Sampling system and sampling method

Abstract

The sampling system includes a chamber, a measuring tube, a first pressure gauge, a second pressure gauge, a storage unit, and an output unit, and samples a sample introduced into an analysis device. In the chamber, a sample is collected. A sample collected into the chamber is introduced into the metering 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 at each kth (k is an integer of 1 or more) analysis time point measured by the first pressure gauge or the second pressure gauge. The output unit outputs the pressure information stored in the storage unit.

Description

Technical Field

[0001] This invention relates to a sampling system and a sampling method. Background Technology

[0002] Gas chromatography (GC) is a known analytical device for separating substances contained in a sample gas according to their different components. The sample gas containing the analyte is introduced into the GC via a sampling system. For example, Patent Document 1 describes a sample injection method that introduces the sample gas into the GC using a gas-tight injector. Alternatively, depending on the pressure or volume of the sample gas, the sample gas is sometimes introduced into the GC using a gas sampler that combines a metering tube and a valve.

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2016-50914 Summary of the Invention The technical problem that the invention aims to solve To analyze sample gases using a gas sampler, it is necessary to be able to fully displace the amount of sample gas inside the metering tube. However, preparing large quantities of sample gas is not easy when samples are scarce or expensive.

[0004] Furthermore, to confirm analytical results, sample gases collected under the same conditions are sometimes analyzed repeatedly. In this case, the required amount of sample gas increases further. The volume of the sample gas can be increased by diluting it. However, the composition of the sample gas changes over time depending on the sampling environment. Moreover, atmospheric impurities are introduced into the sample gas with each collection. Therefore, it is difficult to dilute the sample gas under identical conditions. As a result, the reliability of the analytical results is reduced.

[0005] The purpose of this invention is to provide a sampling system and sampling method that can obtain analytical results with high reliability even when the sample size is small.

[0006] Solution to the above technical problems One aspect of the present invention relates to a sampling system for sampling a sample introduced into an analytical apparatus, the sampling system comprising: a chamber for collecting the sample; a measuring tube for introducing the sample collected into the chamber; a pressure gauge for measuring the pressure of at least one of the chamber and the measuring tube; a storage unit for storing pressure information representing the pressure at each k-th analysis time point (k being an integer greater than or equal to 1) measured by the pressure gauge; and an output unit for outputting the pressure information stored in the storage unit.

[0007] Another aspect of the present invention relates to a sampling system for sampling a sample introduced into an analytical apparatus, the sampling system comprising: a chamber for collecting the sample; a measuring tube for introducing the sample collected into the chamber; a pressure gauge for measuring the pressure of at least one of the chamber and the measuring tube; a flow regulating unit for adjusting the flow rate of the sample introduced from the chamber into the measuring tube; and a flow control unit for controlling the operation of the flow regulating unit based on the pressure at each k-th analysis time point (k being an integer greater than or equal to 1) measured by the pressure gauge, such that a constant amount of sample is introduced into the measuring tube.

[0008] Another aspect of the present invention relates to a sampling method for sampling a sample introduced into an analytical apparatus, the sampling method comprising: collecting a sample into a chamber; introducing the sample collected into the chamber into a measuring tube; measuring the pressure of at least one of the chamber and the measuring tube by a pressure gauge; storing pressure information representing the pressure at each k-th analysis time point (k being an integer greater than or equal to 1) measured by the pressure gauge in a storage unit; and outputting the pressure information stored in the storage unit.

[0009] Another aspect of the present invention relates to a sampling method for sampling a sample introduced into an analytical apparatus, the sampling method comprising: collecting a sample into a chamber; introducing the sample collected into the chamber into a measuring tube; measuring the pressure of at least one of the chamber and the measuring tube by a pressure gauge; adjusting the flow rate of the sample introduced from the chamber into the measuring tube by a flow regulating unit; and controlling the operation of the flow regulating unit such that a constant amount of sample is introduced into the measuring tube based on the pressure at each k-th analysis time point (k being an integer greater than or equal to 1) measured by the pressure gauge.

[0010] Invention Effects According to the present invention, analytical results can be obtained with high reliability even when the sample size is small. Attached Figure Description

[0011]

Figure 1

[0012]

Figure 2

[0013]

Figure 3

[0014]

Figure 4

[0015]

Figure 5

[0016]

Figure 6

[0017]

Figure 7

[0018] 1. First Implementation Method (1) Analyze the structure of the system Hereinafter, the sampling system and sampling method of the present invention will be described in detail with reference to the accompanying drawings. Figure 1 This is a diagram illustrating the structure of an analysis system incorporating the sampling system of the first embodiment of the present invention. (See diagram for example.) Figure 1 As shown, the analysis system 200 includes a sampling system 100, a gas cylinder 110, a carrier gas supply unit 120, a vacuum pump 130, and an analysis device 140.

