Sampling system and sampling method

Abstract

This sampling system includes: a chamber; a measuring tube; a first pressure gauge; a second pressure gauge; a storage unit; and an output unit. The sampling system examines a sample that is introduced into an analysis device. A sample is collected in the chamber. The sample collected in the chamber is introduced into the measuring tube. The first pressure gauge or the second pressure gauge measures the pressure of at least one of the chamber and the measuring tube. The storage unit stores pressure information indicating the pressure measured by the first pressure gauge or the second pressure gauge at the k-th (k is an integer equal to or greater than 1) analysis time point. The output unit outputs the pressure information stored in the storage unit.

Description

Sampling system and sampling method

[0001] The present invention relates to a sampling system and a sampling method.

[0002] Gas chromatographs (GCs) are known as analytical devices that separate substances contained in a sample gas into different components. A sampling system introduces the sample gas to be analyzed into the GC. For example, Patent Document 1 describes a sample injection method in which the sample gas is introduced into the GC using a gas-tight syringe. Alternatively, depending on the pressure or amount of the sample gas, the sample gas may be introduced into the GC using a gas sampler that combines a metering tube and a valve.

[0003] JP 2016-50914 A

[0004] To analyze sample gas using the gas sampler method, a sufficient amount of sample gas is required to replace the inside of the measuring tube. However, if the sample is rare or expensive, it is not easy to prepare a large amount of sample gas.

[0005] Furthermore, to confirm the analysis results, the analysis of sample gas collected under the same conditions may be repeated. In this case, the amount of sample gas required increases. It is possible to increase the volume of sample gas by diluting it. However, depending on the sample gas collection environment, the ratio of components in the sample gas changes over time. Furthermore, each time sample gas is collected, impurities from the atmosphere are mixed into the sample gas. Therefore, it is difficult to dilute the sample gas under the same conditions. As a result, the reliability of the analysis results decreases.

[0006] An object of the present invention is to provide a sampling system and a sampling method that can obtain highly reliable analytical results even when the sample is small in amount.

[0007] One aspect of the present invention relates to a sampling system for sampling a sample to be introduced into an analytical device, comprising: a chamber in which the sample is collected; a measuring tube into which the sample collected in the chamber is introduced; a pressure gauge for measuring the pressure of at least one of the chamber and the measuring tube; a memory unit for storing pressure information indicating the pressure at each of the kth (k is an integer greater than or equal to 1) analysis points measured by the pressure gauge; and an output unit for outputting the pressure information stored in the memory unit.

[0008] Another aspect of the present invention relates to a sampling system for sampling a sample to be introduced into an analytical device, comprising: a chamber in which the sample is collected; a measuring tube into which the sample collected in the chamber is introduced; a pressure gauge for measuring the pressure in at least one of the chamber and the measuring tube; a flow rate adjustment unit for adjusting the flow rate of the sample introduced from the chamber into the measuring tube; and a flow rate control unit for controlling the operation of the flow rate adjustment unit so that a constant amount of sample is introduced into the measuring tube based on the pressure at each of the kth analysis points (k is an integer greater than or equal to 1) measured by the pressure gauge.

[0009] Yet another aspect of the present invention relates to a sampling method for sampling a sample to be introduced into an analytical device, the sampling method including: collecting the sample in a chamber; introducing the sample collected in the chamber into a measuring tube; measuring the pressure of at least one of the chamber and the measuring tube with a pressure gauge; storing pressure information indicating the pressure at each of the kth analysis points measured by the pressure gauge (k is an integer greater than or equal to 1) in a memory unit; and outputting the pressure information stored in the memory unit.

[0010] Yet another aspect of the present invention relates to a sampling method for sampling a sample to be introduced into an analytical device, the sampling method including: collecting the sample in a chamber; introducing the sample collected in the chamber into a measuring tube; measuring the pressure in at least one of the chamber and the measuring tube with a pressure gauge; adjusting the flow rate of the sample introduced from the chamber into the measuring tube with a flow rate adjustment unit; and controlling the operation of the flow rate adjustment unit so that a constant amount of sample is introduced into the measuring tube based on the pressure at each of the kth analysis points (k is an integer greater than or equal to 1) measured by the pressure gauge.

[0011] According to the present invention, highly reliable analytical results can be obtained even when the sample is small in amount.

[0012] FIG. 1 is a diagram showing the configuration of an analysis system including a sampling system according to a first embodiment of the present invention. FIG. 2 is a block diagram of the analysis system for explaining the configuration of the sampling system. FIG. 3 is a block diagram of the analysis system for explaining the configuration of the functional parts of the control unit of FIG. 2. FIG. 4 is a flowchart showing an example of a sampling processing algorithm executed by the control unit of FIG. 3 based on a sampling program. FIG. 5 is a diagram showing the configuration of a sampling system according to a second embodiment of the present invention. FIG. 6 is a block diagram of the analysis system for explaining the configuration of the functional parts of the control unit of FIG. 5. FIG. 7 is a flowchart showing an example of a sampling processing algorithm executed by the control unit of FIG. 6 based on a sampling program.

