Air measurement method using gas chromatograph and gas chromatograph analysis system

Abstract

This air measurement method for injecting air into a gas chromatograph (2) and measuring the air comprises: a liquid suction step for sucking a liquid that will not interfere with the detection of a prescribed component in air by the gas chromatograph (2) into a syringe (16) so as to fill the syringe (16) with the liquid; an air suction step for sucking a prescribed amount of air into the syringe (16) after the liquid suction step; an injection step for injecting the prescribed amount of air that has been sucked into the syringe (16) into the gas chromatograph (2) after the air suction step; and a recording step for acquiring a detection signal for the air injected into the gas chromatograph (2) in the injection step and recording the acquired detection signal in association with the amount of air that was injected into the gas chromatograph (2).

Description

[Technical field]

[0001] The present invention relates to an air measurement method using a gas chromatograph and a gas chromatographic analysis system. [Background technology]

[0002] A gas chromatographic analysis system is a system in which a liquid sample contained in a container is collected by an injector and injected into an injection port, the sample injected from the injection port is vaporized and introduced into a separation column together with a carrier gas, and the components in the sample separated in the separation column are detected by a detector (see, for example, Patent Document 1).

[0003] The solvent of the sample injected into the gas chromatograph contains small amounts of dissolved components such as oxygen and nitrogen. In order to quantify these trace components, it is necessary to prepare a calibration curve that shows the relationship between the concentration of these components and the detection signal of the gas chromatograph. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 072893 Summary of the Invention [Problem to be solved by the invention]

[0005] In order to create a calibration curve for trace components such as oxygen and nitrogen present in a sample solvent, it is possible to inject diluted oxygen and nitrogen gases into a gas chromatograph for measurement, but it is difficult to create a highly accurate calibration curve due to the influence of air contamination. Therefore, it is possible to use air as a sample to obtain detection signals for oxygen and nitrogen. In this case, air is measured and aspirated into the injector syringe to inject a specified amount of air into the gas chromatograph, but it was found that the usual method of simply aspirating air into the syringe and injecting it into the gas chromatograph does not allow air to be injected from the syringe into the gas chromatograph with high precision, and therefore accurate measurement results for air cannot be obtained.

[0006] The present invention has been made in consideration of the above problems, and has an object to make it possible to accurately measure air using a gas chromatograph. [Means for solving the problem]

[0007] The present inventors have found that the accuracy of the amount of air injected into a gas chromatograph can be improved by drawing air into a syringe filled with a liquid such as water and injecting the air into the syringe into a gas chromatograph. The present invention is based on this finding.

[0008] The air measurement method of the present invention is an air measurement method in which air is injected into a gas chromatograph for measurement, and includes a liquid suction step of suctioning a liquid that does not interfere with the detection of a specific component in the air by the gas chromatograph into a syringe to fill the syringe with the liquid, an air suction step of suctioning a specific amount of air into the syringe after the liquid suction step, an injection step of injecting the specific amount of air suctioned into the syringe into the gas chromatograph after the air suction step, and a recording step of acquiring a detection signal for the air injected into the gas chromatograph in the injection step, and recording the acquired detection signal in correspondence with the amount of air injected into the gas chromatograph.

[0009] The gas chromatographic analysis system of the present invention comprises a gas chromatograph that separates and detects components in a sample, an injector having a syringe and for injecting a sample into the gas chromatograph using the syringe, and a control unit that controls the operation of the gas chromatograph and the injector, wherein the control unit is configured, in an operation mode in which air is injected into the gas chromatograph by the injector for measurement, to suck a liquid that does not interfere with the detection of a specific component in the air into the syringe to fill the syringe with the liquid, then suck a specific amount of air into the syringe, and then inject the specific amount of air sucked into the syringe into the gas chromatograph. Effect of the Invention

[0010] According to the air measurement method of the present invention, a liquid that does not interfere with the detection of a predetermined component in air is sucked into a syringe, and when the syringe is filled with the liquid, a predetermined amount of air is sucked into the syringe and the predetermined amount of air is injected into a gas chromatograph, so that the accuracy of the amount of air injected from the syringe into the gas chromatograph is improved, and the measurement of air by the gas chromatograph can be performed accurately. When injecting the air sucked into the syringe into the sample injection section of the gas chromatograph, if the inside of the syringe is filled only with air, it is considered that the air in the syringe is pushed toward the piston by the high pressure in the sample injection section, and the air in the syringe is compressed, so that the desired amount of air is not pushed out of the syringe, or the air leaks out of the syringe through a small gap between the inner wall of the syringe and the piston. By filling the syringe with liquid in advance as in the present invention, the occurrence of these problems is suppressed, and the accuracy of the amount of air injected into the gas chromatograph is improved.