[0019] In cylinder 110, the sample gas containing the analyte is sealed under high pressure. The carrier gas supply unit 120 comprises, for example, a gas cylinder, a pump, a flow control valve, and a flow path switching valve. The carrier gas supply unit 120 supplies carrier gas to the sampling system 100. The carrier gas can be, for example, an inert gas such as helium, or hydrogen.

[0020] The sampling system 100 uses a metering tube to introduce the sample gas sealed in the gas cylinder 110, along with the carrier gas supplied by the carrier gas supply unit 120, into the analysis device 140. A vacuum pump 130 is used to evacuate the metering tube of the sampling system 100. Details of the sampling system 100 will be described later.

[0021] The analytical apparatus 140 is, for example, a GC (gas chromatograph), and includes a separation column 141, a detector 142, and an analytical control unit 143. The separation column 141 is housed in a column oven (not shown) and maintained at a predetermined constant temperature. The separation column 141 separates the sample gas introduced by the sampling system 100 according to 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 analytical control unit 143.

[0022] The analysis control unit 143 is composed of, for example, a CPU (Central Processing Unit), RAM (Random Access Memory), ROM (Read-Only Memory), and a hard disk. The analysis control unit 143 controls the operation of the column oven and the detector 142. Furthermore, the analysis control unit 143 processes the detection signal output from the detector 142 to generate a gas chromatogram representing the relationship between the retention time and detection intensity of each component in the separation column 141.

[0023] In this example, the analytical device 140 is a GC, but the implementation is not limited to this. The analytical device 140 could also be a GCMS (Gas Chromatography-Mass Spectrometry). In this case, the analytical device 140 replaces the detector 142, or a mass spectrometry device is included in addition to the detector 142. The analytical control unit 143 generates a mass spectrum by processing the analytical results obtained from the mass spectrometry device.

[0024] (2) Structure of the sampling system Figure 2 This is a block diagram of the analysis system 200 used to illustrate the structure of the sampling system 100. For example... Figure 2 As shown, the sampling system 100 includes a chamber 10, a metering tube 20, and a processing device 30. Furthermore, the sampling system 100 includes multiple valves v1 to v4 and multiple pressure gauges P1 and P2.

[0025] Valve v1, chamber 10, valve v2, metering tube 20, and valve v3 are arranged in the flow path between gas cylinder 110 and analysis device 140 in this order from upstream to downstream. A carrier gas supply unit 120 is connected via a branch line to the section of the flow path between valve v2 and metering tube 20. Valve v4 is located in the branch line. 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.

[0026] 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 performs sampling processing to introduce sample gas into the analysis device 140 by controlling the operation of valves v1 to v4 and vacuum pump 130, etc.

[0027] The storage unit 32 includes RAM (Random Access Memory), ROM (Read-Only Memory), or a hard disk, etc. The control unit 31 and the storage unit 32 can also be implemented using a microcomputer. The storage unit 32 stores a sampling program used to cause the control unit 31 to perform sampling processing. Furthermore, the storage unit 32 stores pressure information representing the pressure measured by pressure gauges P1 and P2 at a specified time.

[0028] Figure 3 It is used for explanation Figure 2 A block diagram of the structure analysis system 200 for the functional parts of the control unit 31. (See diagram 200 for example.) Figure 3 As shown, the control unit 31, as a functional unit, includes a device control unit 1, a storage control unit 2, an output unit 3, and a calibration unit 4. The control unit 31 executes the sampling program stored in the storage unit 32 to achieve... Figure 3 The functional units of the control unit 31 can also be implemented by hardware such as electronic circuits.

[0029] The device control unit 1 controls the operation of valves v1 to v4 and the vacuum pump 130. The storage control unit 2 stores pressure information, representing the pressure measured by pressure gauges P1 and P2, in the storage unit 32 each time analysis is performed by the analysis device 140. The output unit 3 outputs the pressure information stored in the storage unit 32 for each analysis time point. The correction unit 4 generates correction information based on the pressure information output from the storage unit 32 to correct the analysis results obtained by the analysis device 140 for the case where a constant amount of sample gas is introduced into the analysis device 140.

[0030] (3) Sampling Processing Figure 4 It is shown by Figure 3 A flowchart illustrating an example of the sampling processing algorithm executed by the control unit 31 based on the sampling procedure. Hereinafter, using... Figure 3 Analysis system 200 and Figure 4 The sampling process is illustrated using a flowchart. In the initial state of the sampling process, valves v1 to v4 are closed. Furthermore, metering tube 20 is evacuated by vacuum pump 130.