[0013] 1. First Embodiment (1) Configuration of Analysis System A sampling system and a sampling method according to an embodiment of the present invention will now be described in detail with reference to the drawings. Fig. 1 is a diagram showing the configuration of an analysis system including a sampling system according to a first embodiment of the present invention. As shown in Fig. 1, an analysis system 200 includes a sampling system 100, a gas cylinder 110, a carrier supply unit 120, a vacuum pump 130, and an analysis device 140.

[0014] The gas cylinder 110 contains a sample gas to be analyzed at high pressure. The carrier supply unit 120 is composed of, for example, a gas cylinder, a pump, a flow rate control valve, and a flow path switching valve. The carrier supply unit 120 supplies a carrier gas to the sampling system 100. The carrier gas may be, for example, an inert gas such as helium gas, or may be hydrogen gas.

[0015] Sampling system 100 uses a measuring tube to introduce sample gas sealed in a gas cylinder 110 into an analyzer 140 together with carrier gas supplied by a carrier supply unit 120. Vacuum pump 130 is used to evacuate the measuring tube of sampling system 100. Details of sampling system 100 will be described later.

[0016] The analyzer 140 is, for example, a gas chromatograph (GC) and includes a separation column 141, a detector 142, and an analysis control unit 143. The separation column 141 is housed in a column thermostatic bath (not shown) and maintained at a predetermined constant temperature. The separation column 141 separates the sample gas introduced by the sampling system 100 into individual components based on differences in chemical properties or composition. The detector 142 detects the components of the sample gas separated by the separation column 141 and outputs a detection signal corresponding to the detection intensity to the analysis control unit 143.

[0017] The analysis control unit 143 is configured with, for example, a CPU (Central Processing Unit), RAM (Random Access Memory), ROM (Read Only Memory), and a hard disk, etc. The analysis control unit 143 controls the operation of the column thermostatic bath and the detector 142. The analysis control unit 143 also processes the detection signal output by the detector 142 to generate a gas chromatogram showing the relationship between the retention time of each component in the separation column 141 and the detection intensity.

[0018] In this example, the analyzer 140 is a GC, but the embodiment is not limited to this. The analyzer 140 may be, for example, a GCMS (gas chromatograph mass spectrometer). In this case, the analyzer 140 further includes a mass analyzer instead of or in addition to the detector 142. The analysis control unit 143 processes the analysis results from the mass analyzer to generate a mass spectrum.

[0019] (2) Configuration of the Sampling System Figure 2 is a block diagram of an analysis system 200 to explain the configuration of the sampling system 100. As shown in Figure 2, the sampling system 100 includes a chamber 10, a measuring tube 20, and a processing device 30. The sampling system 100 also includes a plurality of valves v1 to v4 and a plurality of pressure gauges P1 and P2.

[0020] Valve v1, chamber 10, valve v2, metering tube 20, and valve v3 are provided in this order from upstream to downstream in the flow path between gas cylinder 110 and analyzer 140. A carrier supply unit 120 is connected to the portion of the flow path between valve v2 and metering tube 20 through a branch flow path. Valve v4 is provided in the branch flow path. A vacuum pump 130 is connected to metering tube 20. Pressure gauge P1 measures the pressure in chamber 10. Pressure gauge P2 measures the pressure in metering tube 20.

[0021] The processing device 30 includes a control unit 31 and a storage unit 32. The control unit 31 includes, for example, a CPU. The control unit 31 controls the operations of the valves v1 to v4, the vacuum pump 130, etc., to perform a sampling process for introducing the sample gas into the analysis device 140.

[0022] The storage unit 32 includes a RAM (random access memory), a ROM (read only memory), a hard disk, or the like. The control unit 31 and the storage unit 32 may be realized by a microcomputer. The storage unit 32 stores a sampling program for causing the control unit 31 to execute a sampling process. The storage unit 32 also stores pressure information indicating the pressures measured by the pressure gauges P1 and P2 at a predetermined time point.

[0023] Fig. 3 is a block diagram of the analysis system 200 for explaining the configuration of the functional units of the control unit 31 in Fig. 2. As shown in Fig. 3, the control unit 31 includes, as functional units, an apparatus control unit 1, a memory control unit 2, an output unit 3, and a correction unit 4. The functional units in Fig. 3 are realized by the control unit 31 executing a sampling program stored in the memory unit 32. At least some of the functional units of the control unit 31 may be realized by hardware such as electronic circuits.

