Gas-liquid separator, total organic carbon meter and analysis system

Abstract

A gas-liquid separator (50) comprises: a receiving port (51a) to which a sample is supplied; a gas feed pipe (51, 52) for feeding gas in the sample supplied to the receiving port (51a) to the outside; a storage pipe (53) for storing liquid in the sample supplied to the receiving port (51a); and a waste liquid port (54a) for discarding liquid stored in the storage pipe (53) to the outside. The storage pipe (53) includes: a first storage portion (53a) which communicates with the receiving port (51a) and which is disposed in a region vertically below the receiving port (51a); a second storage portion (53b) which communicates with the waste liquid port (54a) and which is disposed in a region vertically below the waste liquid port (54a); and a communicating portion (53c) which provides communication between a vertically lower end portion of the first storage portion (53a) and a vertically lower end portion of the second storage portion (53b).

Description

[Technical Field]

[0001] The present disclosure relates to a gas-liquid separator, a total organic carbon meter and an analysis system. [Background technology]

[0002] BACKGROUND ART Conventionally, a method for measuring the amount of TOC (Total Organic Carbon) in a water sample is known as a method for analyzing the properties of the water sample (for example, Japanese Patent No. 6556699). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6556699 [Non-patent literature]

[0004] [Non-Patent Document 1] Kawasaki, N., Imai, A., Matsushige, K., Komatsu, K., Ogishi, F., Yabata, M., Mikami, H., and Goto, T., "Study of molecular weight distribution of DOC in Lake Kasumigaura using size exclusion chromatography with TOC detector," Abstracts of the 72nd Annual Meeting of the Japanese Society of Limnology, Session ID: 3C05, September 2007. Summary of the Invention [Problem to be solved by the invention]

[0005] Among TOC meters (total organic carbon meters), a device used to measure TOC content, there are so-called wet oxidation TOC meters that irradiate ultraviolet light onto a liquid sample injected into a reaction tube to oxidize the organic matter in the liquid sample, generating carbon dioxide gas (CO2 gas), and then send the generated CO2 gas along with a carrier gas to a detector as a gas sample to measure the TOC content.

[0006] Conventionally, wet oxidation TOC analyzers generally perform batch measurements by injecting a sample into a reaction tube, then stopping the injection and irradiating the reaction tube with ultraviolet light to oxidize the organic matter in the sample and measure the TOC content. This type of conventional batch measurement cannot measure the TOC content continuously (in real time), so it is not possible to continuously measure the time change in the TOC content while continuously sending the sample to the reaction tube.

[0007] In order to continuously measure the time-dependent change in TOC content in a wet oxidation TOC analyzer, it is necessary to continuously and appropriately separate the liquid sample and gas sample after irradiating them with ultraviolet light in the reaction tube. However, the above-mentioned Patent Publication No. 6556699 does not mention this problem or any solution to it.

[0008] The present disclosure has been made to solve the above problems, and an object of the present disclosure is to continuously and appropriately separate a sample containing gas and liquid into the gas and liquid. [Means for solving the problem]

[0009] A gas-liquid separator according to the present disclosure is a gas-liquid separator that separates gas and liquid contained in a sample, and includes a supply port through which the sample is supplied, an air supply pipe having one end connected to the supply port for sending the gas in the sample supplied to the supply port to the outside, a storage pipe for storing the liquid in the sample supplied to the supply port, and a waste liquid outlet for disposing of the liquid stored in the storage pipe to the outside. The storage pipe includes a first storage section connected to the supply port and located in a region vertically below the supply port, a second storage section connected to the waste liquid outlet and located in a region vertically below the waste liquid outlet, and a communication section that communicates between the vertically lower end of the first storage section and the vertically lower end of the second storage section.

[0010] The total organic carbon meter according to the present disclosure comprises the above-mentioned gas-liquid separator, a mixer that mixes a carrier gas with a liquid sample at a predetermined cycle, an oxidation reactor that is disposed between the mixer and the air supply pipe of the gas-liquid separator and irradiates the mixed sample that has passed through the mixer with ultraviolet light, and a non-dispersive infrared absorption detector that detects components in the gas sent from the air supply pipe of the gas-liquid separator.