[0031] First, the device control unit 1 opens valve v1 for a predetermined time and then closes valve v1 again, thereby collecting the sample gas sealed in gas cylinder 110 into chamber 10 (step S1). Furthermore, in this example, chamber 10 is initially sealed with atmospheric air, but it can also be sealed with an inert gas. In this case, impurities can be prevented from contaminating the sample gas collected into chamber 10. Alternatively, chamber 10 can be vacuumed initially. With this structure, even when the pressure of the sample gas in gas cylinder 110 is not very high, the sample gas can be easily collected into chamber 10.

[0032] Next, the device control unit 1 sets variable k to 1 (step S2). Variable k represents the number of the analysis repeatedly performed by the analysis device 140. Therefore, it is shown that the k-th analysis is being performed at the current time. Steps S1 and S2 can be performed either first or simultaneously.

[0033] Next, the storage control unit 2 causes the storage unit 32 to store pressure information representing the pressure of the chamber 10 measured by the pressure gauge P1 (step S3). The pressure information of the chamber 10 corresponds to the molar amount of sample gas collected in the chamber 10. Therefore, by recording the pressure information of the chamber 10, the molar amount of sample gas remaining in the chamber 10 can be managed.

[0034] Afterwards, the device control unit 1 opens valve v2 for a predetermined time and then closes valve v2 again, thereby introducing a portion of the sample gas collected in chamber 10 into metering tube 20 (step S4). In the initial state, metering tube 20 is evacuated, so sample gas can be easily introduced into metering tube 20 by opening and closing valve v2.

[0035] Next, the storage control unit 2 causes the storage unit 32 to store pressure information representing the pressure of the metering tube 20 measured by the pressure gauge P2 (step S5). The pressure information of the metering tube 20 corresponds to the molar amount of sample gas introduced into the metering tube 20. Therefore, by recording the pressure information of the metering tube 20, the molar amount of sample gas introduced into the metering tube 20 can be managed.

[0036] Next, after the device control unit 1 opens valves v3 and v4 for a predetermined time, it closes valves v3 and v4 again, thereby introducing the sample gas introduced into the metering tube 20 and the carrier gas supplied by the carrier gas supply unit 120 into the analysis device 140 (step S6). In the analysis device 140, the introduced sample gas is analyzed for the kth time.

[0037] Next, the output unit 3 outputs the pressure information stored in the storage unit 32 (step S7). Then, the correction unit 4 generates correction information based on the pressure information output in step S7 to correct the k-th analysis result obtained by the analysis device 140 (step S8). The analysis result may be, 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.

[0038] Here, the pressure of metering tube 20 in the k-th analysis is set as P. k In this case, the correction information used to correct the result of the k-th analysis could, for example, be P1 / P. k By multiplying this correction information by the result of the kth analysis, we can obtain the analysis result when the same molar amount of sample gas was introduced into the analysis device 140 in the kth analysis as in the first analysis.

[0039] Next, the device control unit 1 turns on the vacuum pump 130 for a predetermined time and then turns it off again, thereby evacuating the metering tube 20 (step S9). Furthermore, the device control unit 1 increments the variable k by 1 (step S10). Steps S9 and S10 can be executed either first or simultaneously. Afterwards, the process returns to step S3. Thus, steps S3 to S10 corresponding to the (k+1)th analysis are repeated.

[0040] (4) Effects In the sampling system 100 of this embodiment, pressure information representing the pressure of the chamber 10 and the metering tube 20 at each k-th analysis time point is stored in the storage 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 analysis device 140 to the case where a constant amount of sample is introduced into the analysis device 140.

[0041] According to this structure, even when the amount of sample introduced into the metering tube 20 decreases with each repeated analysis, the analysis results of each analysis can be corrected to the analysis results under the condition that a constant amount of sample is introduced into the analysis device 140 using correction information. Therefore, it is not necessary to introduce the sample into the metering tube 20 under the same conditions for each analysis. Furthermore, even when a small amount of sample is introduced, the sample analysis can be repeated, and the same analysis results can be obtained as if the sample were introduced into the analysis device 140 under the same conditions for each analysis. This improves the reliability of the analysis results. As a result, analysis results can be obtained with high reliability even with small sample amounts.

[0042] 2. Second Implementation Method (1) Structure of the sampling system Regarding the sampling system and sampling method of the second embodiment, the differences from those of the sampling system and sampling method of the first embodiment will be explained. Figure 5 This is a diagram illustrating the structure of the sampling system 100 according to the second embodiment of the present invention. Figure 5 As shown, the sampling system 100 also includes a flow regulation unit 40.

