured from the separation unit 14 to the detection unit 16 is measured by the conductivity meter of the detection unit 16. The measurement water has a specific conductivity of deionized water before the carbon dioxide moves, and the conductivity increases due to the movement of carbon dioxide, and the TOC concentration of the sample water is obtained based on the change in the conductivity. It is done.

  The relationship between the TOC concentration of the sample water and the conductivity measured by the detection unit 16 can be easily obtained by preparing a calibration curve by measuring with this apparatus using a standard sample in advance.

  Even in the normal measurement operation, when the measurement of one sample is completed, the cleaning water is taken into the syringe 24 from the cleaning water channel 42, and the cleaning water is pushed out from the syringe 24 to the TOC measurement channel 46. The sample water flow path in the decomposition unit 10 is washed from 46.

  Next, storage and washing operations when not used for a long period of time are shown in FIGS.

  Prior to storage and washing, the sample container 36 at the tip of the sample water sampling channel 34 is removed and replaced with a pure water container for washing, and the phosphoric acid cartridge 40 at the tip of the acid addition channel 38 is also removed to remove pure water for washing. Replace with container. Thereafter, the storage cleaning means 58 is activated from the storage cleaning button 60. When the storage cleaning means 58 is activated, cleaning is executed according to a predetermined order.

  FIG. 4 shows the overall flow of storage and cleaning. As a cleaning sequence, the phosphoric acid addition channel 38 is first cleaned. This is because the contamination of the phosphoric acid addition channel 38 is the largest. Thereafter, the sample water flow path 34 and the TOC measurement flow path 46 are washed, but this order may be performed first. In FIG. 4, the sample water flow path 34 is first cleaned, and then the TOC measurement flow path 46 is performed.

  FIG. 5 shows a cleaning process of the phosphoric acid addition flow path 38. The phosphoric acid addition flow path 38 and the syringe 24 are connected by the valve 20, and pure water is collected from the phosphoric acid addition flow path 38 into the syringe 24. Next, the valve 20 is switched, the syringe 24 and the drain channel 48 are connected, and the wash water collected in the syringe 24 is discharged to the drain. The process of taking wash water through the phosphoric acid addition flow path 38 and discharging it to the drain is repeated a plurality of times, for example, 3 to 5 times.

  Next, the washing water container connected to the phosphoric acid addition channel 38 is removed, and the tip of the phosphoric acid addition channel 38 is opened to the atmosphere. In a state where the syringe 24 and the drain channel 48 are connected, the piston 28 of the syringe 24 is retracted to the base end side from the connection position between the carrier gas channel and the syringe 24, and the carrier gas is taken into the syringe 24. Next, the valve is switched to connect the syringe 24 and the phosphoric acid addition channel 38, the carrier gas in the syringe 24 is sent to the phosphoric acid addition channel 38, and the phosphoric acid addition channel 38 is ventilated and dried. The process of taking the carrier gas into the syringe 24 and venting it to the phosphoric acid addition flow path 38 is repeated a plurality of times, for example, 3 to 5 times. As a result, the inside of the phosphoric acid addition flow path 38 is in a dry state. Thereafter, the front end of the flow path of the phosphoric acid addition flow path 38 is closed with a paraffin film to prevent the outside air from entering.

  FIG. 6 shows a cleaning process of the sample water sampling channel 34. The sample water sampling channel 34 and the syringe 24 are connected by the valve 20, and pure water is sampled from the sample water sampling channel 34 into the syringe 24. Next, the valve 20 is switched, the syringe 24 and the drain channel 48 are connected, and the wash water collected in the syringe 24 is discharged to the drain. The process of taking the wash water through the sample water sampling channel 34 and discharging it to the drain is repeated a plurality of times, for example, 3 to 5 times.

  Next, the washing water container connected to the sample water sampling channel 34 is removed, and the tip of the sample water sampling channel 34 is opened to the atmosphere. In a state where the syringe 24 and the drain channel 48 are connected, the piston 28 of the syringe 24 is retracted to the base end side from the connection position between the carrier gas channel and the syringe 24, and the carrier gas is taken into the syringe 24. Next, the valve is switched to connect the syringe 24 and the sample water sampling channel 34, the carrier gas in the syringe 24 is sent to the sample water sampling channel 34, and the sample water sampling channel 34 is vented and dried. The process of taking the carrier gas into the syringe 24 and venting it to the sample water sampling channel 34 is repeated a plurality of times, for example, 3 to 5 times. Since the inside of the sample water sampling channel 34 is now in a dry state, the tip of the sample water sampling channel 34 is then closed with a paraffin film to prevent outside air from entering.

  FIG. 7 shows a cleaning process of the flow path through which the sample water in the decomposition unit 10 flows from the TOC measurement flow path 46. This cleaning process is performed with the ultraviolet lamp 12 of the disassembly unit 10 turned on. The cleaning water flow path 42 and the syringe 24 are connected by the valve 20 to collect the cleaning water into the syringe 24. The valve 20 is switched to connect the syringe 24 and the TOC measurement channel 46, and the collected washing water flows from the TOC measurement channel 46 to the channel through which the sample water in the decomposition unit 10 flows. This process is repeated a plurality of times, for example, 3 to 5 times.