[0024] The device control unit 1 controls the operation of the valves v1 to v4 and the vacuum pump 130. The memory control unit 2 stores pressure information indicating the pressure measured by the pressure gauges P1 and P2 in the memory unit 32 each time an analysis is performed by the analyzer 140. The output unit 3 outputs the pressure information stored in the memory unit 32 at the time of each analysis. Based on the pressure information output by the memory unit 32, the correction unit 4 generates correction information for correcting the analysis results obtained by the analyzer 140 to analysis results obtained when a fixed amount of sample gas is introduced into the analyzer 140.

[0025] (3) Sampling Process Figure 4 is a flowchart showing an example of a sampling process algorithm executed by the control unit 31 of Figure 3 based on a sampling program. The sampling process will be explained below using the analysis system 200 of Figure 3 and the flowchart of Figure 4. In the initial state of the sampling process, valves v1 to v4 are closed. Furthermore, the measuring tube 20 is evacuated by the vacuum pump 130.

[0026] First, the device control unit 1 opens the valve v1 for a predetermined time and then closes the valve v1 again, thereby collecting the sample gas sealed in the gas cylinder 110 into the chamber 10 (step S1). In this example, the chamber 10 is initially filled with air, but it may also be filled with an inert gas. In this case, impurities are prevented from being mixed into the sample gas collected in the chamber 10. Alternatively, the chamber 10 may be evacuated in the initial state. With this configuration, the sample gas can be easily collected into the chamber 10 even when the pressure of the sample gas in the gas cylinder 110 is not very high.

[0027] Next, the device control unit 1 sets a variable k to 1 (step S2). The variable k indicates the number of the analysis repeatedly performed by the analysis device 140. Therefore, it indicates that the kth analysis is currently being performed. Step S1 and step S2 may be performed either first or simultaneously.

[0028] Next, the memory control unit 2 stores pressure information indicating the pressure of the chamber 10 measured by the pressure gauge P1 in the memory unit 32 (step S3). The pressure information of the chamber 10 corresponds to the molar amount of the sample gas collected in the chamber 10. Therefore, by recording the pressure information of the chamber 10, the molar amount of the sample gas remaining in the chamber 10 can be managed.

[0029] Thereafter, the device control unit 1 opens the valve v2 for a predetermined time and then closes the valve v2 again, thereby introducing a portion of the sample gas collected in the chamber 10 into the metering tube 20 (step S4). Since the metering tube 20 is initially evacuated, the sample gas can be easily introduced into the metering tube 20 by opening and closing the valve v2.

[0030] Next, the memory control unit 2 stores pressure information indicating the pressure of the metering tube 20 measured by the pressure gauge P2 in the memory unit 32 (step S5). The pressure information of the metering tube 20 corresponds to the molar amount of the sample gas introduced into the metering tube 20. Therefore, by recording the pressure information of the metering tube 20, the molar amount of the sample gas introduced into the metering tube 20 can be managed.

[0031] Next, the device control unit 1 opens the valves v3 and v4 for a predetermined time, and then closes the valves v3 and v4 again, thereby introducing the sample gas introduced into the metering tube 20 into the analyzer 140 together with the carrier gas supplied by the carrier supply unit 120 (step S6). The analyzer 140 performs the kth analysis of the introduced sample gas.

[0032] The output unit 3 then outputs the pressure information stored in the memory unit 32 (step S7). Next, the correction unit 4 generates correction information for correcting the kth analysis result obtained by the analyzer 140 based on the pressure information output in step S7 (step S8). The analysis result is, for example, the height or area of ​​each peak in a gas chromatogram. The analysis result may also be the height or area of ​​each peak in a mass spectrum.

[0033] Here, the pressure in the measuring tube 20 in the k-th analysis is P ｋ In this case, the correction information for correcting the k-th analysis result is, for example, P １ / P ｋ By multiplying the kth analysis result by this correction information, it is possible to obtain the analysis result when the same molar amount of sample gas as that introduced into the analysis device 140 in the first analysis is introduced in the kth analysis.

[0034] Next, the device control unit 1 turns on the vacuum pump 130 for a predetermined time, and then turns off the vacuum pump 130 again, thereby evacuating the measuring tube 20 (step S9). The device control unit 1 also adds 1 to the variable k (step S10). Steps S9 and S10 may be executed either first, or simultaneously. Thereafter, the process returns to step S3. Steps S3 to S10 corresponding to the (k+1)th analysis are thereby repeated.

[0035] (4) Effects In the sampling system 100 according to this embodiment, pressure information indicating the pressure in the chamber 10 and the measuring tube 20 at each of the kth analysis times is stored in the memory unit 32, and the pressure information is output by the output unit 3. Based on the pressure information output by the output unit 3, the correction unit 4 generates correction information for correcting the analysis results obtained by the analyzer 140 to the analysis results when a fixed amount of sample is introduced into the analyzer 140.