[0043] The flow regulating unit 40 is, for example, a flow regulating valve, which adjusts the flow rate of the sample gas introduced into the metering tube 20 from the chamber 10 when the valve v2 is open by changing the valve opening degree. In this example, the flow regulating unit 40 is provided in the flow path between the chamber 10 and the valve v2, but the implementation is not limited to this. The position of the flow regulating unit 40 and the position of the valve v2 may also be opposite. In addition, the flow regulating unit 40 may also be a pump.

[0044] Figure 6 It is used for explanation Figure 5A block diagram of the structure analysis system 200 for the functional parts of the control unit 31. (See diagram 200 for example.) Figure 6 As shown, the control unit 31, as a functional unit, includes a flow control unit 5 instead of the output unit 3 and the correction unit 4. Furthermore, in this embodiment, the control unit 31 includes a storage control unit 2 that operates in the same manner as in the first embodiment, but the embodiment is not limited to this. If it is not necessary to store pressure information in the storage unit 32, the control unit 31 may not include the storage control unit 2.

[0045] The flow control unit 5 controls the operation of the flow regulating unit 40 by introducing a constant amount of sample into the metering tube 20 based on the pressure measured by the pressure gauge P1. Specifically, the pressure of the chamber 10 measured by the pressure gauge P1 corresponds to the molar amount of sample gas collected in the chamber 10. Therefore, in the k-th analysis, the molar amount of sample gas corresponding to the difference between the pressure of the chamber 10 in the (k-1)-th analysis and the pressure of the chamber 10 in the k-th analysis is introduced into the metering tube 20.

[0046] Therefore, if the pressure in chamber 10 in the kth analysis is set as P... k In the k-th analysis, P is controlled by the flow regulation unit 40, thereby making P k-1 -P k =P k -P k+1 The sample gas is introduced into the metering tube 20 in this manner. Thus, in subsequent analyses, regardless of the amount of sample gas remaining in the chamber 10, the same amount of sample is introduced into the metering tube 20 as in the first analysis.

[0047] (2) Sampling Processing Figure 7 It is shown by Figure 6 A flowchart illustrating an example of the sampling processing algorithm executed by the control unit 31 based on the sampling procedure. Hereinafter, using... Figure 6 Analysis system 200 and Figure 7 The sampling process of this embodiment will be illustrated using a flowchart. Furthermore, the initial state of the sampling process in this embodiment is the same as the initial state of the sampling process in the first embodiment.

[0048] First, the device control unit 1 opens valve v1 for a predetermined time and then closes valve v1 again, thereby collecting the sample gas sealed in gas cylinder 110 into chamber 10 (step S21). Next, the device control unit 1 sets variable k to 1 (step S22). Then, for the k-th analysis, the flow control unit 5 obtains the pressure in chamber 10 measured by pressure gauge P1 before the sample gas is introduced into metering tube 20 (hereinafter referred to as the pre-introduction pressure) (step S23). The pre-introduction pressure for the k-th analysis is P in the above formula. k .

[0049] Next, the device control unit 1 starts introducing sample gas from chamber 10 into metering tube 20 by opening valve v2 (step S24). Here, the flow control unit 5 determines whether variable k is 2 or more (step S25). If variable k is 2 or more, the flow control unit 5 obtains the pressure of chamber 10 measured by pressure gauge P1 when the sample gas is introduced into metering tube 20 (hereinafter referred to as the introduction pressure) (step S26). The introduction pressure obtained in step S26 is set as P. x .

[0050] Next, the flow control unit 5, based on the P obtained in step S23 corresponding to the (k-1)th and kth analyses respectively, k-1 P k And P obtained in step S26 x The system determines whether a constant amount of sample gas has been introduced into metering tube 20 (step S27). In this example, at P... k-1 -P k =P k -P x At this point, it is determined that a constant amount of sample gas has been introduced into the metering tube 20. Furthermore, at this time, P... x This becomes the pre-introduction pressure (P) obtained in step S23 in the next analysis (the (k+1)th analysis). k+1 ).

[0051] If a constant amount of sample gas has not been introduced into the metering tube 20, the process returns to step S26. In this case, steps S26 and S27 are repeated until a constant amount of sample gas is introduced into the metering tube 20. If a constant amount of sample gas has been introduced into the metering tube 20, the process proceeds to step S28. In step S25, if variable k is not greater than 2, i.e., variable k is 1, the process also proceeds to step S28.