[0011] The analytical system according to the present disclosure includes the above-described total organic carbon meter and a liquid chromatograph that supplies a liquid sample to the mixer of the total organic carbon meter. [Effects of the Invention]

[0012] According to the present disclosure, a sample containing gas and liquid can be continuously and appropriately separated into the gas and liquid. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a diagram schematically illustrating an example of a configuration of an analysis system. [Figure 2] FIG. 2 is a diagram for explaining an example of the principle of detection of sample components by an LC unit. [Figure 3] FIG. 1 is a diagram showing the correspondence relationship between solute size and elution time. [Figure 4] FIG. 2 is a diagram showing an example of the configuration of a mixer, an oxidation reactor, and a gas-liquid separator. [Figure 5] FIG. 2 is a diagram schematically illustrating each step of an analysis process performed by the analysis system. [Figure 6] FIG. 1 is a diagram (part 1) showing the configuration of a gas-liquid separator. [Figure 7] FIG. 2 is a diagram (part 2) showing the configuration of the gas-liquid separator. [Figure 8] FIG. 3 is a diagram (part 3) showing the configuration of a gas-liquid separator. [Figure 9] FIG. 10 is a diagram showing the configuration of a gas-liquid separator (part 4). DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are designated by the same reference numerals, and description thereof will not be repeated.

[0015] <System configuration> 1 is a diagram schematically illustrating an example of the configuration of an analysis system 100 according to this embodiment. The analysis system 100 includes an LC (Liquid Chromatograph) unit U1, a TOC unit U2, an inorganic carbonate removal degassing system 30, a tank 32, and a controller 90.

[0016] The LC unit U1 is a device that injects a sample to be analyzed into a liquid mobile phase, passes it through a column, and detects sample components by utilizing the difference in the interaction between the sample (mobile phase) and the column packing material (stationary phase).

[0017] The LC unit U1 includes a container 20, a pump 2, an analytical flow path 6, an autosampler 8, a column oven 12 that houses a column 10 therein, and a detector .

[0018] A mobile phase (ultrapure water, phosphate buffer solution, etc.) is contained in a container 20. A pump 2 draws the mobile phase from the container 20 and injects it into an analysis flow path 6. In the analysis flow path 6, an autosampler 8, a column 10, and a detector 14 are arranged from upstream to downstream of the flow of the mobile phase.

[0019] An autosampler 8 injects a sample to be analyzed into the mobile phase in the analysis flow path 6. A column 10 separates the sample injected into the mobile phase. A detector 14 detects the sample components separated by the column 10. The detector 14 can be a UV detector and a fluorescence detector connected in series.

[0020] 2 is a diagram illustrating an example of the principle of detection of sample components by the LC unit U1. The LC unit U1 according to this embodiment employs size exclusion chromatography (SEC). Size exclusion chromatography is a method for detecting solute components by utilizing the property that the degree of penetration into a column packing varies depending on the solute size (size of the sample molecules).

[0021] The column 10 is loaded with a column packing material with small holes (pores) as a stationary phase. The time it takes for molecules to enter the pores of the column packing material affects the time it takes for the molecules to be eluted from the column 10 (elution time). That is, small molecules move through the column 10 by penetrating deep into the pores, so they take a long time to be eluted from the column 10, but larger molecules have difficulty entering the pores, so they are eluted from the column 10 correspondingly faster.

[0022] Figure 3 shows the relationship between solute size and elution time. As shown in Figure 3, the larger the solute size, the shorter the migration path and the shorter the elution time. The detector 14 of the LC unit U1 detects sample components based on the difference in elution time as shown in Figure 3.

[0023] 1, the inorganic carbonate removal and degassing system 30 is disposed between the LC unit U1 and the TOC unit U2. The inorganic carbonate removal and degassing system 30 removes impurities (inorganic carbonates) that are not the target of analysis from the liquid sample that has passed through the detector 14 of the LC unit U1 and continuously sends the removed impurities to the TOC unit U2.

[0024] The TOC unit U2 is configured to continuously measure the amount of TOC in a liquid sample continuously sent from the LC unit U1 via the inorganic carbonate removal degassing system 30.

[0025] The TOC unit U2 includes a mixer 34, an oxidation reactor 40, a gas-liquid separator 50, a dehumidifier 60, and a CO2 detector 70. The mixer 34 and the oxidation reactor 40 are connected by a pipe P1, and the oxidation reactor 40 and the gas-liquid separator 50 are connected by a pipe P2.