[0036] According to this configuration, even if the amount of sample introduced into the measuring tube 20 decreases with each repeated analysis, the correction information can be used to correct the analysis results of each analysis to those obtained when a fixed amount of sample is introduced into the analyzer 140. Therefore, it is not necessary to introduce the sample into the measuring tube 20 under the same conditions for each analysis. Furthermore, even if the amount of sample introduced is small, repeated sample analysis can be performed, and the same analysis results as when the sample is introduced into the analyzer 140 under the same conditions for each analysis can be obtained. This improves the reliability of the analysis results. As a result, highly reliable analysis results can be obtained even when the amount of sample is small.

[0037] 2. Second Embodiment (1) Configuration of Sampling System The sampling system and sampling method according to the second embodiment will be described below, focusing on differences from the sampling system and sampling method according to the first embodiment. Fig. 5 is a diagram showing the configuration of a sampling system 100 according to the second embodiment of the present invention. As shown in Fig. 5, the sampling system 100 further includes a flow rate adjustment unit 40.

[0038] The flow rate adjustment unit 40 is, for example, a flow rate adjustment valve, and by changing the valve opening, adjusts the flow rate of the sample gas introduced from the chamber 10 into the metering tube 20 when the valve v2 is open. In this example, the flow rate adjustment unit 40 is provided in the flow path between the chamber 10 and the valve v2, but the embodiment is not limited to this. The position of the flow rate adjustment unit 40 and the position of the valve v2 may be reversed. Furthermore, the flow rate adjustment unit 40 may be a pump.

[0039] Fig. 6 is a block diagram of the analysis system 200 for explaining the configuration of the functional units of the control unit 31 in Fig. 5. As shown in Fig. 6, the control unit 31 includes a flow rate control unit 5 as a functional unit instead of the output unit 3 and the correction unit 4. In this embodiment, the control unit 31 includes a memory control unit 2 that operates in the same manner as in the first embodiment, but the embodiment is not limited to this. In cases where pressure information does not need to be stored in the memory unit 32, the control unit 31 does not need to include the memory control unit 2.

[0040] Based on the pressure measured by pressure gauge P1, flow rate control unit 5 controls the operation of flow rate adjustment unit 40 so that a fixed amount of sample is introduced into metering tube 20. Specifically, the pressure of chamber 10 measured by pressure gauge P1 corresponds to the molar amount of sample gas collected in chamber 10. Therefore, in the kth analysis, a molar amount of sample gas corresponding to the difference between the pressure in chamber 10 at the (k-1)th analysis and the pressure in chamber 10 at the kth analysis is introduced into metering tube 20.

[0041] Therefore, the pressure in the chamber 10 in the kth analysis is P ｋ Then, in the k-th analysis, the flow rate adjusting unit 40 is controlled to obtain P ｋ－１ -P ｋ =P ｋ -P ｋ＋１ Thus, in the second and subsequent analyses, the same amount of sample as in the first analysis can be introduced into the measuring tube 20, regardless of the amount of sample gas remaining in the chamber 10.

[0042] (2) Sampling Process Fig. 7 is a flowchart showing an example of a sampling process algorithm executed by the control unit 31 of Fig. 6 based on a sampling program. The sampling process according to this embodiment will be described below using the analysis system 200 of Fig. 6 and the flowchart of Fig. 7. The initial state of the sampling process according to this embodiment is the same as the initial state of the sampling process according to the first embodiment.

[0043] First, the device control unit 1 opens the valve v1 for a predetermined time, and then closes the valve v1 again to collect the sample gas sealed in the gas cylinder 110 into the chamber 10 (step S21). Next, the device control unit 1 sets the variable k to 1 (step S22). Next, the flow rate control unit 5 acquires the pressure of the chamber 10 measured by the pressure gauge P1 before the sample gas is introduced into the measuring tube 20 for the kth analysis (hereinafter referred to as the pre-introduction pressure) (step S23). The pre-introduction pressure for the kth analysis is calculated by P ｋ This becomes:

[0044] Thereafter, the device control unit 1 starts introducing the sample gas from the chamber 10 into the measuring tube 20 by opening the valve v2 (step S24). Here, the flow rate control unit 5 determines whether the variable k is 2 or greater (step S25). If the variable k is 2 or greater, the flow rate control unit 5 acquires the pressure of the chamber 10 measured by the pressure gauge P1 while the sample gas is being introduced into the measuring tube 20 (hereinafter referred to as the introduction pressure) (step S26). The introduction pressure acquired in step S26 is P ｘ Let's say.