[0052] In step S28, the device control unit 1 stops the introduction of sample gas from chamber 10 to metering tube 20 by closing valve v2 (step S28). Next, the device control unit 1 opens valves v3 and v4 for a predetermined time, then closes valves v3 and v4 again, thereby introducing the sample gas introduced into metering tube 20 along with the carrier gas supplied by carrier gas supply unit 120 into the analysis device 140 (step S29). In the analysis device 140, the introduced sample gas is analyzed for the kth time.

[0053] Next, the device control unit 1 turns on the vacuum pump 130 for a predetermined time and then turns it off again, thereby evacuating the metering tube 20 (step S30). Furthermore, the device control unit 1 increments the variable k by 1 (step S31). Afterwards, the process returns to step S23. Thus, steps S23 to S31 corresponding to the (k+1)th analysis are repeated.

[0054] (3) Effects In the sampling system 100 of this embodiment, the operation of the flow regulating unit 40 is controlled based on the pressure at each k-th analysis time point, thereby introducing a constant amount of sample into the metering tube 20. Therefore, even with a small sample size, sample analysis can be repeated under the same conditions. As a result, the reliability of the analysis results is improved. Consequently, analysis results can be obtained with high reliability even with a small sample size.

[0055] 3. Other implementation methods (1) In the above embodiment, the sampling system 100 includes a vacuum pump 130, but the embodiment is not limited thereto. If the metering tube 20 is not evacuated in the initial state of the sampling process, the sampling system 100 may not include a vacuum pump 130. In this case, Figure 4 In the sampling process, step S9 is skipped. Similarly, in Figure 7 In the sampling process, step S30 is skipped.

[0056] (2) In the above embodiment, the carrier gas is supplied to the metering tube 20, thereby introducing the carrier gas and the sample gas together into the analytical device 140, but the embodiment is not limited to this. The sample gas introduced into the metering tube 20 can also be introduced into the metering tube 20 by suction from the analytical device 140. In this case, the carrier gas may not be supplied to the metering tube 20. Therefore, the sampling system 100 may not have a branch and valve v4.

[0057] (3) In the first embodiment, the output unit 3 outputs the pressure information stored in the storage unit 32 to the correction unit 4, but the embodiment is not limited to this. The output unit 3 may also output the pressure information stored in the storage unit 32 to the analysis control unit 143 of the analysis device 140. In this case, the analysis control unit 143 may also generate correction information based on the output pressure information.

[0058] Alternatively, the output unit 3 may output the pressure information stored in the storage unit 32 to an external information processing device, external storage medium, display device, or printing device of the sampling system 100. In this case, the external information processing device of the sampling system 100 or the user can evaluate the amount of sample introduced into the analysis device 140 for each analysis based on the output pressure information. Furthermore, the external information processing device or the user can generate calibration information based on the output pressure information. If the pressure information is not output to the calibration unit 4, the control unit 31 may not include the calibration unit 4.

[0059] (4) In the first embodiment, the sampling system 100 includes a pressure gauge P1, but the embodiment is not limited thereto. Figure 4 In the sampling process, the pressure information in chamber 10 is not used to generate correction information. Therefore, the sampling system 100 may not include pressure gauge P1.

[0060] (5) In the second embodiment, the sampling system 100 includes a pressure gauge P2, but the embodiment is not limited thereto. Figure 7 In the sampling process, the pressure information from the metering tube 20 is not used for the control of the flow regulating unit 40. Therefore, the sampling system 100 may not include the pressure gauge P2.

[0061] (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 installed in the chamber 10 or in the measuring tube 20. Alternatively, the thermometer may be a room temperature meter, and the temperature of the room in which the sampling system 100 is installed may be used as the temperature of the sample gas for measurement.

[0062] In this structure, whenever the analysis device 140 performs analysis, the storage control unit 2 also causes the storage unit 32 to store temperature information representing the temperature measured by the thermometer. The output unit 3 also outputs the temperature information stored in the storage unit 32. The correction unit 4 also generates correction information based on the temperature information output by the output unit 3.

[0063] Specifically, let the temperature of the sample gas in the k-th analysis be T. k In this case, the correction information used to correct the result of the k-th analysis could, for example, be P1·T. k / (P) k (T1). Based on this structure, more accurate calibration information can be generated. Therefore, by multiplying this calibration information by the result of the k-th analysis, a more accurate analysis result can be obtained when the same molar amount of sample gas as that introduced into the analysis device 140 in the k-th analysis is obtained.

[0064] (7) In the first embodiment, the calibration information may also be generated based on the pressure information of chamber 10 instead of the pressure information of metering tube 20. For example, the pressure of chamber 10 in the kth analysis may be set as P. k In this case, in the k-th analysis, the molar amount of sample gas introduced into metering tube 20 corresponds to P. k -P k+1 Therefore, the correction information used to correct the result of the kth analysis could also be, for example, (P1-P2) / (P k -P k+1 ).