[0011] According to the gas chromatograph analysis system of the present invention, in an operation mode in which air is injected into a gas chromatograph by an injector for measurement, a liquid that does not interfere with the detection of a specific component in the air is drawn into a syringe to fill the syringe with the liquid, and then a specific amount of air is drawn into the syringe, and then the specific amount of air drawn into the syringe is injected into the gas chromatograph, thereby improving the accuracy of the amount of air injected from the syringe into the gas chromatograph and enabling accurate measurement of the air by the gas chromatograph. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram showing an embodiment of a gas chromatograph analysis system. [Diagram 2] 4 is a flowchart showing an example of an air measurement operation in the embodiment. [Diagram 3] This is an example of measurement data when air is injected into a syringe without filling it with water. (A) is a table showing the relationship between each set injection amount and the peak area value of oxygen, and (B) is a correlation graph (calibration curve) between the injection amount and the peak area value created based on the table in (A). [Figure 4] This is an example of measurement data when air is injected into a syringe filled with water. (A) is a table showing the relationship between each set injection amount and the peak area value of oxygen, and (B) is a correlation graph (calibration curve) between the injection amount and the peak area value created based on the table in (A). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] An embodiment of an air measurement method and a gas chromatographic analysis system according to the present invention will now be described with reference to the drawings.

[0014] As shown in FIG. 1, the gas chromatographic analysis system 1 includes a gas chromatograph 2, an injector 4, and a control unit 6.

[0015] The gas chromatograph 2 comprises a separation column 8, a sample injection section 12, and a detector 14. An injection port 10 is provided at the top of the sample injection section 12, and a sample to be analyzed is injected into the sample injection section 12 through the injection port 10. The inside of the sample injection section 12 is at high temperature and pressure, and the sample injected into the sample injection section 12 is guided to the separation column 8 together with a carrier gas supplied to the sample injection section 12. The components in the sample guided to the separation column 8 are separated over time in the separation column 8, and the separated components are sequentially eluted from the separation column 8 and introduced into the detector 14. The detector 14 obtains a detection signal corresponding to the concentration of each component eluted from the separation column 8.

[0016] The injector 4 is a device for injecting a sample into the sample injection section 12 of the gas chromatograph 2 through the injection port 10, and mainly includes a syringe 16 and a drive section 20. The syringe 16 is configured to suck and discharge a fluid by sliding a piston 18 inside. The drive section 20 is configured to drive the piston 18 of the syringe 16, and includes a drive mechanism such as a motor. The syringe 16 is a microsyringe capable of measuring and injecting a fluid of 0.5 μL or less. The injector 4 is provided with a container 22 containing water, which is a liquid that does not interfere with the detection of components such as oxygen and nitrogen in the air by the gas chromatograph 2, and the water can be sucked into the syringe 16. Although a small amount of oxygen and nitrogen are dissolved in the water, the dissolved concentration is on the order of ppm and can be ignored. The liquid drawn into syringe 16 before drawing in air need only contain oxygen and nitrogen to such an extent that they do not affect the measurement of such components by gas chromatograph 2, and does not necessarily have to be water.

[0017] The control unit 6 is a computer device for controlling the operations of the gas chromatograph 2 and the injector 4. The control unit 6 is configured to suck air into the syringe 16 in a state where the syringe 16 is filled with water in an operation mode including an operation of injecting air into the gas chromatograph 2 by the injector 4, for example, in a mode for creating a calibration curve of oxygen and / or nitrogen using air.