[0045] Next, the flow rate control unit 5 calculates the P ｋ－１ , P ｋ and P obtained in step S26 ｘ Based on this, it is determined whether a certain amount of sample gas has been introduced into the measuring tube 20 (step S27). ｋ－１ -P ｋ =P ｋ -P ｘ When this occurs, it is determined that a certain amount of sample gas has been introduced into the measuring tube 20. ｘ is the pre-introduction pressure (P ｋ＋１ )

[0046] If a certain amount of sample gas has not been introduced into the measuring tube 20, the process returns to step S26. In this case, steps S26 and S27 are repeated until a certain amount of sample gas has been introduced into the measuring tube 20. If a certain amount of sample gas has been introduced into the measuring tube 20, the process proceeds to step S28. If the variable k is not 2 or greater in step S25, i.e., if the variable k is 1, the process also proceeds to step S28.

[0047] In step S28, the device control unit 1 closes valve v2, thereby ending the introduction of the sample gas from chamber 10 into metering tube 20 (step S28). Next, the device control unit 1 opens valves v3 and v4 for a predetermined time, and then closes valves v3 and v4 again, thereby introducing the sample gas introduced into metering tube 20 together with the carrier gas supplied by carrier supply unit 120 into analyzer 140 (step S29). In analyzer 140, the kth analysis is performed on the introduced sample gas.

[0048] Next, the device control unit 1 turns on the vacuum pump 130 for a predetermined time, and then turns off the vacuum pump 130 again to evacuate the measuring tube 20 (step S30). The device control unit 1 also adds 1 to the variable k (step S31). Thereafter, the process returns to step S23. This causes steps S23 to S31 corresponding to the (k+1)th analysis to be repeated.

[0049] (3) Effects In the sampling system 100 according to this embodiment, the operation of the flow rate regulator 40 is controlled based on the pressure at each kth analysis point, thereby introducing a constant amount of sample into the metering tube 20. Therefore, even when the sample amount is small, it is possible to repeatedly analyze the sample under the same conditions. This improves the reliability of the analysis results. As a result, highly reliable analysis results can be obtained even when the sample amount is small.

[0050] 3. Other Embodiments (1) In the above embodiment, the sampling system 100 includes the vacuum pump 130, but the embodiment is not limited to this. If the measuring tube 20 is not evacuated in the initial state of the sampling process, the sampling system 100 does not need to include the vacuum pump 130. In this case, step S9 is skipped in the sampling process of FIG. 4. Similarly, step S30 is skipped in the sampling process of FIG. 7.

[0051] (2) In the above embodiment, the carrier gas is supplied to the measuring tube 20, and the carrier gas is introduced into the analyzer 140 together with the sample gas. However, the embodiment is not limited to this. The sample gas introduced into the measuring tube 20 may be introduced into the measuring tube 20 by suction by the analyzer 140. In this case, the carrier gas does not need to be supplied to the measuring tube 20. Therefore, the branch flow path and the valve v4 do not need to be provided in the sampling system 100.

[0052] (3) In the first embodiment, the output unit 3 outputs the pressure information stored in the memory unit 32 to the correction unit 4, but the embodiment is not limited to this. The output unit 3 may output the pressure information stored in the memory unit 32 to the analysis control unit 143 of the analysis device 140. In this case, the analysis control unit 143 may generate correction information based on the output pressure information.

[0053] Alternatively, the output unit 3 may output the pressure information stored in the memory unit 32 to an external information processing device, external storage medium, display device, printer, or the like of the sampling system 100. In this case, the external information processing device or user of the sampling system 100 can evaluate the amount of sample introduced into the analysis device 140 for each analysis based on the output pressure information. In addition, the external information processing device or user can generate correction information based on the output pressure information. If the pressure information is not output to the correction unit 4, the control unit 31 does not need to include the correction unit 4.

[0054] (4) In the first embodiment, the sampling system 100 includes the pressure gauge P1, but the embodiment is not limited to this. In the sampling process of FIG. 4, pressure information of the chamber 10 is not used to generate correction information. Therefore, the sampling system 100 does not need to include the pressure gauge P1.

[0055] (5) In the second embodiment, the sampling system 100 includes the pressure gauge P2, but the embodiment is not limited to this. In the sampling process of Fig. 7, the pressure information of the metering tube 20 is not used to control the flow rate adjuster 40. Therefore, the sampling system 100 does not need to include the pressure gauge P2.

[0056] (6) In the first embodiment, the sampling system 100 may further include a thermometer for measuring the temperature of the sample gas. In this case, the thermometer may be provided in the chamber 10 or in the measuring tube 20. Alternatively, the thermometer may be a room temperature thermometer, and the temperature of the room in which the sampling system 100 is installed may be measured as the temperature of the sample gas.