[0065] By multiplying the correction information by the result of the kth analysis, the analysis result can be obtained if the same molar amount of sample gas was introduced into the analysis device 140 in the kth analysis as in the first 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 may not include the pressure gauge P2.

[0066] Furthermore, in this structure, the correction information can also be generated based on temperature information representing the sample temperature. For example, the temperature of the sample gas in the k-th analysis can be set as T. k In this case, the correction information used to correct the result of the k-th analysis could, for example, be (P1T2-P2T1)T. k T k+1 / (P) k T k+1 -P k+1 T k (T1T2).

[0067] Based on this structure, more accurate calibration information can be generated. Therefore, by multiplying this calibration information by the result of the k-th analysis, a more accurate analysis result can be obtained when the same molar amount of sample gas was introduced into the analysis device 140 in the k-th analysis as in the first analysis.

[0068] (8) In the second embodiment, the flow rate regulating unit 40 may also be controlled 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 regulation unit 40 can also be controlled to P. k-1 / T k-1 -P k / T k =P k / T k -P k+1 / T k+1Based on this structure, a constant amount of sample gas can be introduced into the metering tube 20 more accurately. Therefore, more accurate analytical results can be obtained in the k-th analysis.

[0069] (9) In the second embodiment, the flow rate regulating unit 40 may also be controlled based on the pressure of the metering tube 20 instead of the pressure of the chamber 10. For example, the pressure of the metering tube 20 in the kth analysis may be set to P. k The P k This corresponds to the molar amount of sample gas introduced into metering tube 20 in the k-th analysis. Therefore, in the k-th analysis, the flow rate regulating unit 40 can also be controlled to P. k-1 =P k .

[0070] According to this structure, in subsequent analyses, regardless of the amount of sample gas remaining in chamber 10, the same amount of sample as in the first analysis can be introduced into the metering tube 20. Therefore, accurate analytical results can be obtained in the kth analysis. In this structure, the pressure in chamber 10 is not used to control the flow rate regulating unit 40. Therefore, the sampling system 100 may not need to include the pressure gauge P1.

[0071] Furthermore, in this structure, the flow rate regulating unit 40 can also be controlled based on the temperature of the sample gas. For example, the temperature of the sample gas in the k-th analysis can be set to T. k In this case, in the k-th analysis, the flow regulation unit 40 can also be controlled to P. k-1 / T k-1 =P k / T k Based on this structure, a constant amount of sample gas can be introduced into the metering tube 20 more accurately. Therefore, more accurate analytical results can be obtained in the k-th analysis.

[0072] 4. Method Those skilled in the art will understand that the above-described exemplary embodiments are specific examples of the following approaches.

[0073] (Item 1) On the one hand, the sampling system involved can be a sampling system for sampling samples introduced into the analytical device, possessing: The chamber where the sample is collected; Import the measuring tube containing the sample collected in the chamber; A pressure gauge that measures the pressure of at least one of the chamber and the measuring tube; A storage unit that stores pressure information representing the pressure at each k-th analysis time point (k being an integer greater than or equal to 1) measured by the pressure gauge; And an output unit that outputs the pressure information stored in the storage unit.

[0074] In this sampling system, pressure information representing the pressure of at least one of the chamber and the measuring tube at each k-th analysis time point is stored in the storage unit and output. Therefore, the amount of sample introduced into the analytical apparatus at each analysis can be evaluated based on the pressure information. Furthermore, even if the amount of sample introduced into the measuring tube decreases with each repeated analysis, the analytical results of each analysis can be corrected to the analytical results under the condition that a constant amount of sample is introduced into the analytical apparatus based on the output pressure information.

[0075] Therefore, according to the above structure, it is not necessary to introduce the sample into the measuring tube under the same conditions for each analysis. Furthermore, even with a small amount of sample introduced, the analysis can be repeated, and the same analytical results can be obtained as if the sample were introduced into the analytical apparatus under the same conditions for each analysis. This improves the reliability of the analytical results. As a result, analytical results can be obtained with high reliability even with small sample sizes.

[0076] (Item 2) The sampling system described in Item 1 may further include: The calibration unit generates calibration information based on the pressure information output by the output unit to correct the analysis results obtained by the analysis device for the case where a constant amount of sample is introduced into the analysis device.

[0077] In this case, by using the correction information generated by the correction unit, the analytical results obtained from the analytical apparatus are corrected to the analytical results obtained when a constant amount of sample is introduced into the analytical apparatus. Therefore, analytical results with improved reliability can be easily obtained.