[0026] FIG. 4 is a diagram showing an example of the configuration of the mixer 34, the oxidation reactor 40, and the gas-liquid separator 50.

[0027] The mixer 34 periodically mixes the liquid sample continuously sent from the LC unit U1 with the carrier gas (nitrogen gas) from the tank 32, and supplies the mixture to the pipe P1. As a result, the liquid sample and the carrier gas are alternately supplied to the oxidation reactor 40 in the form of a film.

[0028] The oxidation reactor 40 includes a UV lamp 42 housed inside a UV oxidation tube 41, and a spiral reaction tube 43 wound around the UV lamp 42. The film-like liquid sample and carrier gas supplied from the mixer 34 are supplied from a pipe P1 to the reaction tube 43, pass through the reaction tube 43, and then are supplied to a pipe P2.

[0029] The film-like liquid sample and carrier gas are irradiated with ultraviolet light generated by UV lamp 42 as they flow through reaction tube 43. As a result, organic matter contained in the film-like liquid sample is oxidized to CO gas, which is mixed into the carrier gas. Therefore, the film-like liquid sample containing no organic matter and the gas sample containing CO gas and carrier gas are alternately sent from oxidation reactor 40 to pipe P2.

[0030] The gas-liquid separator 50 is configured to continuously and appropriately separate the liquid sample and the gas sample alternately sent from the pipe P2. The liquid sample separated by the gas-liquid separator 50 is discarded, while the gas sample separated by the gas-liquid separator 50 is sent to the CO2 detector 70. The configuration of the gas-liquid separator 50 will be described in detail later.

[0031] Returning to FIG. 1, the gas sample separated by the gas-liquid separator 50 is sent to the dehumidifier 60, where it is dehumidified and then sent to the CO2 detector 70.

[0032] The CO2 detector 70 uses non-dispersive infrared (NDIR) absorption spectroscopy to detect the amount of CO2 gas contained in the sample after it has been treated by the oxidation reactor 40. Detecting CO2 gas using non-dispersive infrared absorption spectroscopy is a well-known technique. The gas sample detected by the CO2 detector 70 is discharged to the outside. The detection result of the CO2 detector 70 is sent to the controller 90. The controller 90 detects the amount of TOC in the sample based on the detection result of the CO2 detector 70.

[0033] The controller 90 is typically a general-purpose personal computer with a display that is operated by an operator. The controller 90 controls the operations of the LC unit U1 and the TOC unit U2. Specifically, the controller 90 stores an analysis program for controlling the operations of the LC unit U1 and the TOC unit U2 during analysis, and controls the analysis by the LC unit U1 and the analysis by the TOC unit U2 in conjunction with each other in accordance with the analysis program. The analysis results of the LC unit U1 and the TOC unit U2 are displayed, for example, on the display of the controller 90.

[0034] When an operator loads the autosampler 8 with a sample to be analyzed and inputs a command to start the analysis into the controller 90, the analysis process by the analysis system 100 begins.

[0035] 5 is a diagram showing a schematic diagram of each step of the analytical process performed by the analytical system 100. In the analytical process, the sample is processed in the order of steps S1 to S8.

[0036] Steps S1 to S3 are processes within the LC unit U1. In step S1, a sample is injected into the mobile phase from the autosampler 8. In the next step S2, the sample injected into the mobile phase is separated in the column 10. In the next step S3, the sample components separated in the column 10 are detected by the detector 14 (UV detector and fluorescence detector).

[0037] The next step S4 is a process in the inorganic carbonate removal and degassing system 30. In step S4, the inorganic carbonate removal and degassing system 30 removes impurities (inorganic carbonates: IC) from the liquid sample sent from the detector 14 of the LC unit U1.

[0038] The next steps S5 to S8 are processes within the TOC unit U2. In step S5, the liquid sample is mixed with a carrier gas at predetermined intervals by the mixer 34. As a result, the liquid sample in the form of a film and the carrier gas are alternately supplied to the oxidation reactor 40, as described above.

[0039] In the next step S6, ultraviolet light is irradiated onto the film-like liquid sample and carrier gas supplied from the mixer 34 in the oxidation reactor 40. As a result, as described above, the organic matter in the film-like liquid sample is oxidized to CO gas, which is mixed into the carrier gas (e.g., N). Therefore, the film-like liquid sample containing no organic matter and the gas sample containing CO gas and carrier gas are alternately sent to the gas-liquid separator 50.