[0018] An example of the air measurement operation in the gas chromatographic analysis system 1 will be described with reference to the flow chart of FIG. 2 together with FIG.

[0019] First, the user sets the amount of air to be injected into the gas chromatograph 2 in the control unit 6 (step 101). When creating a calibration curve, multiple injection amounts can be set in this step. Once the setting of the amount of air to be injected is completed, the injector 4 causes the syringe 16 to suck water from the container 22 to fill the syringe 16 with water (step 102).

[0020] Thereafter, the injector 4 causes the syringe 16 to draw in the amount of air set as the amount of air to be injected into the gas chromatograph 2 (step 103). When multiple air injection amounts are set, the smallest amount of air among the set air injection amounts may be drawn into the syringe 16. After the predetermined amount of air is drawn into the syringe 16, the tip of the syringe 16 is inserted into the injection port 10, and the predetermined amount of air drawn into the syringe 16 is injected into the sample injection section 12 (step 104). At this time, the air in the syringe 16 is pushed out by water, which has a lower compressibility than air, due to the high pressure in the sample injection section 12, so that an accurate amount of air is injected into the sample injection section 12 without being affected by the compression of the air. In addition, when air is injected into the sample injection section 12, a part of the water that has reached the tip of the syringe 12 may be unintentionally injected into the sample injection section 12 due to discrimination, but since the concentrations of oxygen and nitrogen dissolved in water are on the order of ppm, the influence of oxygen and nitrogen on the measurement can be ignored.

[0021] When a predetermined amount of air is injected from the syringe 16 into the sample injection section 12, the injected air is mixed with the carrier gas, and oxygen and nitrogen are introduced in a diluted state into the separation column 8 and separated from each other, and a detection signal corresponding to their concentrations is obtained in the detector 14. The control section 6 records the detection signal obtained in the detector 14 in association with the amount of air injected into the gas chromatograph 2 (step 105).

[0022] When multiple air injection amounts are set, steps 103 to 105 are repeatedly executed for each set value with the syringe 16 filled with water (step 106). Note that the present invention is not limited to this, and steps 102 to 105 may be repeatedly executed for each set value.

[0023] FIG. 3 shows peak area value data of oxygen at each injection amount (set value) obtained by injecting air into gas chromatograph 2 without filling syringe 16 with water, and FIG. 4 shows peak area value data of oxygen at each injection amount (set value) obtained by injecting air into gas chromatograph 2 with syringe 16 filled with water.

[0024] Comparing the peak area values ​​for each injection amount in FIG. 3 and FIG. 4, it can be seen that the peak area is larger when air is injected into the gas chromatograph with the syringe 16 filled with water than when air is injected into the gas chromatograph 2 without filling the syringe 16 with water.

[0025] In the measurement of FIG. 4, only the amount of air set as the injection amount is sucked into the syringe 16 filled with water and injected into the gas chromatograph 2, so that air exceeding the set amount is never injected into the gas chromatograph 2. That is, the peak area value at each injection amount in FIG. 4 does not become larger than the original peak area value. Therefore, the peak area values ​​in FIG. 3 that are smaller than the peak area values ​​in FIG. 4 have a larger error from the original peak area value than the peak area values ​​in FIG. 4 and are less accurate. From this, it can be seen that if air injection into the gas chromatograph 2 is performed with the syringe 16 filled with water, the measurement of air by the gas chromatograph 2 can be performed with high accuracy.

[0026] The embodiment described above is merely one example of the air measurement method and gas chromatographic analysis system according to the present invention. The embodiment of the air measurement method and gas chromatographic analysis system according to the present invention is as follows.

[0027] In one embodiment of the air measurement method of the present invention, the air measurement method injects air into a gas chromatograph to measure the air, and includes a liquid suction step of suctioning a liquid that does not interfere with the detection of a specific component in the air by the gas chromatograph into a syringe to fill the syringe with the liquid, an air suction step of suctioning a specific amount of air into the syringe after the liquid suction step, an injection step of injecting the specific amount of air suctioned into the syringe into the gas chromatograph after the air suction step, and a recording step of acquiring a detection signal for the air injected into the gas chromatograph in the injection step, and recording the acquired detection signal in correspondence with the amount of air injected into the gas chromatograph.