[0078] (Item 3) The sampling system described in Item 2, wherein, The pressure gauge measures the pressure in the measuring tube. And the pressure of the metering tube in the k-th analysis is set to P. k In this case, the correction unit can also adjust P1 / P k The correction information is generated as the correction information used to correct the results of the kth analysis.

[0079] In this case, correction information can be generated with a simple structure.

[0080] (Item 4) The sampling system described in Item 2, wherein, The pressure gauge measures the pressure in the chamber. And the pressure in the chamber during the k-th analysis is set to P. k In this case, the correction unit can also adjust (P1-P2) / (P k -P k+1This is generated as the correction information used to correct the results of the kth analysis.

[0081] In this case, correction information can be generated with a simple structure.

[0082] (Item 5) The sampling system described in Item 2, wherein the storage unit further stores temperature information representing the temperature of the sample at each k-th analysis time point, The output unit also outputs the temperature information stored in the storage unit. The calibration unit may also generate the calibration information based on the temperature information output by the output unit.

[0083] In this case, more accurate correction information can be generated.

[0084] (Item 6) The sampling system described in Item 1, wherein the output unit may also output the pressure information to the analysis device.

[0085] According to this structure, in the analysis device, the analysis results of each analysis can be corrected to the analysis results when a constant amount of sample is introduced into the analysis device based on the output pressure information.

[0086] (Item 7) On the other hand, the sampling system involved can be a sampling system for sampling a sample introduced into an analytical device, and has the following features: The chamber where the sample is collected; Import the measuring tube containing the sample collected in the chamber; A pressure gauge that measures the pressure of at least one of the chamber and the measuring tube; A flow regulating unit that adjusts the flow rate of the sample introduced into the metering tube from the chamber; And a flow control unit that controls the operation of the flow regulating unit by introducing a constant amount of sample into the metering tube based on the pressure at each k-th analysis time point (k is an integer greater than or equal to 1) measured by the pressure gauge.

[0087] In this sampling system, the flow regulator is controlled based on the pressure at each k-th analysis time point, thereby introducing a constant amount of sample into the metering tube. Therefore, even with small sample quantities, sample analysis can be repeated under the same conditions. This improves the reliability of the analytical results. As a result, analytical results can be obtained with high reliability even with small sample quantities.

[0088] (Item 8) The sampling system described in Item 7, wherein, The pressure gauge measures the pressure in the chamber. And the pressure in the chamber during the k-th analysis is set to P. kIn the case of P, the flow control unit can also, in the k-th analysis, make P k-1 -P k =P k -P k+1 The operation of the flow regulating unit is controlled in a manner that allows for control of the flow rate.

[0089] In this case, a constant amount of sample can be introduced into the measuring tube with a simple structure.

[0090] (Item 9) The sampling system described in Item 7, wherein, The pressure gauge measures the pressure in the measuring tube. And the pressure of the metering tube in the k-th analysis is set to P. k In the case of P, the flow control unit can also, in the k-th analysis, make P k-1 =P k The operation of the flow regulating unit is controlled in a manner that allows for control of the flow rate.

[0091] In this case, a constant amount of sample can be introduced into the measuring tube with a simple structure.

[0092] (Item 10) The sampling system of Item 7, wherein the flow regulation unit obtains the temperature of the sample at each k-th analysis time point, and may also control the flow control unit based on the obtained temperature.

[0093] In this case, a constant amount of sample can be introduced into the measuring tube more accurately.

[0094] (Item 11) Another aspect of the sampling method may be a sampling method for sampling a sample introduced into an analytical device, including: The sample is collected into the chamber; The sample collected in the chamber is introduced into a measuring tube; The pressure of at least one of the chamber and the metering tube is measured by a pressure gauge; Pressure information representing the pressure at each k-th analysis time point (k being an integer greater than or equal to 1) measured by the pressure gauge is stored in the storage unit; And output the pressure information stored in the storage unit.

[0095] According to this sampling method, it is not necessary to introduce the sample into the measuring tube under the same conditions for each analysis. Furthermore, even with a small amount of sample introduced, the analysis can be repeated, and the same analytical results can be obtained as if the sample were introduced into the analytical apparatus under the same conditions for each analysis. Therefore, the reliability of the analytical results is improved. As a result, analytical results can be obtained with high reliability even with small sample sizes.