[0040] In the next step S7, the liquid sample and the gas sample alternately sent from the oxidation reactor 40 are separated in the gas-liquid separator 50. The gas sample separated in the gas-liquid separator 50 is sent to the CO2 detector 70.

[0041] In the next step S8, the CO2 detector 70 detects the amount of CO2 gas (TOC amount) in the gas sample separated in the gas-liquid separator 50.

[0042] Thus, in the analysis system 100 according to this embodiment, by combining the LC unit U1 and the TOC unit U2, substances that cannot be detected by the detector 14 (e.g., a UV detector or a fluorescence detector) of the LC unit U1 can be detected as CO2 gas amounts (TOC amounts) in the TOC unit U2.

[0043] <Configuration of the gas-liquid separator 50> 6 is a diagram showing the configuration of the gas-liquid separator 50. The gas-liquid separator 50 includes a supply port 51a, gas supply pipes 51 and 52, a storage pipe 53, a waste liquid port 54a, a drain pipe 54, and a depressurization pipe 55.

[0044] The inlet 51a is supplied with the sample after oxidation in the oxidation reactor 40, that is, the liquid sample and the gas sample containing CO2 gas as described above, from the pipe P2.

[0045] The air supply pipes 51 and 52 are pipes for sending the gas sample supplied to the supply port 51a to the external CO2 detector 70. One end of the air supply pipe 51 is connected to the supply port 51a, and the other end is connected to one end of the air supply pipe 52. The other end of the air supply pipe 52 is connected to the CO2 detector 70. The inner diameter of the air supply pipe 51 is larger than that of the air supply pipe 52. In this embodiment, as shown in FIG. 6, the ratio of the inner diameter of the air supply pipe 51 to the inner diameter of the air supply pipe 52 is approximately 2:1. However, the ratio of the inner diameter of the air supply pipe 51 to the inner diameter of the air supply pipe 52 is not limited to approximately 2:1. The optimum range of the ratio of the inner diameter of the air supply pipe 51 to the inner diameter of the air supply pipe 52 is, for example, from approximately 10:1 to approximately 1.5:1. In this embodiment, the inner diameter of the air supply pipe 51 is approximately constant, and the inner diameter of the air supply pipe 52 is also approximately constant.

[0046] Storage pipe 53 is a pipe for storing a certain amount of liquid sample supplied to inlet 51a, and includes first storage section 53a, second storage section 53b, and communication section 53c.

[0047] First storage section 53a and second storage section 53b both extend vertically and are arranged adjacent to each other horizontally. First storage section 53a has an upper vertical end connected to supply inlet 51a and is arranged in a region vertically below supply inlet 51a. Second storage section 53b has an upper vertical end connected to waste liquid outlet 54a and is arranged in a region vertically below waste liquid outlet 54a. Communication section 53c connects the lower vertical end of first storage section 53a with the lower vertical end of second storage section 53b. Storage pipe 53 according to this embodiment is formed in a U-shape.

[0048] Waste liquid outlet 54a is a discharge port for disposing of the liquid stored in storage pipe 53 to the outside through drain pipe 54. Waste liquid outlet 54a is located vertically below supply inlet 51a by a predetermined distance α. Pressure relief pipe 55 is configured to communicate the vertically upper end of second storage section 53b with the outside.

[0049] As described above, the gas-liquid separator 50 according to this embodiment has gas supply pipes 51 and 52 for sending the gas sample after oxidation in the oxidation reactor 40 to the CO2 detector 70, a storage pipe 53 having a capacity for storing a certain amount of liquid sample after oxidation in the oxidation reactor 40, and a waste liquid port 54a and a drain pipe 54 for disposing of the liquid sample stored in the storage pipe 53.

[0050] This allows the sample after oxidation in oxidation reactor 40 to be continuously separated into a gas sample and a liquid sample. That is, by introducing the sample continuously oxidized in oxidation reactor 40 into gas-liquid separator 50 together with the carrier gas, the liquid sample moves vertically downward from inlet 51a due to its own weight, as indicated by arrow A2 in Fig. 6, and is stored in U-shaped storage tube 53. The liquid sample stored in storage tube 53 blocks the flow path through which the gas sample escapes from inlet 51a to waste outlet 54a and depressurization tube 55, allowing the gas sample to be supplied to CO2 detector 70 without leakage, as indicated by arrow A1 in Fig. 6.