  Next, the washing water container 44 is removed from the washing water flow path 42, and the washing water flow path 42 and the TOC measurement flow path 46 are dried by aeration. This method is the same as the drying of the other flow paths. The carrier gas is taken into the syringe 24, the carrier gas is passed from the TOC measurement flow path 46 to the sample water flow path of the decomposition unit 10, and the cleaning water flow is switched by switching the valve 20. The carrier gas is also vented to the path 42. This aeration of the washing water channel 42 and the TOC measurement channel 46 with the carrier gas is repeated about 10 times. As a result, the sample water channel and the washing water channel 42 in the decomposition unit 10 are dried from the TOC measurement channel 46. Thereafter, the tip of the sample water channel of the decomposition unit 10 and the tip of the washing water channel 42 are closed with a paraffin film.

  Thus, the flow paths through which the sample water of the sample introduction unit 4 and the TOC measurement unit 2 flow are all washed and dried, and the tip is blocked so that the outside air does not enter. It will be ready.

2 TOC Measurement Unit 4 Sample Introduction Unit 6 Control Device 10 Organic Oxidation Decomposition Unit 14 Carbon Dioxide Separation Unit 16 Detection Unit 20 Channel Switching Valve 22 Common Port 24 Syringe 34 Sample Water Collection Channel 38 Phosphoric Acid Addition Channel 42 Washing Water Channel 46 TOC measurement flow path 48 Drain flow path 50 Measurement section control section 52 Valve control section 54 Syringe control section 56 Sample introduction control section 58 Storage cleaning means 60 Storage cleaning button

Claims (5)

An organic matter oxidative decomposition unit that oxidizes organic matter in the supplied sample water by ultraviolet irradiation to convert it into carbon dioxide, and carbon dioxide in the sample water that has passed through the organic matter oxidative decomposition unit is made of deionized water through a gas permeable membrane. And a flow path through which at least the sample water of the carbon dioxide separation unit flows is provided with a carbon dioxide separation unit to be moved to and a detection unit for measuring the conductivity of the measurement water passing through the carbon dioxide separation unit to obtain the carbon dioxide concentration An all-organic carbon measurement unit that is a microchannel formed in the chip;
A flow path switching valve capable of switching and connecting a common port to each of the plurality of ports, a syringe connected to the common port of the flow path switching valve, and supplying sample water connected to each of the plurality of ports Sample water sampling flow path, acid addition flow path for supplying carbon-free inorganic acid, wash water flow path for supplying wash water, TOC measurement flow path connected to the organic matter oxidative decomposition unit, and drain flow path opened to the drain The syringe is composed of a cylinder and a piston that slides inside the cylinder, and the cylinder has a distal end connected to the common port, and a proximal end of the piston is retracted toward the proximal end of the cylinder. A sample introduction part connected to a gas pipe for supplying a carrier gas containing no carbon component in the cylinder;
A measurement unit control unit for controlling the conductivity measurement operation by the all-organic carbon measurement unit, a valve control unit for controlling the operation of the flow path switching valve, a syringe control unit for controlling the operation of the syringe, the valve control unit, and The sample introduction control unit that controls the operation of the sample introduction unit via the syringe control unit, the acid addition channel and the sample water sampling channel are each set to suck pure water and washed for storage. Storage cleaning button to be instructed, and when storage cleaning is instructed from the storage cleaning button, the following cleaning and drying processing steps (A), (B) and (C) are performed via the valve control unit and the syringe control unit. And a total organic carbon measuring device provided with a control device provided with a storage cleaning means.
(A) The acid addition flow path is washed by sucking pure water from the acid addition flow path into the syringe and discharging it from the drain flow path, and then the carrier gas from the gas pipe is added to the acid by the syringe. Operation for supplying to the flow path and drying the acid addition flow path.
(B) The sample water sampling channel is washed by sucking pure water from the sample water sampling channel into the syringe and discharging it from the drain channel, and then the carrier gas from the gas pipe is An operation of supplying the sample water sampling channel and drying the sample water sampling channel.
(C) Flow through which the sample water of the organic matter oxidative decomposition section flows by sucking the wash water from the wash water flow path into the syringe and supplying the sample water of the organic matter oxidative decomposition section from the TOC measurement flow path The operation of washing the channel and then supplying the carrier gas from the gas pipe to the channel through which the sample water of the organic matter oxidative decomposition unit flows by the syringe to dry the channel through which the sample water of the organic matter oxidative decomposition unit flows.   The total organic carbon measuring device according to claim 1, wherein the inorganic acid not containing carbon supplied from the acid addition channel is phosphoric acid.   Of the steps (A), (B) and (C), the step (A) is first processed, the step (B) or (C) is subsequently processed, and finally the step (B) or (C The total organic carbon measuring device according to claim 2, wherein the remaining steps are processed.   The said process (C) irradiates an ultraviolet-ray to this flow path at the time of wash | cleaning the flow path through which the sample water of the said organic substance oxidation decomposition part flows with washing | cleaning water, The all existence as described in any one of Claim 1 to 3 Airframe carbon measuring device. In the step (C), after washing the flow path through which the sample water of the organic matter oxidative decomposition section flows, the flow path through which the sample water of the organic matter oxidative decomposition section is opened is opened at the washing water container side of the wash water flow path. total organic carbon measuring apparatus according to claims 1 to perform the drying of the washing water flow path to any one of 4 with drying.

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