[0057] In this configuration, the memory control unit 2 causes the memory unit 32 to further store temperature information indicating the temperature measured by the thermometer each time an analysis is performed by the analysis device 140. The output unit 3 further outputs the temperature information stored in the memory unit 32. The correction unit 4 generates correction information further based on the temperature information output by the output unit 3.

[0058] Specifically, the temperature of the sample gas in the k-th analysis is T ｋ In this case, the correction information for correcting the k-th analysis result is, for example, P １ ・T ｋ / (P ｋ ・T １ ) may be used. This configuration allows more accurate correction information to be generated. Therefore, by multiplying the kth analysis result by this correction information, more accurate analysis results can be obtained when the same molar amount of sample gas as that introduced into the analyzer 140 during the first analysis is introduced during the kth analysis.

[0059] (7) In the first embodiment, the correction information may be generated based on the pressure information of the chamber 10, rather than the pressure information of the measuring tube 20. For example, the pressure of the chamber 10 in the k-th analysis may be expressed as P ｋ In this case, the molar amount of the sample gas introduced into the measuring tube 20 in the k-th analysis is P ｋ -P ｋ＋１ Therefore, the correction information for correcting the k-th analysis result corresponds to, for example, (P １ -P ２ ) / (P ｋ -P ｋ＋１ ) may also be used.

[0060] By multiplying this correction information by the kth analysis result, it is possible to obtain the analysis result for when the same molar amount of sample gas as that introduced into the analyzer 140 during the first analysis is introduced in the kth analysis. In this configuration, the pressure information of the metering tube 20 is not used to generate the correction information. Therefore, the sampling system 100 does not need to include the pressure gauge P2.

[0061] In this configuration, the correction information may also be generated based on temperature information indicating the temperature of the sample. For example, if the temperature of the sample gas in the k-th analysis is T ｋ In this case, the correction information for correcting the k-th analysis result is, for example, (P １ T ２ -P ２ T １ ) T ｋ T ｋ＋１ / ((P ｋ T ｋ＋１ -P ｋ＋１ T ｋ ) T １ T ２ ) may also be used.

[0062] This configuration allows for more accurate correction information to be generated, and therefore, by multiplying the kth analysis result by this correction information, more accurate analysis results can be obtained when the same molar amount of sample gas as that introduced into the analyzer 140 in the first analysis is introduced in the kth analysis.

[0063] (8) In the second embodiment, the flow rate adjusting unit 40 may be controlled further based on the temperature of the sample gas. For example, the temperature of the sample gas in the kth analysis may be set to T ｋ In this case, in the k-th analysis, the flow rate adjusting unit 40 calculates P ｋ－１ / T ｋ－１ -P ｋ / T ｋ =P ｋ / T ｋ -P ｋ＋１ / T ｋ＋１According to this configuration, a constant amount of sample gas can be introduced more accurately into the measuring tube 20. As a result, more accurate analysis results can be obtained in the kth analysis.

[0064] (9) In the second embodiment, the flow rate adjusting unit 40 may be controlled based on the pressure in the measuring tube 20, rather than the pressure in the chamber 10. For example, the pressure in the measuring tube 20 in the k-th analysis may be set to P ｋ Let this P ｋ corresponds to the molar amount of the sample gas introduced into the measuring tube 20 in the k-th analysis. Therefore, in the k-th analysis, the flow rate adjusting unit 40 adjusts P ｋ－１ =P ｋ The control may be performed so that

[0065] With this configuration, in the second and subsequent analyses, the same amount of sample as in the first analysis can be introduced into the measuring tube 20, regardless of the amount of sample gas remaining in the chamber 10. This allows accurate analysis results to be obtained in the kth analysis. In this configuration, the pressure in the chamber 10 is not used to control the flow rate adjuster 40. Therefore, the sampling system 100 does not need to include a pressure gauge P1.

[0066] In this configuration, the flow rate adjusting unit 40 may also be controlled based on the temperature of the sample gas. For example, the temperature of the sample gas in the k-th analysis may be set to T ｋ In this case, in the k-th analysis, the flow rate adjusting unit 40 calculates P ｋ－１ / T ｋ－１ =P ｋ / T ｋ According to this configuration, a constant amount of sample gas can be introduced more accurately into the measuring tube 20. As a result, more accurate analysis results can be obtained in the kth analysis.

[0067] 4. Aspects It will be understood by those skilled in the art that the above exemplary embodiments are examples of the following aspects.

[0068] (Item 1) A sampling system according to one embodiment is a sampling system for sampling a sample to be introduced into an analytical device, and may include: a chamber from which the sample is collected; a measuring tube into which the sample collected in the chamber is introduced; a pressure gauge for measuring the pressure of at least one of the chamber and the measuring tube; a memory unit for storing pressure information indicating the pressure at each of the kth (k is an integer greater than or equal to 1) analysis points measured by the pressure gauge; and an output unit for outputting the pressure information stored in the memory unit.