[0051] The capacity of storage tube 53 is set so that the pressure generated in storage tube 53 by the carrier gas flow rate does not cause all of the liquid sample in storage tube 53 to flow into drain tube 54. This ensures that the flow path through which the gas sample escapes from inlet 51a to waste outlet 54a is properly sealed.

[0052] If the gas flow path to the CO2 detector 70 is blocked for some reason, the pressure inside the gas supply pipes 51 and 52 will rise, causing all of the liquid stored in the storage pipe 53 to be discharged from the waste liquid outlet 54a to the drain pipe 54, leaving the gas supply pipes 51 and 52 open to the atmosphere. This makes it possible to prevent breakdowns and liquid leaks caused by an abnormal rise in pressure inside the gas-liquid separator 50.

[0053] Furthermore, waste liquid outlet 54a is located at a predetermined distance α lower than supply inlet 51a. This allows the liquid level of the liquid sample stored in first reservoir 53a to be lower than supply inlet 51a by the predetermined distance α, thereby preventing contact between the liquid sample stored in reservoir tube 53 and the gas sample newly entering gas-liquid separator 50 from supply inlet 51a. This prevents CO2 gas, the target of analysis, from being trapped again in the liquid sample. Furthermore, by minimizing the predetermined distance α, the dead volume of the gas layer between supply inlet 51a and the liquid level of the liquid sample stored in first reservoir 53a can be minimized.

[0054] Furthermore, the gas-liquid separator 50 according to this embodiment, configured as described above, can continuously separate a gas sample and a liquid sample. Therefore, the TOC unit U2 according to this embodiment can continuously measure the TOC amount, rather than batch measurement as in the past. Therefore, the TOC amount can be measured continuously (over time) while maintaining the information on the difference in elution time obtained by separation in the column 10 of the LC unit U1 in the TOC unit U2. Therefore, the LC unit U1 and TOC unit U2 can be combined to form a SEC-TOC analyzer.

[0055] Furthermore, gas-liquid separator 50 according to the present embodiment includes pressure relief pipe 55 that connects the vertically upper end of second reservoir 53b to the outside. Therefore, the vertically upper end of second reservoir 53b is open to the atmosphere, and the liquid sample in second reservoir 53b can be smoothly discharged from waste liquid outlet 54a to drain pipe 54.

[0056] [Variation 1] The CO2 detector 70 of the TOC unit U2 is configured to measure CO2 using a steady-state signal value as a baseline when a CO2-free carrier gas is flowed through the CO2 detector 70 at a constant flow rate and pressure. Therefore, during measurement by the CO2 detector 70, UV irradiation by the oxidation reactor 40 is temporarily stopped and a process of detecting the baseline is periodically performed. If the flow rate or pressure of the carrier gas fluctuates during baseline detection, the baseline signal value also fluctuates, which can become a source of noise. Therefore, it is desirable to always keep the flow rate and pressure of the carrier gas stable during measurement by the CO2 detector 70.

[0057] If a liquid film forms on the air supply pipes 51 and 52 of the gas-liquid separator 50, the liquid film may temporarily block the flow of carrier gas, causing fluctuations in the flow rate and pressure of the carrier gas, which may cause the baseline of the CO2 detector 70 to fluctuate.

[0058] In particular, since the sample heated by ultraviolet irradiation from UV lamp 42 in oxidation reactor 40 is sent to gas-liquid separator 50, as the gas sample flows through air supply pipes 51 and 52, which are at room temperature, the vapor in the gas sample cools and some of it becomes liquid, which easily forms a liquid film by adhering to the wall surfaces of air supply pipes 51 and 52 as water droplets. After the liquid film is formed, if the pressure in air supply pipes 51 and 52 increases above a certain level, the liquid film will be pushed by the pressure and burst, or will continue to move inside air supply pipes 51 and 52 as a liquid film. If this process is repeated, the baseline of CO2 detector 70 will become unstable, which may result in noise.

[0059] Therefore, in the present modified example 1, a spherical cooling volume is provided immediately after the inlet 51a of the gas-liquid separator 50, thereby increasing the area of ​​the wall surface to enhance the cooling effect and creating a structure that makes it difficult for a liquid film to occur.