[0028] In a first aspect of one embodiment of the air measurement method, a setting step is provided for setting multiple injection amounts of air into the gas chromatograph before the liquid intake step, and after the syringe is filled with the liquid in the liquid intake step, the intake and intake step, the injection step, and the recording step are executed for each of the multiple injection amounts set in the setting step. With this aspect, it is possible to omit the repetition of the liquid intake step and shorten the time required for measurement with multiple injection amounts of air.

[0029] In a second aspect of the embodiment of the air measurement method, water is used as the liquid.

[0030] One embodiment of the gas chromatograph analysis system according to the present invention comprises a gas chromatograph that separates and detects components in a sample, an injector having a syringe and using the syringe to inject a sample into the gas chromatograph, and a control unit that controls the operation of the gas chromatograph and the injector, wherein the control unit is configured, in an operation mode in which air is injected into the gas chromatograph by the injector for measurement, to aspirate a liquid that does not interfere with the detection of a specific component in the air into the syringe to fill the syringe with the liquid, then aspirate a specific amount of air into the syringe, and then inject the specific amount of air aspirated into the syringe into the gas chromatograph.

[0031] In a first aspect of one embodiment of the gas chromatograph analysis system, the operation mode is a mode in which the injector injects air into the gas chromatograph multiple times, and the control unit is configured to repeatedly draw air into the syringe and inject the air into the gas chromatograph while the syringe is filled with the liquid. With this aspect, it is possible to omit the repeated drawing of liquid into the syringe and shorten the time required for multiple air injections.

[0032] In a second aspect of one embodiment of the gas chromatography analysis system, the liquid is water. [Explanation of symbols]

[0033] 1. Gas chromatograph analysis system 2. Gas chromatograph 4 Injectors 6. Control Unit 8. Separation Column 10 Injection port 12 Sample injection section 14 Detector 16 Syringe 18 Piston 20 Control section 22 Container (water)

Claims

1. An air measurement method in which air is injected into a gas chromatograph and measured, comprising: a liquid intake step of intake-discharge liquid from one end of a syringe, the one end of which is slidably moved by a piston inside the syringe, the liquid not interfering with detection of a predetermined component in air by a gas chromatograph, and filling the syringe with the liquid; an air intake step of intake a predetermined amount of air into the syringe from the one end of the syringe after the liquid intake step; an injection step of injecting the entire amount of the predetermined amount of air sucked into the syringe into the gas chromatograph after the air sucking step; an air measurement method comprising: a recording step of acquiring a detection signal for the air injected into the gas chromatograph in the injection step; and recording the acquired detection signal in correspondence with the amount of air injected into the gas chromatograph.

2. A setting step of setting a plurality of injection amounts of air into the gas chromatograph before the liquid intake step, 2. The air measurement method according to claim 1, wherein after the syringe is filled with the liquid in the liquid inhalation step, the air inhalation step, the injection step, and the recording step are performed for each of the multiple injection amounts set in the setting step.

3. 3. The air measurement method according to claim 1, wherein the liquid is water.

4. A gas chromatograph for separating and detecting components in a sample; an injector having a syringe that draws in and discharges a fluid from one end by sliding a piston inside the syringe, for injecting a sample into the gas chromatograph using the syringe; a control unit that controls the operation of the gas chromatograph and the injector, the control unit is configured, in an operating mode in which air is injected into the gas chromatograph using the injector for measurement, to suck a liquid that does not interfere with the detection of a predetermined component in the air into the one end of the syringe to fill the syringe with the liquid, then suck a predetermined amount of air into the syringe from the one end of the syringe, and then inject the entire amount of the predetermined amount of air sucked into the syringe into the gas chromatograph.

5. the operation mode is a mode in which the injector injects air into the gas chromatograph multiple times; 5. The gas chromatograph analysis system according to claim 4, wherein the control unit is configured to repeatedly draw air into the syringe and inject the air into the gas chromatograph while the syringe is filled with the liquid.

6. 6. The gas chromatographic analysis system according to claim 4, wherein the liquid is water.

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