[0069] In this sampling system, pressure information indicating the pressure in at least one of the chamber and the metering tube at each kth analysis time point is stored in a memory unit, and the pressure information is output. Therefore, it is possible to evaluate the amount of sample introduced into the analyzer for each analysis based on the pressure information. Furthermore, even if the amount of sample introduced into the metering tube decreases with each analysis, it is possible to correct the analysis results of each analysis to those obtained when a constant amount of sample is introduced into the analyzer based on the output pressure information.

[0070] Therefore, with the above configuration, it is not necessary to introduce a sample into the measuring tube under the same conditions for each analysis. Furthermore, even if the amount of sample introduced is small, repeated sample analysis is possible, and the same analysis results as when the sample is introduced into the analytical device under the same conditions for each analysis are obtained. This improves the reliability of the analysis results. As a result, highly reliable analysis results can be obtained even with small amounts of sample.

[0071] (2) The sampling system described in paragraph 1 may further include a correction unit that generates correction information based on the pressure information output by the output unit to correct the analysis results obtained by the analysis device to the analysis results when a fixed amount of sample is introduced into the analysis device.

[0072] In this case, by using the correction information generated by the correction unit, the analysis results obtained by the analyzer are corrected to the analysis results obtained when a fixed amount of sample is introduced into the analyzer, thereby making it easy to obtain analysis results with improved reliability.

[0073] (Item 3) In the sampling system described in item 2, the pressure gauge measures the pressure in the measuring tube, and the pressure in the measuring tube in the k-th analysis is expressed as P ｋ In this case, the correction unit １ / P ｋ may be generated as the correction information for correcting the k-th analysis result.

[0074] In this case, the correction information can be generated with a simple configuration.

[0075] (4) In the sampling system according to the second aspect, the pressure gauge measures the pressure in the chamber, and the pressure in the chamber in the k-th analysis is expressed as P ｋ In this case, the correction unit calculates (P １ -P ２ ) / (P ｋ -P ｋ＋１ ) may be generated as the correction information for correcting the kth analysis result.

[0076] In this case, the correction information can be generated with a simple configuration.

[0077] (Item 5) In the sampling system described in item 2, the memory unit may further store temperature information indicating the temperature of the sample at each of the kth analysis points, the output unit may further output the temperature information stored in the memory unit, and the correction unit may generate the correction information further based on the temperature information output by the output unit.

[0078] In this case, more accurate correction information can be generated.

[0079] (Item 6) In the sampling system described in item 1, the output section may output the pressure information to the analyzer.

[0080] According to this configuration, the analytical device can correct the analytical results of each analysis to the analytical results when a fixed amount of sample is introduced into the analytical device, based on the output pressure information.

[0081] (Item 7) A sampling system according to another aspect is a sampling system for sampling a sample to be introduced into an analytical device, and may include: a chamber in which the sample is collected; a measuring tube into which the sample collected in the chamber is introduced; a pressure gauge that measures the pressure in at least one of the chamber and the measuring tube; a flow rate adjustment unit that adjusts the flow rate of the sample introduced from the chamber into the measuring tube; and a flow rate control unit that controls the operation of the flow rate adjustment unit so that a fixed amount of sample is introduced into the measuring tube based on the pressure at each of the kth analysis points (k is an integer greater than or equal to 1) measured by the pressure gauge.

[0082] In this sampling system, the operation of the flow rate regulator is controlled based on the pressure at each kth analysis time point, thereby introducing a constant amount of sample into the measuring tube. Therefore, even if the sample amount is small, it is possible to repeatedly analyze the sample under the same conditions. This improves the reliability of the analysis results. As a result, highly reliable analysis results can be obtained even with small sample amounts.

[0083] (Item 8) In the sampling system according to item 7, the pressure gauge measures the pressure of the chamber, and the pressure of the chamber in the k-th analysis is expressed as P ｋ In this case, the flow rate control unit calculates P ｋ－１ -P ｋ =P ｋ -P ｋ＋１ The operation of the flow rate adjusting unit may be controlled so as to

[0084] In this case, a fixed amount of sample can be introduced into the measuring tube with a simple configuration.

[0085] (Item 9) In the sampling system described in item 7, the pressure gauge measures the pressure in the measuring tube, and the pressure in the measuring tube in the k-th analysis is expressed as P ｋ In this case, the flow rate control unit calculates P ｋ－１ =P ｋ The operation of the flow rate adjusting unit may be controlled so as to

[0086] In this case, a fixed amount of sample can be introduced into the measuring tube with a simple configuration.

[0087] (Item 10) In the sampling system described in item 7, the flow rate adjustment unit may acquire the temperature of the sample at each of the kth analysis points, and control the flow rate control unit further based on the acquired temperature.