[0060] 7 is a diagram showing the configuration of a gas-liquid separator 50A according to Modification 1. In the gas-liquid separator 50A according to Modification 1, the gas pipe 51 of the gas-liquid separator 50 according to the above-described embodiment is changed to a gas pipe 51A.

[0061] The air supply pipe 51A has a spherical shape immediately behind the supply inlet 51a. As a result, the inner diameter d2 of the air supply pipe 51A near the supply inlet 51a is set to a value significantly larger than the inner diameter d1 of the air supply pipe 52. In the example shown in FIG. 7, the ratio of the inner diameter d1 of the air supply pipe 52 to the inner diameter d2 of the air supply pipe 51A near the supply inlet 51a is approximately 6:1. This makes it difficult for a liquid film to form near the supply inlet 51a of the air supply pipe 51A. Note that the ratio of the inner diameter d1 of the air supply pipe 52 to the inner diameter d2 of the air supply pipe 51A near the supply inlet 51a is not limited to approximately 6:1. The optimal range for the ratio of the inner diameter d1 of the air supply pipe 52 to the inner diameter d2 of the air supply pipe 51A near the supply inlet 51a is, for example, from approximately 20:1 to approximately 2.5:1.

[0062] Furthermore, whereas the inner diameter of the air supply pipe 51 in the above-described embodiment was substantially constant, the inner diameter of the air supply pipe 51A in this modified example 1 is tapered so that it becomes smaller the further away from the supply / receive port 51a. As a result, the air supply pipe 51A in this modified example 1 has a larger wall area than the air supply pipe 51 in the above-described embodiment, and can cool the gas sample more efficiently. Therefore, the vapor in the gas sample can be liquefied in the air supply pipe 51A with a large inner diameter, making it difficult for the gas sample containing the vapor to flow into the air supply pipe 52. As a result, it is difficult for a liquid film to form in the air supply pipe 52 with a small inner diameter.

[0063] As described above, in the gas-liquid separator 50A according to the first modification, a spherical cooling volume is provided near the inlet 51a of the air supply pipe 51A, making it difficult for a liquid film to form in the air supply pipes 51A and 52. This stabilizes the baseline of the CO2 detector 70, enabling highly sensitive measurements.

[0064] [Variation 2] 8 is a diagram showing the configuration of a gas-liquid separator 50B according to Modification 2. In the gas-liquid separator 50B according to Modification 2, the gas pipe 51 of the gas-liquid separator 50 according to the above-described embodiment is changed to a gas pipe 51B.

[0065] While the inner wall of the air supply pipe 51 in the above-described embodiment has a flat shape, the inner wall of the air supply pipe 51B in this modified example 2 has an uneven shape. As a result, the air supply pipe 51B in this modified example 2 has a larger wall area than the air supply pipe 51 in the above-described embodiment, and can cool the gas sample more efficiently. Therefore, the vapor in the gas sample can be liquefied in the air supply pipe 51B, which has a large inner diameter, and it is difficult for a liquid film to form in the air supply pipe 52, which has a small inner diameter.

[0066] In this way, the cooling effect of the air supply pipe 51B may be enhanced by forming an uneven inner wall of the air supply pipe 51B. In this way, the vapor is liquefied on the inner wall of the air supply pipe 51B, making it difficult for the vapor-containing gas sample to flow into the air supply pipe 52. As a result, it is difficult for a liquid film to form in the air supply pipe 52, which has a small inner diameter. This stabilizes the baseline of the CO2 detector 70, enabling highly sensitive measurements.

[0067] [Variation 3] 9 is a diagram showing the configuration of a gas-liquid separator 50C according to Modification 3. In the gas-liquid separator 50C according to Modification 3, the air supply pipe 51A according to Modification 1 described above is changed to an air supply pipe 51C.

[0068] Whereas the air supply pipe 51A according to the above-described modified example 1 has a spherical cooling volume, the air supply pipe 51C according to the present modified example 3 has an oblong cooling volume. Even with this modification, as with the above-described modified example 1, it is possible to make it difficult for a liquid film to form in the air supply pipes 51C and 52, thereby stabilizing the baseline of the CO2 detector 70 and enabling highly sensitive measurements.