[0096] (Item 12) Another aspect of the sampling method can be a sampling method for sampling a sample introduced into an analytical device, including: The sample is collected into the chamber; The sample collected in the chamber is introduced into a measuring tube; The pressure of at least one of the chamber and the metering tube is measured by a pressure gauge; The flow rate of the sample introduced into the metering tube from the chamber is adjusted by the flow regulating unit; The flow regulation unit controls the operation of the flow regulating unit by introducing a constant amount of sample into the metering tube based on the pressure at each k-th analysis time point (k is an integer greater than or equal to 1) measured by the pressure gauge.

[0097] According to this sampling method, since a constant amount of sample is introduced into the measuring tube, the analysis of the sample can be repeated under the same conditions even with small sample sizes. This improves the reliability of the analytical results. As a result, analytical results can be obtained with high reliability even with small sample sizes.

Claims

1. A sampling system for sampling samples introduced into an analytical device, characterized in that, have: The chamber where the sample is collected; Import the measuring tube containing the sample collected in the chamber; A pressure gauge that measures the pressure of at least one of the chamber and the measuring tube; A storage unit that stores pressure information representing the pressure at each k-th analysis time point measured by the pressure gauge, where k is an integer greater than or equal to 1; And an output unit that outputs the pressure information stored in the storage unit.

2. The sampling system according to claim 1, characterized in that, It also has: The calibration unit generates calibration information based on the pressure information output by the output unit to correct the analysis results obtained by the analysis device for the case where a constant amount of sample is introduced into the analysis device.

3. The sampling system according to claim 2, characterized in that, The pressure gauge measures the pressure in the measuring tube. Let the pressure of the metering tube in the kth analysis be P. k In this case, the correction unit will P1 / P k The correction information is generated as the correction information used to correct the results of the kth analysis.

4. The sampling system according to claim 2, characterized in that, The pressure gauge measures the pressure in the chamber. Let the pressure of the chamber in the k-th analysis be P. k In this case, the correction unit will (P1-P2) / (P k -P k+1 This is generated as the correction information used to correct the results of the kth analysis.

5. The sampling system according to claim 2, characterized in that, The storage unit also stores temperature information representing the temperature of the sample at each k-th analysis time point. The output unit also outputs the temperature information stored in the storage unit. The correction unit also generates the correction information based on the temperature information output by the output unit.

6. The sampling system according to claim 1, characterized in that, The output unit outputs the pressure information to the analysis device.

7. A sampling system for sampling samples introduced into an analytical device, characterized in that, have: The chamber where the sample is collected; Import the measuring tube containing the sample collected in the chamber; A pressure gauge that measures the pressure of at least one of the chamber and the measuring tube; A flow regulating unit that adjusts the flow rate of the sample introduced into the metering tube from the chamber; And a flow control unit that controls the operation of the flow regulating unit by introducing a constant amount of sample into the metering tube based on the pressure at each k-th analysis time point measured by the pressure gauge, wherein k is an integer greater than or equal to 1.

8. The sampling system according to claim 7, characterized in that, The pressure gauge measures the pressure in the chamber. Let the pressure of the chamber in the k-th analysis be P. k In the case where the flow control unit, in the k-th analysis, causes P to... k-1 -P k =P k -P k+1 The operation of the flow regulating unit is controlled in a manner that allows for control of the flow rate.

9. The sampling system according to claim 7, characterized in that, The pressure gauge measures the pressure in the measuring tube. Let the pressure of the metering tube in the kth analysis be P. k In the case where the flow control unit, in the k-th analysis, causes P to... k-1 =P k The operation of the flow regulating unit is controlled in a manner that allows for control of the flow rate.

10. The sampling system according to claim 7, characterized in that, The flow regulation unit obtains the temperature of the sample at each k-th analysis time point, and also controls the flow control unit based on the obtained temperature.

11. A sampling method for sampling a sample introduced into an analytical device, characterized in that, include: The sample is collected into the chamber; The sample collected in the chamber is introduced into a measuring tube; The pressure of at least one of the chamber and the metering tube is measured by a pressure gauge; Pressure information representing the pressure at each k-th analysis time point measured by the pressure gauge is stored in the storage unit, where k is an integer greater than or equal to 1; And output the pressure information stored in the storage unit.

12. A sampling method for sampling a sample introduced into an analytical device, characterized in that, include: The sample is collected into the chamber; The sample collected in the chamber is introduced into a measuring tube; The pressure of at least one of the chamber and the metering tube is measured by a pressure gauge; The flow rate of the sample introduced into the metering tube from the chamber is adjusted by the flow regulating unit; And based on the pressure at each k-th analysis time point measured by the pressure gauge, the operation of the flow regulating unit is controlled by introducing a constant amount of sample into the metering tube, where k is an integer greater than or equal to 1.

Images