[0088] In this case, a constant amount of sample can be introduced into the measuring tube more accurately.

[0089] (Item 11) A sampling method according to yet another aspect is a sampling method for sampling a sample to be introduced into an analytical device, and may include: collecting the sample in a chamber; introducing the sample collected in the chamber into a measuring tube; measuring the pressure of at least one of the chamber and the measuring tube with a pressure gauge; storing pressure information indicating the pressure at each of the kth analysis points measured by the pressure gauge (k is an integer greater than or equal to 1) in a memory unit; and outputting the pressure information stored in the memory unit.

[0090] This sampling method eliminates the need to introduce a sample into the measuring tube under the same conditions for each analysis. Furthermore, even if the amount of sample introduced is small, repeated analysis of the sample is possible, and the same analysis results as when the sample is introduced into the analyzer under the same conditions for each analysis are obtained. This improves the reliability of the analysis results. As a result, highly reliable analysis results can be obtained even with small sample amounts.

[0091] (Clause 12) A sampling method according to yet another aspect is a sampling method for sampling a sample to be introduced into an analytical device, and may include: collecting the sample in a chamber; introducing the sample collected in the chamber into a measuring tube; measuring the pressure of at least one of the chamber and the measuring tube with a pressure gauge; adjusting the flow rate of the sample introduced from the chamber into the measuring tube with a flow rate adjustment unit; and controlling the operation of the flow rate adjustment unit so that a fixed amount of sample is introduced into the measuring tube based on the pressure at each of the kth analysis points (k is an integer greater than or equal to 1) measured by the pressure gauge.

[0092] This sampling method allows a fixed amount of sample to be introduced into the measuring tube, making it possible to repeatedly analyze the sample under the same conditions, even when the sample volume is small. This improves the reliability of the analysis results. As a result, highly reliable analysis results can be obtained even when the sample volume is small.

Claims

1. A sampling system for sampling a sample to be introduced into an analytical device, comprising: a chamber in which the sample is taken; a measuring tube into which the collected sample is introduced into the chamber; a pressure gauge for measuring the pressure in at least one of the chamber and the metering tube; a storage unit that stores pressure information indicating the pressure measured by the pressure gauge at each of k-th analysis times (k is an integer of 1 or more); an output unit that outputs the pressure information stored in the storage unit; A sampling system comprising: a correction unit that generates correction information for correcting the analysis results obtained by the analysis device to the analysis results when a fixed amount of sample is introduced into the analysis device based on the pressure information output by the output unit.

2. the pressure gauge measures the pressure in the metering tube; The pressure in the measuring tube in the k-th analysis is P ｋ In this case, the correction unit １ / P ｋ The sampling system according to claim 1 , wherein the correction information for correcting the k-th analysis result is generated as follows:

3. the pressure gauge measures the pressure in the chamber; The pressure in the chamber in the k-th analysis is P ｋ In this case, the correction unit calculates (P １ -P ２ ) / (P ｋ -P ｋ＋１ 2. The sampling system according to claim 1, wherein the k-th analysis result is generated as the correction information for correcting the k-th analysis result.

4. the storage unit further stores temperature information indicating the temperature of the sample at each of the k-th analysis times; the output unit further outputs the temperature information stored in the storage unit; The sampling system according to claim 1 , wherein the correction unit generates the correction information further based on the temperature information output by the output unit.

5. A sampling system for sampling a sample to be introduced into an analytical device, comprising: a chamber in which the sample is taken; a measuring tube into which the collected sample is introduced into the chamber; a pressure gauge for measuring the pressure in at least one of the chamber and the metering tube; a flow rate adjusting unit that adjusts the flow rate of the sample introduced from the chamber into the measuring tube; A sampling system comprising a flow control unit that controls the operation of the flow adjustment unit so that a fixed amount of sample is introduced into the measuring tube based on the pressure at each of the kth analysis points (k is an integer greater than or equal to 1) measured by the pressure gauge.

6. the pressure gauge measures the pressure in the chamber; The pressure in the chamber in the k-th analysis is P ｋ In this case, the flow rate control unit calculates P ｋ－１ -P ｋ =P ｋ -P ｋ＋１ The sampling system according to claim 5 , wherein the operation of the flow rate adjusting unit is controlled so that:

7. the pressure gauge measures the pressure in the metering tube; The pressure in the measuring tube in the k-th analysis is P ｋ In this case, the flow rate control unit calculates P ｋ－１ =P ｋ The sampling system according to claim 5 , wherein the operation of the flow rate adjusting unit is controlled so that:

8. The sampling system according to claim 5 , wherein the flow rate control unit acquires the temperature of the sample at each kth analysis time point, and controls the flow rate adjustment unit further based on the acquired temperature.