[0069] [Variation 4] In the above embodiment, an example has been described in which the size exclusion (SEC) mode is used as the separation mode of the LC unit U1 (see FIG. 2 above). However, the separation mode of the LC unit U1 is not limited to the size exclusion mode. For example, the separation mode of the LC unit U1 may be any of the adsorption mode, partition mode, and ion exchange mode.

[0070] In the above embodiment, an example in which the LC unit U1 and the TOC unit U2 are combined has been described, but it is also possible to omit the LC unit U1. That is, the sample components may be entirely measured in the TOC unit U2 without separating them in the LC unit U1.

[0071] [Aspect] It will be understood by those skilled in the art that the above-described embodiments and their modifications are specific examples of the following aspects.

[0072] (Item 1) A gas-liquid separator according to one embodiment is a gas-liquid separator that separates gas and liquid contained in a sample, and includes a supply port through which the sample is supplied, an air supply pipe having one end connected to the supply port for sending the gas in the sample supplied to the supply port to the outside, a storage pipe for storing the liquid in the sample supplied to the supply port, and a waste liquid outlet for disposing of the liquid stored in the storage pipe to the outside. The storage pipe includes a first storage section connected to the supply port and located in a region vertically below the supply port, a second storage section connected to the waste liquid outlet and located in a region vertically below the waste liquid outlet, and a communication section that communicates between the vertically lower end of the first storage section and the vertically lower end of the second storage section.

[0073] According to the gas-liquid separator described in paragraph 1, the gas in the sample supplied to the inlet is sent to the gas supply pipe, while the liquid in the sample moves vertically downward from the inlet due to its own weight and is stored in the storage pipe. The liquid sample stored in the storage pipe seals the flow path through which the gas sample flows from the inlet to the waste liquid outlet. This allows the sample containing gas and liquid to be continuously and appropriately separated into gas and liquid.

[0074] (Item 2) In the gas-liquid separator described in item 1, the waste liquid port is disposed at a position vertically below the supply / receive port by a predetermined distance.

[0075] According to the gas-liquid separator described in paragraph 2, the liquid level of the liquid sample stored in the first storage section can be set lower by a predetermined distance than the supply port. This prevents gas newly entering the gas-liquid separator from the supply port from coming into contact with the liquid stored in the storage tube. This prevents the gas to be analyzed from being trapped in the liquid stored in the storage tube.

[0076] (Item 3) The gas-liquid separator according to item 1 or 2 further comprises a pressure relief pipe that connects the vertically upper end of the second storage section to the outside.

[0077] According to the gas-liquid separator described in paragraph 3, the vertically upper end of the second reservoir is connected to the outside and is open to the atmosphere, so that the liquid sample in the second reservoir can be smoothly discharged from the waste liquid outlet.

[0078] (Item 4) In the gas-liquid separator according to any one of Items 1 to 3, the air supply pipe includes a first air supply pipe connected to the supply port and a second air supply pipe connected to the first air supply pipe. The inner diameter of the first air supply pipe is larger than the inner diameter of the second air supply pipe.

[0079] According to the gas-liquid separator described in paragraph 4, by making the inner diameter of the first air supply pipe connected to the supply port larger than the inner diameter of the second air supply pipe, it is possible to make it difficult for the liquid supplied to the supply port to form a liquid film in the first air supply pipe, thereby stabilizing the gas flow rate and pressure in the air supply pipe.

[0080] (Item 5) In the gas-liquid separator described in item 4, the inner diameter of the first air supply pipe becomes smaller as it is farther from the supply port, and the inner diameter of the second air supply pipe is approximately constant.

[0081] According to the gas-liquid separator described in paragraph 5, by making the inner diameter of the first air supply pipe not substantially constant but tapering it so that it becomes smaller as it moves away from the supply port, the wall area of ​​the first air supply pipe can be increased and the gas flowing through the first air supply pipe can be cooled more efficiently. Therefore, the vapor in the gas can be liquefied in the first air supply pipe, making it difficult for the vapor to flow into the second air supply pipe. As a result, it is difficult for a liquid film to form in the second air supply pipe.

[0082] (Item 6) In the gas-liquid separator according to any one of Items 1 to 3, the air supply pipe includes a first air supply pipe connected to the supply port and a second air supply pipe connected to the first air supply pipe. The inner wall of the second air supply pipe has a flat shape. The inner wall of the first air supply pipe has an uneven shape.

[0083] According to the gas-liquid separator described in paragraph 6, by making the inner wall of the first air supply pipe uneven rather than flat, the area of ​​the wall surface of the first air supply pipe can be increased and the gas flowing through the first air supply pipe can be cooled more efficiently. Therefore, the vapor in the gas can be liquefied in the first air supply pipe, making it difficult for the vapor to flow into the second air supply pipe. As a result, it is difficult for a liquid film to form in the second air supply pipe.

[0084] (Item 7) A total organic carbon meter according to one embodiment includes the gas-liquid separator described in any one of Items 1 to 6, a mixer that mixes a carrier gas with a liquid sample at a predetermined cycle, an oxidation reactor that is disposed between the mixer and the gas-liquid separator's air supply pipe and irradiates the mixed sample that has passed through the mixer with ultraviolet light, and a non-dispersive infrared absorption detector that detects components in the gas sent from the gas supply pipe of the gas-liquid separator.

[0085] With this total organic carbon meter, a sample containing gas and liquid can be continuously and appropriately separated into gas and liquid using a gas-liquid separator, making it possible to continuously measure the components in the gas using a detector.

[0086] (Item 8) An analytical system according to one embodiment includes the total organic carbon meter according to item 7, and a liquid chromatograph that supplies a liquid sample to a mixer of the total organic carbon meter.

[0087] According to this analytical system, the components of a sample continuously supplied from a liquid chromatograph can be continuously detected by a total organic carbon meter.

[0088] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive. The scope of the present invention is defined by the claims, not by the description of the above embodiments, and is intended to include all modifications within the meaning and scope of the claims. [Explanation of symbols]

[0089] 2 Pump, 6 Analysis flow path, 8 Autosampler, 10 Column, 12 Column oven, 14 Detector, 20 Container, 30 Inorganic carbonate removal degassing system, 32 Tank, 34 Mixer, 40 Oxidation reactor, 41 UV oxidation tube, 42 Lamp, 43 Reaction tube, 50, 50A, 50B, 50C Gas-liquid separator, 51, 51A, 51B, 51C, 52 Air supply pipe, 51a Inlet, 53 Storage pipe, 53a First storage section, 53b Second storage section, 53c Communication section, 54 Drain pipe, 54a Waste liquid outlet, 55 Pressure relief pipe, 70 CO2 detector, 60 Dehumidifier, 90 Controller, 100 Analysis system, P1, P2 Piping, U1 LC unit, U2 TOC unit.

Claims

1. A gas-liquid separator that separates gas and liquid contained in a sample, a receiving port through which the sample is supplied; an air supply pipe having one end connected to the supply port for sending the gas in the sample supplied to the supply port to the outside; a reservoir tube for storing the liquid in the sample supplied to the receiving port; a waste liquid port for disposing of the liquid stored in the storage tube to the outside, The storage tube is a first storage section that is connected to the supply port and is disposed in a region vertically below the supply port; a second reservoir communicating with the waste liquid port and disposed in a region vertically below the waste liquid port; a communication portion that communicates a vertically lower end of the first storage portion with a vertically lower end of the second storage portion, The air supply pipe is a first air supply pipe connected to the air supply port; a second air supply pipe connected to the first air supply pipe, the inner wall of the second air line has a flat shape; a gas-liquid separator, wherein the inner wall of the first air supply pipe has an uneven shape;

2. The gas-liquid separator according to claim 1 , wherein the waste liquid port is disposed at a position vertically below the supply port by a predetermined distance.

3. The gas-liquid separator according to claim 1 , further comprising a pressure relief pipe communicating a vertically upper end of the second storage portion with the outside.

4. A gas-liquid separator as described in claim 1, wherein the inner diameter of the first air supply pipe is larger than the inner diameter of the second air supply pipe.

5. The gas-liquid separator according to claim 1; a mixer that mixes a carrier gas with a liquid sample at a predetermined cycle; an oxidation reactor disposed between the mixer and the air pipe of the gas-liquid separator, for irradiating the mixed sample that has passed through the mixer with ultraviolet light; a non-dispersive infrared absorption detector that detects components in the gas sent from the gas supply pipe of the gas-liquid separator.

6. a total organic carbon meter according to claim 5; a liquid chromatograph that supplies a liquid sample to the mixer of the total organic carbon meter.

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